CN107254055B - Method for directly crystallizing I crystal from isotactic poly-1-butene body - Google Patents
Method for directly crystallizing I crystal from isotactic poly-1-butene body Download PDFInfo
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- CN107254055B CN107254055B CN201710472011.3A CN201710472011A CN107254055B CN 107254055 B CN107254055 B CN 107254055B CN 201710472011 A CN201710472011 A CN 201710472011A CN 107254055 B CN107254055 B CN 107254055B
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- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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Abstract
Disclosed herein is a process for the direct crystallization of I crystals from isotactic poly-1-butene bulk comprising the steps of: after the I crystal in the iP-1-B is completely melted, cooling to room temperature to obtain a II crystal, and after the II crystal is heated to be melted again, cooling to the temperature between 30 ℃ and-30 ℃ to directly obtain the I crystal in the iP-1-B body, wherein the preferable temperature range is between 10 ℃ and-10 ℃. If the temperature is increased and decreased for a plurality of times within the temperature range to the melting point of the I crystal, more I crystals can be obtained by directly crystallizing from the iP-1-B body. The proportion of I crystal generation can be regulated and controlled within a certain range by controlling the cycle number, the low-end temperature in the cycle process and the like. The method provides a feasible way for regulating and controlling the crystal structure in the melt processing process of iP-1-B to obtain thermodynamically stable I crystal.
Description
Technical Field
The invention belongs to the technical field of polymer processing, and particularly relates to a method for directly crystallizing in an isotactic poly-1-butene (iP-1-B) body to obtain I crystals.
Background
Isotactic poly-1-butene (iP-1-B) has a plurality of crystal forms, wherein the crystal form I is a hexagonally stacked crystal with a thermodynamically stable 3/1 helical conformation. The physical properties of the I crystal iP-1-B, such as toughness, tensile strength, flexibility, bending strength, stress cracking resistance, impact resistance, abrasion resistance, high temperature resistance, heat insulation performance and the like, are superior to those of other polyolefins, so that the iP-1-B has great industrial value and becomes a competitive material for manufacturing hot water pipe pressure tanks. Although isotactic poly-1-butene which is a commercially available raw material is mostly in the I crystal form after being placed at room temperature for a long time, iP-1-B often forms metastable II crystals which are 11/3 spiral-stacked tetragonal crystals when being melted, and then the II-I conversion is completed within 10 days or more at room temperature and normal pressure, so that all indexes such as tensile strength, hardness and density of the material are continuously changed during the quite long crystal form structure conversion period, the size is difficult to stabilize, and the problem of shrinkage of the surface of a molded sample is caused. These undoubtedly greatly limit the application and popularization of isotactic poly-1-butene. It would therefore be of great interest to develop a process that can efficiently crystallize I crystals directly from the bulk of iP-1-B.
The prior art shows that the I' crystal form (sometimes called I crystal) can be directly obtained by melt crystallization under high pressure, crystallization under ultra-thin film conditions, matrix epitaxial growth or monomer copolymerization, etc., and is generally considered to have 3/1 spiral conformation stacking crystal structure similar to the I crystal phase, but the melting point is about 95 ℃ which is far lower than that of the I crystal, about 127 ℃. Although the results show that some I crystals can be obtained by the I seed method, the method is difficult to be applied in the melt processing process.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for directly crystallizing I crystal from an iP-1-B body, wherein the I crystal is directly formed by controlling iP-1-B to crystallize at low temperature, so that a feasible way is provided for developing an effective regulation and control technology for directly crystallizing I crystal in the iP-1-B melting processing process.
The technical purpose of the invention is realized by the following technical scheme:
a method for directly crystallizing I crystal from isotactic poly-1-butylene body comprises the following steps:
step 1, heating and melting the I crystal isotactic poly-1-butene, and cooling to room temperature to obtain II crystal iP-1-B;
specifically, weighing a sample of iP-1-B crystal, heating to 200-220 ℃ at a speed of 5-10 ℃/min, keeping the temperature constant for 2-5 min, and then cooling to room temperature of 20-25 ℃ at a speed of 10-15 ℃/min to obtain iP-1-B crystal II.
And 2, heating the II crystal iP-1-B obtained in the step 1 to a temperature higher than the melting point of the II crystal, melting, preserving heat, cooling to a temperature between-30 ℃ and preserving heat, and directly crystallizing from the isotactic poly-1-butylene body to generate I crystal.
Specifically, heating the II crystal iP-1-B obtained in the step 1 to a temperature higher than the melting point of the II crystal at a speed of 10-30 ℃/min for melting, for example, heating to 125-130 ℃, keeping the temperature for a certain time, for example, 2-5 min, then cooling to a temperature between-30 ℃ and 30 ℃ at a cooling speed of 10-15 ℃/min, for example, 10-10 ℃, and keeping the temperature for 2-5 min.
Heating the iP-1-B sample obtained in the step 2 to 200 ℃ at a certain heating rate, such as 10 ℃/min, a melting peak around 133 ℃ can be observed, wherein the peak is I crystal directly obtained from bulk crystallization of iP-1-B, and a melting curve of the directly formed I crystal at 133 ℃ obtained by cooling to 10 ℃ in the step 2 is shown in figure 5, wherein the melting peak at 129 ℃ is the melting peak of the I crystal obtained by II-I transformation, and the melting point is slightly higher than the melting point 127 ℃ of the I crystal obtained after the II-I transformation is basically completed in figure 2 at the early formation stage;
repeating the temperature rising and reducing process (i.e. rising to a temperature above the melting point of the II crystal and reducing to a temperature between-30 ℃ and 30 ℃) in the step 2, after a plurality of cycles, the DSC curve can show more I crystals directly obtained from iP-1-B bulk crystallization, as shown in FIG. 6, the DSC melting curve of the sample obtained after 10 cycles is shown, and as shown in FIG. 7, the 1D-WAXS curves corresponding to 80 ℃, 122 ℃ and 145 ℃ are shown. As can be seen from FIG. 6, the proportion of I crystal can be controlled by controlling the cycle number. Meanwhile, the temperature of the temperature range of minus 30 ℃ to 30 ℃ and the holding time are adjusted, and the directly formed I crystals with different contents can be obtained.
The technical method provided by the invention is particularly suitable for homopolymerization iP-1-B with excellent mechanical property, and the thermodynamically metastable II crystal can be obtained by cooling and crystallizing the melt under normal conditions, while the thermodynamically stable I crystal can be directly obtained by crystallizing the bulk by adopting the technical method provided by the invention. By using the technical method provided by the invention, I crystal can be directly crystallized from the iP-1-B melt, and in addition, a feasible technical approach is provided for realizing the regulation and control of the proportion of directly generating I crystal in the melt by controlling the temperature rise and fall cycle times, the low-end temperature in the cycle process and the like, namely, the regulation and control of the proportion of directly generating I crystal in the melt is realized by the temperature rise and fall cycle times and the low-end temperature in the cycle process.
Drawings
FIG. 1 is a DSC melting curve diagram of iP-1-B as raw material I crystal.
FIG. 2 is a 1D-WAXS diagram of iP-1-B crystal of raw material I.
FIG. 3 is a DSC melting curve of sample II crystal iP-1-B.
FIG. 4 is a 1D-WAXS diagram of sample II, crystal iP-1-B.
FIG. 5 is a DSC temperature-rising melting curve of 133 ℃ directly formed in a sample by melting sample II crystal iP-1-B to 125 ℃ and then cooling back to 10 ℃ to obtain the I crystal.
FIG. 6 is a DSC plot of sample iP-1-B (isotacticity 94%) after cycling 10 times between 10 ℃ and 125 ℃.
FIG. 7 is a DSC plot of sample iP-1-B (isotacticity 94%) after cycling 10 times between 10 ℃ and 125 ℃.
FIG. 8 is a DSC temperature-rising melting curve of 133 ℃ directly formed crystal I in the sample obtained by melting iP-1-B of the sample II to 125 ℃ and then cooling back to 30 ℃ and keeping the temperature for 2min in example 2.
FIG. 9 is a DSC temperature-rising melting curve of 133 ℃ directly formed in the sample obtained by melting iP-1-B of the sample II crystal to 125 ℃, then cooling back to-30 ℃ and keeping the temperature for 2min in example 3.
FIG. 10 is a DSC melting curve at 133 ℃ of directly formed I crystal in the sample obtained by melting iP-1-B of the sample II crystal to 125 ℃ and then cooling back to-10 ℃ and keeping the temperature for 2min in example 4.
FIG. 11 is a DSC melting curve at 133 ℃ directly formed in the sample by melting iP-1-B of the sample II crystal to 125 ℃, then cooling back to-10 ℃ and keeping the temperature for 60min in example 5.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments below:
example 1: 10mg of iP-1-B (isotacticity 94%, eastern macro chemical industry Co., Ltd.) is weighed, the DSC and 1D-WAXS graphs of the iP-1-B are shown in figures 1 and 2, the iP-1-B is placed into an aluminum crucible and then placed into DSC (Q2000, TA Co., Ltd.) equipment, the temperature is raised to 200 ℃ at the rate of 5 ℃/min and is kept constant for 2min, then the temperature is lowered to 20 ℃ at the rate of 15 ℃/min, and the obtained sample is II crystal iP-1-B, and the DSC and 1D-WAXS graphs of the iP-1-B are shown in figures 3 and 4; then raising the temperature to 125 ℃ at 10 ℃/min, then lowering the temperature to 10 ℃ at 15 ℃/min to obtain the DSC melting curve of the directly formed I crystal as shown in figure 5, for example, cycling 10 times at 10-125 ℃ to obtain the DSC melting curve as shown in figure 6, and obtaining 1D-WAXS graphs as shown in figure 7 at 80 ℃, 122 ℃ and 145 ℃ respectively, as can be seen from figure 6, the proportion of the generated I crystal can be regulated and controlled by controlling the cycle times.
Example 2: 10mg of iP-1-B (isotacticity 94%, Oriental macro chemical Co., Ltd.) is weighed, the DSC and 1D-WAXS graphs are shown in figures 1 and 2, the mixture is placed into an aluminum crucible and then placed into DSC (Q2000, TA Co.) equipment, the temperature is raised to 200 ℃ at the rate of 5 ℃/min and is kept constant for 2min, then the temperature is lowered to room temperature at the rate of 15 ℃/min, and the sample is obtained to be II crystal iP-1-B, and the DSC and 1D-WAXS graphs are shown in figures 3 and 4; then heating to 125 deg.C at 10 deg.C/min, cooling to 30 deg.C at 15 deg.C/min, and holding for 2min to obtain DSC melting curve of directly formed crystal I as shown in FIG. 8, wherein the obtained crystallinity of directly formed crystal I is 0.06%.
Example 3: 10mg of iP-1-B (isotacticity 94%, Oriental macro chemical Co., Ltd.) is weighed, the DSC and 1D-WAXS graphs are shown in figures 1 and 2, the mixture is placed into an aluminum crucible and then placed into DSC (Q2000, TA Co.) equipment, the temperature is raised to 200 ℃ at the rate of 5 ℃/min and is kept constant for 2min, then the temperature is lowered to room temperature at the rate of 15 ℃/min, and the sample is obtained to be II crystal iP-1-B, and the DSC and 1D-WAXS graphs are shown in figures 3 and 4; then heating to 125 deg.C at 10 deg.C/min, cooling to-30 deg.C at 15 deg.C/min, and holding for 2min to obtain DSC melting curve of directly formed crystal I as shown in FIG. 9, wherein the obtained degree of crystallinity of directly formed crystal I is 0.70%.
Example 4: 10mg of iP-1-B (isotacticity 94%, Oriental macro chemical Co., Ltd.) is weighed, the DSC and 1D-WAXS graphs are shown in figures 1 and 2, the mixture is placed into an aluminum crucible and then placed into DSC (Q2000, TA Co.) equipment, the temperature is raised to 200 ℃ at the rate of 5 ℃/min and is kept constant for 2min, then the temperature is lowered to room temperature at the rate of 15 ℃/min, and the sample is obtained to be II crystal iP-1-B, and the DSC and 1D-WAXS graphs are shown in figures 3 and 4; then heating to 125 deg.C at 10 deg.C/min, cooling to-10 deg.C at 15 deg.C/min, and holding at constant temperature for 2min to obtain DSC melting curve of directly formed crystal I as shown in FIG. 10, wherein the obtained crystallinity of directly formed crystal I is 0.77%.
Example 5: 10mg of iP-1-B (isotacticity 94%, Oriental macro chemical Co., Ltd.) is weighed, the DSC and 1D-WAXS graphs are shown in figures 1 and 2, the mixture is placed into an aluminum crucible and then placed into DSC (Q2000, TA Co.) equipment, the temperature is raised to 200 ℃ at the rate of 5 ℃/min and is kept constant for 2min, then the temperature is lowered to room temperature at the rate of 15 ℃/min, and the sample is obtained to be II crystal iP-1-B, and the DSC and 1D-WAXS graphs are shown in figures 3 and 4; then heating to 125 deg.C at 10 deg.C/min, cooling to-10 deg.C at 15 deg.C/min, and holding for 60min to obtain DSC melting curve of directly formed crystal I as shown in FIG. 11, with the obtained degree of crystallinity of directly formed crystal I being 0.86%.
The I crystal can be directly formed by adjusting the process parameters of temperature rise and temperature reduction according to the content recorded in the invention, and the crystallinity of the I crystal can be adjusted by the process parameters. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (4)
1. A process for the direct crystallization of I crystals from isotactic poly-1-butene bulk, characterized in that it is carried out according to the following steps:
step 1, heating and melting I crystal isotactic poly-1-butylene, cooling to room temperature to obtain II crystal iP-1-B, namely weighing an I crystal iP-1-B sample, heating to 200-220 ℃ at the speed of 5-10 ℃/min, keeping the temperature for 2-5 min, and then cooling to the room temperature of 20-25 ℃ at the speed of 10-15 ℃/min to obtain II crystal iP-1-B;
step 2, heating the II crystal iP-1-B obtained in the step 1 to a temperature above the melting point of the II crystal, melting and preserving heat, then cooling to a temperature between minus 30 ℃ and preserving heat, so that I crystal can be directly crystallized from the isotactic poly-1-butene body, namely heating the II crystal iP-1-B obtained in the step 1 to a temperature above the melting point of the II crystal at a speed of 10-30 ℃/min, melting, keeping the temperature for 2-5 min, then cooling to a temperature between minus 30 ℃ and 30 ℃ at a cooling speed of 10-15 ℃/min, and preserving heat for 2-5 min;
and (3) repeating the heating and cooling processes in the step (2), namely heating to a temperature above the melting point of the crystal II, cooling to a temperature between minus 30 ℃ and 30 ℃, and after a plurality of cycles, more crystals I can be directly obtained from the iP-1-B body through crystallization.
2. The method for directly crystallizing I crystals from an isotactic poly-1-butene bulk according to claim 1, wherein in the step 2, the temperature of the II crystals iP-1-B obtained in the step 1 is increased to 125-130 ℃ at the speed of 10-30 ℃/min, the temperature is kept for 2-5 min, and then the temperature is decreased to-10 ℃ at the speed of 10-15 ℃/min, and the temperature is kept for 2-5 min.
3. The method for directly crystallizing I crystals from the bulk of isotactic poly-1-butene according to claim 1, wherein the proportion of I crystals formed is controlled by controlling the number of cycles.
4. The method for directly crystallizing I crystals from isotactic poly-1-butene bulk according to claim 1, wherein the temperature of the temperature range of-30 ℃ to 30 ℃ and the time for holding are adjusted to obtain different contents of directly formed I crystals.
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| CN201710472011.3A CN107254055B (en) | 2017-06-20 | 2017-06-20 | Method for directly crystallizing I crystal from isotactic poly-1-butene body |
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| CN110903493B (en) * | 2018-09-17 | 2022-08-02 | 天津大学 | Method for regulating and controlling transformation of crystal form II-crystal form I by adding liquid additive capable of matching with melt processing process of isotactic poly-1-butene |
| CN113402818B (en) * | 2020-03-16 | 2022-08-02 | 天津大学 | Method for generating crystal form III through crystallization from isotactic poly-1-butene body |
| CN113493584A (en) * | 2020-03-18 | 2021-10-12 | 天津大学 | Method for regulating and controlling content of isotactic poly-1-butene crystal form III through cooling rate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4359544A (en) * | 1982-02-01 | 1982-11-16 | Shell Oil Company | Synergistic co-nucleants for butene-1 polymer compositions |
| CN104610552A (en) * | 2013-11-01 | 2015-05-13 | 天津大学 | Method for accelerating crystallization of isotactic poly 1-butylene by shear flow |
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- 2017-06-20 CN CN201710472011.3A patent/CN107254055B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4359544A (en) * | 1982-02-01 | 1982-11-16 | Shell Oil Company | Synergistic co-nucleants for butene-1 polymer compositions |
| CN104610552A (en) * | 2013-11-01 | 2015-05-13 | 天津大学 | Method for accelerating crystallization of isotactic poly 1-butylene by shear flow |
Non-Patent Citations (1)
| Title |
|---|
| "Kinetics of Nucleation and Growth of Form II to I Polymorphic Transition in Polybutene‑1 as Revealed by Stepwise Annealing";Yongna Qiao et al.;《Macromolecules》;20160714;第49卷;第5126-5136页 * |
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