CN109021151B - Preparation method of polybutene-1 with narrow molecular weight distribution - Google Patents
Preparation method of polybutene-1 with narrow molecular weight distribution Download PDFInfo
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- CN109021151B CN109021151B CN201810993271.XA CN201810993271A CN109021151B CN 109021151 B CN109021151 B CN 109021151B CN 201810993271 A CN201810993271 A CN 201810993271A CN 109021151 B CN109021151 B CN 109021151B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/08—Butenes
Abstract
The invention provides a preparation method of polybutene-1 with narrow molecular weight distribution, which comprises the following steps: dissolving a polybutene-1 sample in a mixed solvent at 120-150 ℃ to obtain a sample solution with the concentration of 0.5-1.5 wt%; the mixed solvent comprises a good solvent and a poor solvent with the volume ratio of 70-95: 5-30; the good solvent is selected from one or more of 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2, 4-trichlorobenzene, dichlorobenzene and xylene; the poor solvent is selected from ethyl cellosolve and/or butyl cellosolve; and (2) cooling the sample solution to 10-30 ℃, loading the sample on the filler, completely replacing the mixed solvent with a poor solvent after balancing, heating to 100-130 ℃, sequentially increasing the volume percentage content of the good solvent, balancing, and leaching to respectively obtain the polybutene-1 with narrow molecular weight distribution and molecular weight from low to high.
Description
Technical Field
The invention belongs to the technical field of solvent gradient grading, and particularly relates to a preparation method of polybutene-1 with narrow molecular weight distribution.
Background
Polybutene-1 (PB-1) is prepared by polymerizing 1-butene monomer in the presence of catalyst in slurry process, bulk process or gas phase process, has three stereo structures of isotactic, syndiotactic and atactic, and especially isotactic polybutene-1 (iPB-1) (isotactic content higher than 96%) has outstanding heat creep resistance, environmental stress cracking resistance, good toughness and wear resistance, chemical resistance, etc. it has the reputation of "plastic gold", and is widely used in various fields of pipes, films, etc. (prog. Polym. Sci.1988,13(1): 37-62). At high temperature, the creep resistance and the stress cracking resistance of the PB-1 are better than those of polyethylene and polypropylene, and the PB-1 is more suitable for hot water pipes; under the low temperature condition, the PB-1 also has better low-temperature impact resistance, and the pipe cannot be frozen to crack. Therefore, the PB-1 pipe can be used for a long time at the temperature of-30 ℃ to 100 ℃, and the service life is as long as 50 to 100 years. The film made of PB-1 has excellent tear strength and rubber elasticity, and can be used for packaging, such as peelable easy-to-tear films. With the development of technology and the reduction of production cost, PB-1 has been increasingly widely used due to its excellent properties.
PB-1 is a polymorphic polymer, and five crystal forms, namely I, I ', II' and III, have been found, and the properties of the crystal forms vary greatly from one crystal form to another (Macromolecules,1999,32: 4975-4982). The most important in practical application are the crystal form I and the crystal form II. Form I is a thermodynamically stable state and form II is a thermodynamically metastable state. iPB-1, cooling and crystallizing at normal pressure to form crystal form II, wherein the crystal form II can be completely converted into stable crystal form I after 7-14 days at normal temperature, and the solid-solid phase conversion is irreversible. The PB-1 resin has the problem of crystal form transformation in the using process, so that the production efficiency is seriously influenced, and the large-scale commercial production and application of the PB-1 resin are directly restricted. In addition, the transition from metastable form II to stable form I can cause changes in various physical properties, such as increased melting point, density, strength, and hardness. Therefore, the research on the PB-1 crystallization behavior and the crystal form transformation has important academic significance and important industrial application value. Although a great deal of research on factors influencing the crystallization behavior and the crystal form transformation (J.Macromol. Sci. part B,2005,44:377-396) is carried out, in the research, the narrow molecular weight distribution fraction is difficult to obtain, so that some research results are contradictory, and a systematic and exact influence rule cannot be given, thereby seriously influencing the popularization of the practical application.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a process for producing polybutene-1 having a narrow molecular weight distribution, which is capable of fractionating polybutene-1 into molecular weights and obtaining fractions having a narrow molecular weight distribution.
The invention provides a preparation method of polybutene-1 with narrow molecular weight distribution, which comprises the following steps:
dissolving a polybutene-1 sample in a mixed solvent at 120-150 ℃ to obtain a sample solution with the concentration of 0.5-1.5 wt%; the mixed solvent comprises a good solvent and a poor solvent with the volume ratio of 70-95: 5-30; the good solvent is selected from one or more of 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2, 4-trichlorobenzene, dichlorobenzene and xylene; the poor solvent is selected from ethyl cellosolve and/or butyl cellosolve;
and cooling the sample solution to 10-30 ℃, loading the sample on the filler, completely replacing the mixed solvent with a poor solvent after balancing, heating to 100-130 ℃, sequentially increasing the volume percentage content of a good solvent, balancing, and leaching to respectively obtain the polybutene-1 with narrow molecular weight distribution and high molecular weight.
Preferably, the mixed solvent is selected from a good solvent and a poor solvent of 70-80: 20-30.
Preferably, the mixed solvent is selected from mixed solvents of 1,2, 4-trimethylbenzene and butyl cellosolve in a volume ratio of 70: 30; or a mixed solvent of 1,3, 5-trimethylbenzene and butyl cellosolve in a volume ratio of 80: 20; or a mixed solvent of xylene and butyl cellosolve in a volume ratio of 70: 30; or a mixed solvent of xylene and butyl cellosolve in a volume ratio of 80: 20; or a mixed solvent of 1,2, 4-trichlorobenzene and ethyl cellosolve in a volume ratio of 75: 25; or a mixed solvent of 1,2, 4-trichlorobenzene and ethyl cellosolve in a volume ratio of 70: 30; or a mixed solvent of dichlorobenzene and butyl cellosolve in a volume ratio of 70: 30; or a mixed solvent of dichlorobenzene and butyl cellosolve in a volume ratio of 80: 20.
Preferably, the sample solution is cooled to 10-30 ℃ at a cooling rate of 0.5-2 ℃/h.
Preferably, the method further comprises the following steps:
and respectively precipitating the leached leacheate with the molecular weight from low to high by adopting a precipitator, and sequentially filtering, washing and drying to obtain the polybutene-1 with different narrow molecular weight distributions.
Preferably, the mixed solvent is completely replaced by a poor solvent after balancing for 20-28 h.
Preferably, the precipitating agent is selected from acetone and/or ethanol.
Preferably, the good solvent is leached after being balanced for 22-26 hours after the volume percentage content of the good solvent is increased once.
Preferably, the filler is 60-80 mesh glass beads or quartz sand.
The invention provides a preparation method of polybutene-1 with narrow molecular weight distribution, which comprises the following steps: dissolving a polybutene-1 sample in a mixed solvent at 120-150 ℃ to obtain a sample solution with the concentration of 0.5-1.5 wt%; the mixed solvent comprises a good solvent and a poor solvent with the volume ratio of 70-95: 5-30; the good solvent is selected from one or more of 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2, 4-trichlorobenzene, dichlorobenzene and xylene; the poor solvent is selected from ethyl cellosolve and/or butyl cellosolve; and cooling the sample solution to 10-30 ℃, loading the sample on the filler, completely replacing the mixed solvent with a poor solvent after balancing, heating to 100-130 ℃, sequentially increasing the volume percentage content of a good solvent, balancing, and leaching to respectively obtain the polybutene-1 with narrow molecular weight distribution and high molecular weight. According to the invention, the polybutene-1 sample is treated by adopting a specific kind of mixed solvent under specific conditions, so that the molecular weight of the polybutene-1 sample is classified, and the fraction with narrow molecular weight distribution is obtained.
Drawings
Fig. 1 is a schematic structural view of a classifying apparatus used in the present invention.
Detailed Description
The invention provides a preparation method of polybutene-1 with narrow molecular weight distribution, which comprises the following steps:
dissolving a polybutene-1 sample in a mixed solvent at 120-150 ℃ to obtain a sample solution with the concentration of 0.5-1.5 wt%; the mixed solvent comprises a good solvent and a poor solvent with the volume ratio of 70-95: 5-30; the good solvent is selected from one or more of 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2, 4-trichlorobenzene, dichlorobenzene and xylene; the poor solvent is selected from ethyl cellosolve and/or butyl cellosolve;
and cooling the sample solution to 10-30 ℃, loading the sample on the filler, completely replacing the mixed solvent with a poor solvent after balancing, heating to 100-130 ℃, sequentially increasing the volume percentage content of a good solvent, balancing, and leaching to respectively obtain the polybutene-1 with narrow molecular weight distribution and high molecular weight.
According to the invention, the polybutene-1 sample is treated by adopting a specific kind of mixed solvent under specific conditions, so that the molecular weight of the polybutene-1 sample is classified, and the fraction with narrow molecular weight distribution is obtained.
The invention adopts a grading device to grade the molecular weight of a polybutene-1 sample; as shown in fig. 1, fig. 1 is a schematic structural diagram of a classifying device used in the present invention. In the separation column in fig. 1, packing is provided.
According to the invention, a polybutene-1 sample is dissolved in a mixed solvent at 120-150 ℃ to obtain a sample solution with the concentration of 0.5-1.5 wt%. In the invention, the polybutene-1 sample is prepared by polymerizing the monomeric 1-butene in the presence of a catalyst by a slurry method, a bulk method or a gas phase method, and has three stereo structures of isotactic, syndiotactic and atactic.
The method preferably dissolves the polybutene-1 sample at 130-150 ℃. In specific embodiments, the temperature of dissolution is 130 ℃, 135 ℃, 140 ℃ or 150 ℃. The dissolving time is preferably 3-6 h.
In the invention, the mixed solvent comprises a good solvent and a poor solvent with a volume ratio of 70-95: 5-30; preferably 70-80: 20-30 of good solvent and poor solvent; more preferably, the mixed solvent is selected from mixed solvents of 1,2, 4-trimethylbenzene and butyl cellosolve in a volume ratio of 70: 30; or a mixed solvent of 1,3, 5-trimethylbenzene and butyl cellosolve in a volume ratio of 80: 20; or a mixed solvent of xylene and butyl cellosolve in a volume ratio of 70: 30; or a mixed solvent of xylene and butyl cellosolve in a volume ratio of 80: 20; or a mixed solvent of 1,2, 4-trichlorobenzene and ethyl cellosolve in a volume ratio of 75: 25; or a mixed solvent of 1,2, 4-trichlorobenzene and ethyl cellosolve in a volume ratio of 70: 30; or a mixed solvent of dichlorobenzene and butyl cellosolve in a volume ratio of 70: 30; or a mixed solvent of dichlorobenzene and butyl cellosolve in a volume ratio of 80: 20.
After a sample solution is obtained, the temperature of the sample solution is reduced to 10-30 ℃, so that a sample is loaded on a filler, a poor solvent is adopted for replacement after balance, the temperature is increased to 100-130 ℃, then the volume percentage content of a good solvent is sequentially increased, and the polybutene-1 with narrow molecular weight distribution and molecular weight from low to high is respectively obtained after balance and leaching.
According to the invention, the sample solution is preferably transferred to a fractionating column and is stabilized for 30-60 min, and then the temperature is reduced. The sample solution is preferably cooled to 10-30 ℃ at a cooling rate of 0.5-2 ℃/h. Loading the sample on the filler in the process of cooling to 10-30 ℃; the filler is preferably selected from 60-80 mesh glass beads or quartz sand.
According to the invention, after the balance is preferably carried out for 20-28 h, the poor solvent is adopted to completely replace the mixed solvent, and room temperature fractions dissolved in the mixed solvent are obtained at the same time.
After the mixed solvent is completely replaced, heating to the grading temperature of 100-130 ℃; in specific embodiments, the classification temperature is specifically 100 ℃, 130 ℃, 120 ℃, 110 ℃, 105 ℃, 125 ℃ or 120 ℃. The invention preferably adopts an oil bath heating mode to raise the temperature to the required grading temperature. The oil enters the separation device through the circulating bath inlet in the device shown in fig. 1 and is discharged through the circulating bath outlet for recycling.
In the present invention, the volume percentages of the good solvents in the sequential increase of the volume percentages of the good solvents are 10%, 20%, 30%, 40% and 50% in sequence. In the invention, the good solvent and the poor solvent are preferably mixed to obtain the mixed solvent with the required percentage content of the good solvent, and then the mixed solvent is rinsed. According to the invention, the good solvent is preferably balanced for 22-26 h and then is subjected to spray washing after the volume percentage content of the good solvent is increased once, and the better solvent is more preferably 23-25 h; in a specific embodiment, the rinsing after 24h of equilibration is preferred.
In the present invention, it is preferable that the method further comprises, after the rinsing:
and respectively precipitating the leached leacheate with the molecular weight from low to high by adopting a precipitator, and sequentially filtering, washing and drying to obtain the polybutene-1 with different narrow molecular weight distributions.
In the present invention, the precipitating agent is preferably acetone and/or ethanol. The present invention preferably adds twice the volume of leacheate to effect precipitation. The invention preferably provides polybutene-1 with a narrow molecular weight distribution by vacuum drying at 30 ℃.
In order to further illustrate the present invention, the following examples are given to describe the preparation of polybutene-1 with narrow molecular weight distribution in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Solvent gradient grading PB-1 specific steps:
1) dissolving a sample: dissolving a resin sample in a mixed solvent of 1,2, 4-Trimethylbenzene (TMB) serving as a good solvent and Butyl Cellosolve (BCS) serving as a poor solvent at a high temperature of 140 ℃ in a ratio of TMB to BCS being 70:30, wherein the solution concentration is 1.5 wt% and the dissolving time is 6 h.
2) Loading a sample: transferring the sample solution into a classification column (the filler is glass beads with 60-80 meshes), stabilizing at 140 ℃ for 60min, and then cooling to room temperature at a constant cooling rate of 1.5 ℃/h, so that the polymer is precipitated from the mixed solvent and loaded onto the glass beads filled in the column.
3) Leaching the sample: after the temperature reduction procedure is finished, after the mixture is balanced for 24 hours at room temperature, the mixed solvent in the fractionating column is replaced by 100 percent poor solvent BCS, meanwhile, room temperature fractions (1-1# fractions) dissolved in the mixed solvent are washed out, then the temperature is raised to 130 ℃, and different fractions (respectively marked as 1-2# fractions, 1-3# fractions, 1-4# fractions, 1-5# fractions and 1-6# fractions) with high molecular weights can be obtained by sequentially increasing the percentage content of good solvent TMB (respectively 0 percent, 10 percent, 20 percent, 30 percent and 40 percent). Wherein, dissolving the corresponding fractions in each ratio of mixed solvent requires equilibration for 24 hours in order to complete equilibration and separation. And cooling the leached solution, and standing.
4) Precipitation, filtration and drying of the sample: adding acetone solvent with twice volume of the leaching solution to precipitate, then filtering and washing, and drying the obtained fraction at 40 ℃ in vacuum to constant weight.
The mass of each fraction obtained by classification is shown in the following table 1:
table 1 mass of each fraction fractionated in example 1
The results of Gel Permeation Chromatography (GPC) measurements of the fractions are shown in table 2 below:
table 2 GPC test results for the fractionated fractions prepared in example 1
Example 2
1) Dissolving a sample: a resin sample was dissolved in a mixed solvent of TMB and BCS at 80:20 (TMB: BCS) at 140 ℃ for 4 hours using 1,3, 5-Trimethylbenzene (TMB) as a good solvent and Butyl Cellosolve (BCS) as a poor solvent, at a solution concentration of 1.0 wt%.
2) Loading a sample: transferring the sample solution into a classification column (the filler is quartz sand with 60-80 meshes), stabilizing at 140 ℃ for 30min, and then cooling to room temperature at a cooling rate of 1 ℃/h to enable the polymer to be precipitated from the mixed solvent and loaded on the quartz sand filled in the column.
3) Leaching the sample: after the temperature reduction procedure is finished and the mixture is balanced for 24 hours at room temperature, the mixed solvent in the fractionating column is replaced by 100 percent of poor solvent BCS, and meanwhile, room temperature fractions (2-1# fractions) dissolved in the mixed solvent are washed out. Then, the grading temperature is increased to 120 ℃, and by sequentially increasing the percentage content (0%, 10%, 20%, 30% and 40% respectively) of the good solvent TMB, the fractions with the molecular weight from low to high (respectively marked as 2-2# fraction, 2-3# fraction, 2-4# fraction, 2-5# fraction and 2-6# fraction) can be respectively obtained. Wherein, dissolving the corresponding fractions in each ratio of mixed solvent requires equilibration for 24 hours in order to complete equilibration and separation. And cooling the leached solution, and standing.
4) Precipitation, filtration and drying of the sample: adding acetone solvent with twice volume of the leaching solution to precipitate, then filtering and washing, and drying the obtained fraction at 30 ℃ in vacuum to constant weight.
The mass of each fraction obtained by classification is shown in the following table 3:
table 3 mass of each fraction fractionated in example 2
The results of GPC testing of the fractionated fractions are shown in table 4 below:
table 4 GPC test results for the fractionated fractions prepared in example 2
Example 3
1) Dissolving a sample: xylene is used as a good solvent, Butyl Cellosolve (BCS) is used as a poor solvent, and a resin sample is dissolved in a mixed solvent of the xylene and the BCS at a temperature of 70:30 at a temperature of 130 ℃, wherein the solution concentration is 0.5wt%, and the dissolving time is 5 h.
2) Loading a sample: transferring the sample solution into a classification column (the filler is glass beads with 60-80 meshes), stabilizing at 130 ℃ for 60min, and then cooling to room temperature at a cooling rate of 1 ℃/h to enable the polymer to be precipitated from the mixed solvent and loaded on the glass beads filled in the column.
3) Leaching the sample: after the temperature reduction procedure is finished and the mixture is balanced at room temperature for 24 hours, the mixed solvent in the fractionating column is replaced by 100 percent of poor solvent BCS, and meanwhile, room temperature fractions (3-1# fractions) dissolved in the mixed solvent are washed out. Then the grading temperature is raised to 100 ℃, and by sequentially increasing the percentage content (0%, 10%, 20% and 30% respectively) of good solvent xylene, the fractions with the molecular weight from low to high (3-2 # fraction, 3-3# fraction, 3-4# fraction and 3-5# fraction respectively) can be obtained. Wherein, dissolving the corresponding fractions in each ratio of mixed solvent requires equilibration for 24 hours in order to complete equilibration and separation. And cooling the leached solution, and standing.
4) Precipitation, filtration and drying of the sample: precipitating the eluate with twice volume of ethanol solvent, filtering, washing, and vacuum drying the obtained fraction at 30 deg.C to constant weight.
The mass of each fraction obtained by classification is shown in the following table 5:
TABLE 5 quality of each fraction fractionated in example 3
The results of GPC testing of the fractionated fractions are shown in table 6 below:
table 6 GPC test results for the fractionated fractions prepared in example 3
Example 4
1) Dissolving a sample: xylene is used as a good solvent, Butyl Cellosolve (BCS) is used as a poor solvent, and a resin sample is dissolved in a mixed solvent of xylene and BCS (80: 20) at a high temperature of 130 ℃, wherein the solution concentration is 1.0 wt%, and the dissolving time is 5 h.
2) Loading a sample: transferring the sample solution into a classification column (the filler is glass beads with 60-80 meshes), stabilizing at 130 ℃ for 60min, and then cooling to room temperature at a cooling rate of 0.5 ℃/h to enable the polymer to be precipitated from the mixed solvent and loaded onto the glass beads filled in the column.
3) Leaching the sample: after the temperature reduction procedure is finished and the mixture is balanced at room temperature for 24 hours, the mixed solvent in the fractionating column is replaced by 100 percent of poor solvent BCS, and meanwhile, room temperature fractions (4-1# fractions) dissolved in the mixed solvent are washed out. Then the grading temperature is raised to 110 ℃, and by sequentially increasing the percentage content (0%, 10%, 20% and 30% respectively) of good solvent xylene, the fractions with the molecular weight from low to high (4-2 # fraction, 4-3# fraction, 4-4# fraction and 4-5# fraction respectively) can be obtained. Wherein, dissolving the corresponding fractions in each ratio of mixed solvent requires equilibration for 24 hours in order to complete equilibration and separation. And cooling the leached solution, and standing.
4) Precipitation, filtration and drying of the sample: adding acetone solvent with twice volume of the leaching solution to precipitate, then filtering and washing, and drying the obtained fraction at 30 ℃ in vacuum to constant weight.
The mass of each fraction obtained by fractionation is shown in the following table 7:
table 7 mass of each fraction fractionated in example 4
The results of GPC testing of the fractionated fractions are shown in table 8 below:
table 8 GPC test results for the fractionated fractions prepared in example 4
Example 5
1) Dissolving a sample: trichlorobenzene (TCB) is used as a good solvent, Ethyl Cellosolve (ECS) is used as a poor solvent, and a resin sample is dissolved in a mixed solvent of TCB and ECS of 75:25 at a high temperature of 135 ℃, wherein the solution concentration is 1.0 wt%, and the dissolving time is 5 h.
2) Loading a sample: transferring the sample solution into a classification column (the filler is glass beads with 60-80 meshes), stabilizing at 135 ℃ for 40min, and then cooling to room temperature at a cooling rate of 0.5 ℃/h to enable the polymer to be precipitated from the mixed solvent and loaded onto the glass beads filled in the column.
3) Leaching the sample: after the temperature reduction procedure is finished and the mixture is balanced at room temperature for 24 hours, the mixed solvent in the fractionating column is changed into 100 percent poor solvent ECS, and meanwhile, room temperature fractions (5-1# fractions) dissolved in the mixed solvent are washed out. Then the grading temperature is raised to 110 ℃, and by sequentially increasing the percentage content (0%, 10%, 20% and 30% respectively) of the good solvent TCB, the fractions with the molecular weight from low to high (5-2 # fraction, 5-3# fraction, 5-4# fraction and 5-5# fraction respectively) can be obtained. Wherein, dissolving the corresponding fractions in each ratio of mixed solvent requires equilibration for 24 hours in order to complete equilibration and separation. And cooling the leached solution, and standing.
4) Precipitation, filtration and drying of the sample: adding acetone solvent with twice volume of the leaching solution to precipitate, then filtering and washing, and drying the obtained fraction at 30 ℃ in vacuum to constant weight.
The mass of each fraction obtained by fractionation is shown in the following table 9:
TABLE 9 quality of each fraction fractionated in example 5
The results of GPC testing of the fractionated fractions are shown in table 10 below:
table 10 GPC test results for the fractionated fractions prepared in example 5
Example 6
Solvent gradient grading PB-1 specific steps:
1) dissolving a sample: trichlorobenzene (TCB) is used as a good solvent, Ethyl Cellosolve (ECS) is used as a poor solvent, and a resin sample is dissolved in a mixed solvent of TCB and ECS of 70:30 at a high temperature of 130 ℃, wherein the solution concentration is 0.5wt%, and the dissolving time is 5 h.
2) Loading a sample: transferring the sample solution into a classification column (the filler is glass beads with 60-80 meshes), stabilizing at 130 ℃ for 40min, and then cooling to room temperature at a cooling rate of 1 ℃/h to enable the polymer to be precipitated from the mixed solvent and loaded on the glass beads filled in the column.
3) Leaching the sample: after the temperature reduction procedure is finished and the mixture is balanced at room temperature for 24 hours, the mixed solvent in the fractionating column is changed into 100 percent poor solvent ECS, and simultaneously room temperature fractions (6-1# fractions) dissolved in the mixed solvent are washed out. Then, the classification temperature is raised to 105 ℃, and by sequentially increasing the percentage content (0%, 10%, 20% and 30% respectively) of the good solvent TCB, the fractions with the molecular weight from low to high (6-2 # fraction, 6-3# fraction, 6-4# fraction and 6-5# fraction respectively) can be obtained. Wherein, dissolving the corresponding fractions in each ratio of mixed solvent requires equilibration for 24 hours in order to complete equilibration and separation. And cooling the leached solution, and standing.
4) Precipitation, filtration and drying of the sample: adding acetone solvent with twice volume of the leaching solution to precipitate, then filtering and washing, and drying the obtained fraction at 30 ℃ in vacuum to constant weight.
The mass of each fraction obtained by fractionation is shown in the following table 11:
TABLE 11 quality of each fraction fractionated in example 6
The GPC test results for the fractionated fractions are shown in table 12 below:
table 12 GPC test results for the fractionated fractions prepared in example 6
Example 7
Solvent gradient grading PB-1 specific steps:
1) dissolving a sample: dichlorobenzene is used as a good solvent, Butyl Cellosolve (BCS) is used as a poor solvent, and a resin sample is dissolved in a mixed solvent of dichlorobenzene and BCS (70: 30) at a high temperature of 150 ℃, wherein the solution concentration is 0.5wt%, and the dissolving time is 5 h.
2) Loading a sample: transferring the sample solution into a classification column (the filler is glass beads with 60-80 meshes), stabilizing at 150 ℃ for 30min, and then cooling to room temperature at a cooling rate of 0.5 ℃/h to enable the polymer to be precipitated from the mixed solvent and loaded onto the glass beads filled in the column.
3) Leaching the sample: after the temperature reduction procedure is finished and the mixture is balanced at room temperature for 24 hours, the mixed solvent in the fractionating column is replaced by 100 percent of poor solvent BCS, and meanwhile, room temperature fractions (7-1# fractions) dissolved in the mixed solvent are eluted. Then the grading temperature is raised to 125 ℃, and by sequentially increasing the percentage content of good solvent dichlorobenzene (respectively 0%, 10%, 20% and 30%), low-to-high molecular weight fractions (respectively marked as 7-2# fraction, 7-3# fraction, 7-4# fraction and 7-5# fraction) can be respectively obtained. Wherein, dissolving the corresponding fractions in each ratio of mixed solvent requires equilibration for 24 hours in order to complete equilibration and separation. And cooling the leached solution, and standing.
4) Precipitation, filtration and drying of the sample: adding acetone solvent with twice volume of the leaching solution to precipitate, then filtering and washing, and drying the obtained fraction at 30 ℃ in vacuum to constant weight.
The mass of each fraction obtained by fractionation is shown in the following table 13:
TABLE 13 quality of each fraction fractionated in example 7
The results of GPC testing of the fractionated fractions are shown in table 14 below:
table 14 GPC test results for the fractionated fractions prepared in example 7
Example 8
Solvent gradient grading PB-1 specific steps:
1) dissolving a sample: dichlorobenzene was used as a good solvent, Butyl Cellosolve (BCS) was used as a poor solvent, and a resin sample was dissolved in a mixed solvent of dichlorobenzene and BCS 80:20 at a high temperature of 140 ℃ at a solution concentration of 1.0 wt% for a dissolution time of 5 hours.
2) Loading a sample: transferring the sample solution into a classification column (the filler is glass beads with 60-80 meshes), stabilizing at 140 ℃ for 60min, and then cooling to room temperature at a cooling rate of 1 ℃/h to enable the polymer to be precipitated from the mixed solvent and loaded on the glass beads filled in the column.
3) Leaching the sample: after the temperature reduction procedure is finished and the mixture is balanced at room temperature for 24 hours, the mixed solvent in the fractionating column is replaced by 100 percent of poor solvent BCS, and meanwhile, room temperature fractions (8-1# fractions) dissolved in the mixed solvent are washed out. Then the grading temperature is raised to 120 ℃, and by sequentially increasing the percentage content of good solvent dichlorobenzene (respectively 0%, 10%, 20% and 30%), low-to-high molecular weight fractions (respectively 8-2# fraction, 8-3# fraction, 8-4# fraction and 8-5# fraction) can be respectively obtained. Wherein, dissolving the corresponding fractions in each ratio of mixed solvent requires equilibration for 24 hours in order to complete equilibration and separation. And cooling the leached solution, and standing.
4) Precipitation, filtration and drying of the sample: adding acetone solvent with twice volume of the leaching solution to precipitate, then filtering and washing, and drying the obtained fraction at 30 ℃ in vacuum to constant weight.
The mass of each fraction obtained by fractionation is shown in the following table 15:
TABLE 15 quality of each fraction obtained by fractionation in example 8
The GPC test results for the fractionated fractions are shown in table 16 below:
table 16 GPC test results for the fractionated fractions prepared in example 8
As can be seen from the above examples, the present invention provides a process for preparing polybutene-1 with narrow molecular weight distribution, comprising the steps of: dissolving a polybutene-1 sample in a mixed solvent at 120-150 ℃ to obtain a sample solution with the concentration of 0.5-1.5 wt%; the mixed solvent comprises a good solvent and a poor solvent with the volume ratio of 70-95: 5-30; the good solvent is selected from one or more of 1,2, 4-trimethylbenzene, 1,3, 5-trimethylbenzene, 1,2, 4-trichlorobenzene, dichlorobenzene and xylene; the poor solvent is selected from ethyl cellosolve and/or butyl cellosolve; and cooling the sample solution to 10-30 ℃, loading the sample on the filler, completely replacing the mixed solvent with a poor solvent after balancing, heating to 100-130 ℃, sequentially increasing the volume percentage content of a good solvent, balancing, and leaching to respectively obtain the polybutene-1 with narrow molecular weight distribution and high molecular weight. According to the invention, the polybutene-1 sample is treated by adopting a specific kind of mixed solvent under specific conditions, so that the molecular weight of the polybutene-1 sample is classified, and the fraction with narrow molecular weight distribution is obtained.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (1)
1. A process for the preparation of narrow molecular weight distribution polybutene-1 comprising the steps of:
dichlorobenzene is used as a good solvent, butyl cellosolve is used as a poor solvent, and the dichlorobenzene and the butyl cellosolve are mixed in a mixed solvent with the volume ratio of 70:30 at 150oC, dissolving the polybutene-1 sample at high temperature, wherein the solution concentration is 0.5wt%, and the dissolving time is 5 hours;
transferring the sample solution to a fractionating column at 150oAfter C is stabilized for 30min, 0.5 is addedoCooling the temperature of the C/h to room temperature, so that the polymer is precipitated from the mixed solvent and loaded onto the 60-80-mesh glass beads filled in the column;
after the temperature reduction procedure is finished, after the mixture is balanced for 24 hours at room temperature, the mixed solvent in the fractionating column is replaced by 100 percent of poor solventButyl cellosolve, and simultaneously eluting the room-temperature fraction dissolved in the mixed solvent; the temperature of the fraction was then raised to 125 deg.CoC, sequentially increasing the percentage content of the good solvent dichlorobenzene to respectively obtain fractions with the molecular weights from low to high; dissolving the corresponding fractions in each proportion of mixed solvent requires equilibration for 24h in order to complete equilibration and separation; cooling the leached solution, and standing;
after the washing, the method also comprises the following steps:
and respectively precipitating the eluted washing liquid with the molecular weight from low to high by using acetone, and sequentially filtering, washing and drying to obtain the polybutene-1 with different narrow molecular weight distributions.
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| Microstructure characterization of one high-speed extrusion coating polyethylene resin fractionated by solvent gradient fractionation;Pei Li，et al.;《Journal of polymer research》;20180411;第25卷(第5期);113 * |
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