CN104610552A - Method for accelerating crystallization of isotactic poly 1-butylene by shear flow - Google Patents
Method for accelerating crystallization of isotactic poly 1-butylene by shear flow Download PDFInfo
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- CN104610552A CN104610552A CN201310539040.9A CN201310539040A CN104610552A CN 104610552 A CN104610552 A CN 104610552A CN 201310539040 A CN201310539040 A CN 201310539040A CN 104610552 A CN104610552 A CN 104610552A
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Abstract
The invention discloses a method for accelerating crystallization of isotactic poly 1-butylene by shear flow, when the temperature is reduced from heat treatment temperature to the crystallization temperature, the isotactic poly 1-butylene is applied with shear flow, and is fully crystallized by maintaining for enough time. The heat treatment temperature is 200 DEG C, and thermal history can be eliminated by maintaining for 5min at the heat treatment temperature. The isothermal crystallization temperature is 85 DEG C, the shear rate is 10-40s<-1>, and the shear time is 5S. According to the method, macromolecular chains in mesomorphic phase are in directional arrangement along flow direction, the entropy of crystallization can be reduced, the number of crystal nucleus is increased significantly, and the crystal growth period is decreased to accelerate the crystallization of 1-butylene.
Description
Technical field
The invention belongs to Crystallization Kinetics of Polymers field, more particularly, relate to and shearing action is applied to accelerate the method for Crystallization Kinetics of Polymers to polymkeric substance subcooling films.
Background technology
The structural formula of poly 1-butene is--(H2C-CH (C2H5)) n--, Tg=-25 DEG C, Tm=96-136 DEG C, belong to semi-crystalline polymer, heat-resisting creep properties under this material flexibility, high temperature, stress cracking resistance is good, resistance to wet-milling simultaneously, chemical-resistant reagent, tasteless, nontoxic, odorless, especially can at 90-100 DEG C of temperature life-time service, therefore can be used as hot-water line; Its performance is similar to PVC softwood, can be blended thus expand its range of application with other polyolefins superpolymer.The poly 1-butene (i-PB) of high isotactic high-crystallinity is called as " plastics gold ", is one of most advanced chemical material in the world.
Isotactic 1-polybutylene can exist with multiple crystal formation, the tetragonal Π type crystal formation piled up by 11/3 coiled strand is generated under crystallization normal pressure from melt, when not adding nucleator or not applying outer field action, nucleation number is less and forming rate of crystals is slower, affect its industrial application, the kinetics of crystallization process therefore studying isotactic 1-polybutylene has great importance.In the crystallisation process middle-molecular-weihydroxyethyl of poly 1-butene, molecular weight distribution, nucleator, outer field action, processing conditionss etc. all can affect its kinetics of crystallization process and crystallization shape, and then change the microstructure of crystal, and finally cause the change of product performance, such as Chen have studied the crystallization behavior of iPP/SWCNTs matrix material in Shearing Flow, research find when pure iPP in the quiescent state crystallization time, Avrami index is 4.0, polymkeric substance is under certain shear field during crystallization, n value is 1.82, show that adding of shearing is that the three dimensional growth of crystallization under static state becomes one-dimensional growth.Meanwhile, the crystallization semi-period is reduced to 29.5min by original 150.3min, illustrates that adding of shearing have impact on iPP isothermal crystal process greatly.The people such as Monasse study the shear flow poly crystallization behavior of isotactic after the match, and shear and make to form more nucleation site in polymer melt, the row's core produced in shear history causes the anisotropy of crystal growth, and think that shearing has a significant impact Avrami.
Summary of the invention
Technical purpose of the present invention is to overcome the deficiencies in the prior art, a kind of method of shear flow work in order to accelerate polymer crystallization poly 1-butene subcooling films being applied to suitable degree is provided, improves kinetics of crystallization process by increase nucleus number and crystal radial growth speed.
Technical purpose of the present invention is achieved by following technical proposals.
Accelerate a method for isotactic 1-polybutylene crystallization with shear flow, after temperature is dropped to Tc by thermal treatment temp, shear flow effect is applied to isotactic 1-polybutylene, and keeps time enough to make its crystallization complete.
Described thermal treatment temp is on the melt temperature of isotactic 1-polybutylene.
Specifically, carry out according to following step:
Step one, with vulcanizing press, poly 1-butene particle is pressed into print;
Step 2, sheet poly 1-butene press mold is placed in shear cell, makes thermal station temperature be raised on melt temperature with certain speed;
The height value of step 3, adjustment shear cell, makes the thickness that sample reaches predetermined; Make sample keep for some time to eliminate its thermal history in thermal treatment temp simultaneously;
Step 4, with certain speed, thermal station is dropped to Tc from thermal treatment temp;
Step 5, temperature apply shear flow effect to sample with certain shear after dropping to Tc at once;
Step 6, Tc keep time enough make sample crystallization complete.
Described thermal treatment temp is 200 degrees Celsius, is heated to thermal treatment temp 200 DEG C with the speed of 30 DEG C/min, keeps 5min to eliminate its thermal history in thermal treatment temp.
Described isothermal crystal temperature is 85 DEG C, reduces the temperature to Tc 85 DEG C with the speed of 30 DEG C/min, and shearing rate is 10-40s
-1, shear time is 5s.
As thermoplastic resin, poly 1-butene is in machine-shaping as being subject to shearing action in injection moulding or extrusion, and therefore this patent this patent proposes a kind of method accelerating poly 1-butene kinetics of crystallization with shear flow.Shearing action makes polymkeric substance subcooling films Middle molecule chain there occurs stretching, extension orientation, the higher part of molecular weight due to time of relaxation the longer post crystallization in shearing action and lax competition in more the preserving of oriented structure, the molecular chain of orientation is assembled arrangement and is formed initial nucleus (row's core or shishs) along shear flow direction, folded chain is perpendicular to nucleus epitaxy afterwards, the columned crystal of final formation.Simultaneously because shearing action molecular chain arranges along shear direction, the free energy difference between mesomorphic state and molten state increases, and promotes the increase of nucleus; In addition molecular chain assemble on shear direction arrangement also make the formation of nucleus be more prone to.
Accompanying drawing explanation
Fig. 1 is the stationary crystallization change in process figure of polarized light microscope observing poly 1-butene, and wherein isothermal crystal temperature is 85 DEG C.
Fig. 2 is that polarized light microscope observing poly 1-butene shears crystallisation process variation diagram, and wherein isothermal crystal temperature is 85 DEG C, and shearing rate is 10s-1, and shear time is 5s.
Fig. 3 is that polarized light microscope observing poly 1-butene shears crystallisation process variation diagram, and wherein isothermal crystal temperature is 85 DEG C, and shearing rate is 20s-1, and shear time is 5s.
Fig. 4 is that polarized light microscope observing poly 1-butene shears crystallisation process variation diagram, and wherein isothermal crystal temperature is 85 DEG C, and shearing rate is 40s-1, and shear time is 5s.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.Shearing action is applied on isotactic 1-polybutylene and then the device that affects its crystallization behavior is the CSS450 shear cell that linkam company of Britain produces.The polarizing microscope used is Olympus microscope TH4-200.
Embodiment 1:
1, vulcanizing press temperature is raised to 170 DEG C, pressure 20bar keeps 5min, and poly 1-butene particle is pressed into certain thickness print;
2, laminar poly 1-butene press mold is placed in shear cell, is heated to thermal treatment temp 200 DEG C with the speed of 30 DEG C/min;
3, regulate the height value of shear cell, make the thickness 10um that sample reaches predetermined; Meanwhile, sample is made to keep 5min to eliminate its thermal history in thermal treatment temp;
4, Tc 85 DEG C is reduced the temperature to the speed of 30 DEG C/min;
5, time enough is kept to make sample crystallization complete in Tc.
As shown in Figure 1, under the condition of static isothermal crystal, only have spherocrystal to generate, and spherocrystal number is less, size is larger.
Embodiment 2:
1, the laminar poly 1-butene press mold by compression molding mechanism in embodiment 1 is placed in shear cell, is heated to thermal treatment temp 200 DEG C with the speed of 30 DEG C/min;
2, regulate the gap value of shear cell, make the thickness 10um that sample reaches predetermined; Meanwhile, sample is made to keep 5min to eliminate its thermal history in thermal treatment temp;
3, Tc 85 DEG C is reduced the temperature to the speed of 30 DEG C/min;
4, temperature applies Shearing Flow effect to sample after dropping to Tc at once, and shearing rate is 10s-1, and shear time is 5s;
5, time enough is kept to make sample crystallization complete in Tc.
As shown in Figure 2, when shearing rate is 10-1s, spherocrystal number increases, and the situation that the time that crystal covers with the visual field compares embodiment 1 shortens, and shears the kinetics of crystallization process accelerating isotactic 1-polybutylene.
Embodiment 3:
1, the laminar poly 1-butene press mold by compression molding mechanism in embodiment 1 is placed in shear cell, is heated to thermal treatment temp 200 DEG C with the speed of 30 DEG C/min;
2, regulate the gap value of shear cell, make the thickness 10um that sample reaches predetermined; Meanwhile, sample is made to keep 5min to eliminate its thermal history in thermal treatment temp;
3, Tc 85 DEG C is reduced the temperature to the speed of 30 DEG C/min;
4, temperature applies Shearing Flow effect to sample after dropping to Tc at once, and shearing rate is 20s-1, and shear time is 5s;
5, time enough is kept to make sample crystallization complete in Tc.
As shown in Figure 3, when shearing rate is 20-1s, then system first generates column crystal just has spherocrystal to generate.Spherocrystal number compares embodiment 1 and embodiment 2 increases, and crystal covers with the time shorten in the visual field.
Embodiment 4:
1, the laminar poly 1-butene press mold by compression molding mechanism in embodiment 1 is placed in shear cell, is heated to thermal treatment temp 200 DEG C with the speed of 30 DEG C/min;
2, regulate the gap value of shear cell, make the thickness 10um that sample reaches predetermined; Meanwhile, sample is made to keep 5min to eliminate its thermal history in thermal treatment temp;
3, Tc 85 DEG C is reduced the temperature to the speed of 30 DEG C/min;
4, temperature applies Shearing Flow effect to sample after dropping to Tc at once, and shearing rate is 40s-1, and shear time is 5s;
5, time enough is kept to make sample crystallization complete in Tc.
As shown in Figure 4, when shearing rate is 40-1s, column crystal and spherocrystal number all significantly increase, and crystallization is accelerated.
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.
Claims (3)
1. accelerate the method for isotactic 1-polybutylene crystallization with shear flow for one kind, it is characterized in that, after temperature is dropped to Tc by thermal treatment temp, shear flow effect is applied to isotactic 1-polybutylene, and keeping time enough to make its crystallization complete, described thermal treatment temp is on the melt temperature of isotactic 1-polybutylene.
2. a kind of method accelerating isotactic 1-polybutylene crystallization with shear flow according to claim 1, it is characterized in that, described thermal treatment temp is 200 degrees Celsius, is heated to thermal treatment temp 200 DEG C with the speed of 30 DEG C/min, keeps 5min to eliminate its thermal history in thermal treatment temp.
3. a kind of method accelerating isotactic 1-polybutylene crystallization with shear flow according to claim 1, it is characterized in that, described isothermal crystal temperature is 85 DEG C, reduces the temperature to Tc 85 DEG C with the speed of 30 DEG C/min, and shearing rate is 10-40s
-1, shear time is 5s.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107254055A (en) * | 2017-06-20 | 2017-10-17 | 天津大学 | A kind of brilliant crystallization generation I method directly from isotactic poly- 1 butylene body |
| CN108239291A (en) * | 2016-12-26 | 2018-07-03 | 天津大学 | A kind of regulation and control method of isotactic poly-1-butylene melt direct crystallization generation I ' crystalline substances |
| CN108264596A (en) * | 2017-01-04 | 2018-07-10 | 天津大学 | A kind of monomer copolymerization promotes iP-1-B directly from the method for melt composition I ' crystalline substances |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839442A (en) * | 2012-09-25 | 2012-12-26 | 揭阳市粤海化纤有限公司 | High-strength low-shrinkage polypropylene filament yarn and production method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102839442A (en) * | 2012-09-25 | 2012-12-26 | 揭阳市粤海化纤有限公司 | High-strength low-shrinkage polypropylene filament yarn and production method thereof |
Non-Patent Citations (2)
| Title |
|---|
| C.HADINATA: ""Comparison of shear–induced crystallization behavior of PB-1 samples with different molecular weight distribution"", 《JOURNAL OF RHEOLOGY》 * |
| G.KALAY ET AL.: ""Interlocking Shish-Kebab Morphology in Polybutene-1"", 《JOURNAL OF POLYMER SCIENCE:PART B》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108239291A (en) * | 2016-12-26 | 2018-07-03 | 天津大学 | A kind of regulation and control method of isotactic poly-1-butylene melt direct crystallization generation I ' crystalline substances |
| CN108264596A (en) * | 2017-01-04 | 2018-07-10 | 天津大学 | A kind of monomer copolymerization promotes iP-1-B directly from the method for melt composition I ' crystalline substances |
| CN108264596B (en) * | 2017-01-04 | 2020-05-12 | 天津大学 | Method for promoting iP-1-B to directly form I' crystal from melt by monomer copolymerization |
| CN107254055A (en) * | 2017-06-20 | 2017-10-17 | 天津大学 | A kind of brilliant crystallization generation I method directly from isotactic poly- 1 butylene body |
| CN107254055B (en) * | 2017-06-20 | 2019-12-31 | 天津大学 | Method for directly crystallizing I crystal from isotactic poly-1-butene body |
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