CN114702720B - Polybutylene foam material, preparation method thereof, prefabricated product and application - Google Patents
Polybutylene foam material, preparation method thereof, prefabricated product and application Download PDFInfo
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- CN114702720B CN114702720B CN202210370127.7A CN202210370127A CN114702720B CN 114702720 B CN114702720 B CN 114702720B CN 202210370127 A CN202210370127 A CN 202210370127A CN 114702720 B CN114702720 B CN 114702720B
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08J2203/06—CO2, N2 or noble gases
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/048—Bimodal pore distribution, e.g. micropores and nanopores coexisting in the same foam
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract
The invention discloses a polybutylene foam material, a preparation method thereof, a prefabricated product and application. The preparation method comprises the following steps: (1) Annealing polybutylene resin to obtain a preform; the annealing treatment mode comprises supercritical CO 2 Annealing treatment or normal temperature and normal pressure annealing treatment; supercritical CO 2 The annealing treatment comprises the following steps: in supercritical CO 2 In the presence of the resin, carrying out heat preservation and pressure maintaining on the polybutylene resin, and relieving pressure to obtain the polybutylene resin; the pressure relief rate is 0.1-1 MPa/min; the normal temperature and pressure annealing treatment comprises the following steps: melting polybutene resin, and cooling at normal temperature and pressure to obtain the final product; (2) In supercritical CO 2 In the presence of (2), performing heat preservation and pressure maintaining on the prefabricated product, and relieving pressure to obtain the finished product; wherein the pressure relief rate is 5-300 MPa/s. The polybutene foaming material prepared by the preparation method disclosed by the invention has a controllable bimodal cell structure size, and the application of the polybutene foaming material in the fields of heat insulation, sound absorption and the like is widened.
Description
Technical Field
The invention relates to the technical field of polymer foam materials, in particular to a polybutylene foam material, a preparation method thereof, a prefabricated product and application thereof.
Background
The polymer foam material is widely applied to the fields of packaging, construction, heat insulation, sound absorption, tissue support, oil absorption and the like due to the porous structure, light weight, good impact toughness, heat insulation, sound absorption and the like. Compared with a foaming material with a unimodal cell structure, the polymer micro-foaming material with the bimodal cell structure can provide good mechanical property, heat insulation property and the like due to small cells, and apparent density of the material can be reduced due to large cells, so that more excellent performance is shown.
At present, the main methods for preparing foams having bimodal cell structures are a two-step batch foaming method and a dual-blowing agent continuous extrusion foaming method. Patent CN105385024a discloses a method for preparing polypropylene foam with bimodal distribution and a preparation method thereof, which prepares foam with bimodal cell structure by adding porous inorganic particles. CN105419093A discloses a foam material containing a bimodal cell structure and a preparation method thereof, and is characterized in that a continuous extrusion foaming method is adopted, two or more polymers and monoglyceride are blended, and supercritical CO is adopted to prepare the foam material 2 Foaming produces a foam having a bimodal cell structure.
As a precious C4 resource product, the utilization rate of the polybutene in China is low, and the polybutene has good physical and mechanical properties, outstanding creep resistance, chemical resistance, low temperature resistance, environmental stress cracking resistance, good mechanical strength and high toughness. The polybutene foaming material has a double-peak cell structure, expands the application field of polybutene, improves the utilization rate of the polybutene, and has good practical significance for promoting the development of polybutene industry in China.
Disclosure of Invention
The invention provides a polybutene foaming material, a preparation method thereof, a prefabricated product and application, and aims to obtain the polybutene foaming material with a bimodal cell structure. The polybutene foaming material prepared by the preparation method disclosed by the invention has a controllable bimodal cell structure size, and the application of the polybutene foaming material in the fields of heat insulation, sound absorption and the like is widened.
The invention solves the technical problems through the following technical scheme.
The invention provides a preparation method of a polybutylene foam material, which comprises the following steps:
(1) Annealing polybutene resin microparticles to obtain a preform;
the annealing treatment mode comprises supercritical CO 2 Annealing treatment or normal temperature and normal pressure annealing treatment;
when the annealing treatment mode is supercritical CO 2 During annealing treatment, the supercritical CO 2 The annealing treatment comprises the following steps: in supercritical CO 2 In the presence of the resin, carrying out heat preservation and pressure maintaining on the polybutylene resin particles, and relieving pressure to obtain the polybutylene resin particles;
wherein the temperature of the heat preservation and pressure maintaining is 80-140 ℃, and the pressure of the heat preservation and pressure maintaining is 5-20 MPa;
when the sizes of the polybutylene resin particles are that a is less than or equal to 5mm, b is less than or equal to 5mm, and c is less than or equal to 5mm, the heat preservation and pressure maintaining time is 5-85 min; wherein a, b and c represent the maximum sizes of the polybutylene resin particles in the X-axis direction, the Y-axis direction and the Z-axis direction in a coordinate system;
the pressure relief rate is 0.1-1 MPa/min;
when the annealing treatment mode is normal-temperature normal-pressure annealing treatment, the normal-temperature normal-pressure annealing treatment comprises the following steps: fusing polybutylene resin particles, and cooling at normal temperature and normal pressure to obtain the polybutylene resin particles;
(2) Foaming: in supercritical CO 2 In the presence of the pressure relief agent, performing heat preservation and pressure maintaining on the prefabricated product, and performing pressure relief to obtain the pressure relief agent; wherein the pressure relief rate is 5-300 MPa/s.
In step (1) of the present invention, the polybutene-based resin may be one or more of isotactic polybutene, syndiotactic polybutene and polybutene alloy.
Wherein the polybutene alloy is a 1-butene/propylene copolymer, and the molecular weight distribution of the 1-butene/propylene copolymer is preferably Mw/Mn = 1-10; preferably, the 1-butene/propylene copolymer has a 1-butene molar content of 70-99% and a propylene molar content of 1-30%.
In the step (1) of the present invention, the isotactic degree of the polybutene-based resin may be 50 to 99%, for example, 95%. The crystallinity of the polybutene-based resin may be 20 to 60%, for example, 45%. The polybutene-based resin may have a melt index of 0.1g to 5g/10min, for example 0.5g/10min.
In step (1) of the present invention, the polybutene-based resin fine particles may have a single crystal form or two crystal forms.
And/or, the polybutylene-based resin particle may be in the form of a pellet or a sheet.
It was found that when the melt index is too small, the matrix is poor in fluidity and difficult to foam, and when the melt index exceeds 5g/10min, high fluidity is exhibited and the cell breakage is caused by the decrease in melt strength.
In the invention, when the annealing treatment mode is supercritical CO 2 During annealing treatment, the sizes of the polybutene resin particles are a is not more than 50mm, b is not more than 50mm, c is not more than 30mm, and the heat preservation and pressure maintaining time of the polybutene resin particles is 5-150 min.
Preferably, the size of the polybutylene resin particles is more than or equal to 5mm and less than or equal to 30mm, more than or equal to 2mm and less than or equal to 30mm, and the heat preservation and pressure maintaining time of the polybutylene resin particles is 20-140 min.
Preferably, the size of the polybutene-based resin particles is 10mm < a > 20mm,10mm < b > 20mm, and 5mm < c > 20mm, and the heat preservation and pressure maintaining time of the polybutene-based resin particles is 40-120 min.
Preferably, the sizes of the polybutylene resin particles are 1 mm-4 mm, 1mm-4 mm and 1mm-4 mm, and the heat preservation and pressure maintaining time of the polybutylene resin particles is 10-80 min.
Preferably, the size of the polybutylene resin particles is a =2mm, b =2mm, c =2mm, and the heat and pressure retention time of the polybutylene resin particles is 20min to 60min, such as 30min, 40min or 50min.
In step (1) of the present invention, the temperature of the heat-preserving and pressure-maintaining may be 90 ℃ to 120 ℃, for example, 100 ℃, 105 ℃, 110 ℃ or 115 ℃.
In step (1) of the present invention, the pressure of the heat-preserving and pressure-maintaining may be 6MPa to 18MPa, for example, 10MPa or 15MPa.
In step (1) of the present invention, the supercritical CO 2 During the annealing process, slow pressure relief is generally performed. The rate of pressure release is preferably 0.3MPa/min. The slow venting was performed to ensure that the sample did not foam during the annealing process.
In the present invention, the supercritical CO 2 It means CO corresponding to a state where the temperature and pressure are at or above a critical temperature (31.1 ℃) and a critical pressure (7.37 MPa) 2 A fluid.
In step (1) of the present invention, the supercritical CO 2 The annealing treatment is generally carried out in an autoclave.
In step (1) of the present invention, when the annealing treatment is normal temperature and pressure annealing treatment, the time for cooling may be 1h to 168h, preferably 2h to 72h, for example 24h.
In the invention, the normal temperature and the normal pressure are 20-25 ℃ and 101Kpa.
In the step (1) of the present invention, when the annealing treatment mode is normal temperature and pressure annealing treatment, the melting mode may be hot-press melting or melt extrusion. Wherein, the melt extrusion is generally carried out by a twin-screw extruder.
In the research process of the inventor, the annealing treatment on the polybutylene resin particles can enable two different crystal forms to be formed in the polybutylene resin. Because different crystal forms show different melt strengths at the same temperature, crystal regions of the first crystal form are basically molten, and thus, the diameter of a cell is larger; the existence of a large number of crystal regions of the second crystal form limits the growth of cells, so that the diameters of the cells are smaller, and the difference of the pore diameters of the cells in different crystal forms enables the foaming material to have a bimodal cell structure. The polybutene resin with two crystal forms in different proportion can be obtained by adjusting the annealing condition, so that the foaming material with different bimodal distribution can be prepared after intermittent physical foaming.
In the step (1), when supercritical CO is adopted 2 During the annealing treatment, supercritical CO is used 2 With polybutenesThe interaction of the alkene resin particles leads the polybutylene resin particles to be partially melted, and the polybutylene resin particles can form two different crystal forms. And obtaining prefabricated products with different crystal form proportions according to different annealing times.
In the step (1), when normal-temperature normal-pressure annealing treatment is adopted, an unstable third crystal form is generated after the polybutene resin is melted, the third crystal form is spontaneously converted into the second crystal form in the normal-temperature normal-pressure cooling process, and a preform with two different crystal forms is obtained by controlling the room-temperature annealing time to regulate the conversion ratio of the crystal forms, so that the polybutene foaming material with the bimodal cell structure is prepared.
In step (2) of the present invention, the pressure for maintaining the temperature and pressure may be 5MPa to 20MPa, preferably 7MPa to 18MPa, for example 10MPa.
In the step (2), the time for heat preservation and pressure maintaining can be 10-60 min; preferably 20min to 50min, for example 40min.
In step (2) of the present invention, the temperature of the heat preservation and pressure maintaining may be 90 ℃ to 115 ℃, preferably 100 ℃ to 110 ℃, for example 105 ℃.
In step (2) of the present invention, the pressure release rate is preferably 10 to 200MPa/s, for example, 100MPa/s.
In step (2) of the present invention, the expansion ratio of the foaming may be 6 to 32, preferably 10 to 28, for example, 12.1, 15.3, 20.8, 27.6 or 27.7.
In step (2) of the present invention, the foaming is generally carried out in an autoclave.
The invention also provides a prefabricated product of the polybutylene foaming material, which is prepared by the step (1) of the preparation method of the polybutylene foaming material.
The invention also provides a polybutylene foam material prepared by the preparation method of the polybutylene foam material.
The invention also provides an application of the polybutylene foam material in the field of heat insulation or sound absorption.
The invention also provides a polybutylene foam material which has a double-peak cell structure and large cellsThe average diameter of the pores is 12-200 μm, and the average diameter of the small pores is 1.5-40 μm; the relative density of the nano-particles is 0.038g/cm 3 ～0.18g/cm 3 。
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
according to the preparation method, annealing treatment is carried out before foaming, the crystal structure in the prefabricated product of the polybutylene foam material is regulated, so that the polybutylene foam material with the size-adjustable double-peak cell structure is prepared, and the application of the polybutylene foam material in the fields of heat insulation, sound absorption and the like is widened.
In addition, the preparation method can also reduce the foaming temperature of the polybutene, and two crystal forms reserved in the foaming material can reduce the secondary forming processing temperature, thereby laying a foundation for the forming processing of the polybutene foaming material.
Drawings
FIG. 1 is a scanning electron microscope image of the foamed polybutene material prepared in example 1.
FIG. 2 is a scanning electron microscope image of the foamed polybutylene material prepared in example 2.
FIG. 3 is a scanning electron microscope image of the foamed polybutene material prepared in example 3.
FIG. 4 is a scanning electron microscope image of the foamed polybutylene material obtained in example 4.
FIG. 5 is a scanning electron microscope image of the foamed polybutene material prepared in example 5.
FIG. 6 is a scanning electron micrograph of the polybutene foam obtained in example 6.
FIG. 7 is a scanning electron microscope image of the foamed polybutene material prepared in example 7.
FIG. 8 is a scanning electron microscope image of the polybutene foam prepared in comparative example 1.
FIG. 9 is a scanning electron microscope image of the polybutene foam prepared in comparative example 2.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the invention thereto. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The polybutene-based resin fine particles used in examples 1 to 7 of the present invention and comparative example 1 were isotactic polybutene fine particles for experiments, and the following conditions were satisfied: the crystal has a single crystal form, the isotacticity is 95%, the crystallinity is 50%, and the melt index is 0.5g/10min; the dimensions are a =2mm, b =2mm, c =2mm.
The polybutylene resin particles used in comparative example 2 of the present invention are polybutylene alloy particles, specifically: the molar content of the butene is 90 percent; the mol content of the propylene is 10 percent, the isotacticity is 95 percent, the crystallinity is 48 percent, and the melt index is 0.2g/10min; the dimensions are a =2mm, b =2mm, c =2mm.
Example 1
(1) Putting experimental isotactic polybutene particles into an autoclave, and using CO with the pressure less than 1MPa 2 Purging the autoclave to remove air and moisture in the autoclave; then the temperature of the autoclave is raised to 115 ℃, and then supercritical CO is filled in the autoclave 2 Raising the pressure to 15MPa, keeping the temperature and the pressure for 10min after the temperature and the pressure are reached, partially melting the isotactic polybutylene particles, and slowly releasing the pressure at the speed of 0.3MPa/min to obtain a prefabricated product 1 with two crystal forms;
(2) Raising the temperature of the high-pressure kettle to 90 ℃ again, maintaining the pressure of the high-pressure kettle at 10MPa, and keeping the temperature and the pressure for 40min; and (3) carrying out controllable pressure relief on the high-pressure kettle at the pressure relief rate of 100MPa/s, then placing the high-pressure kettle in a water bath for cooling, and taking out the polybutylene foaming material after cooling is finished, wherein the foaming ratio is between 5 and 10.
Example 2
(1) Putting experimental isotactic polybutene particles into an autoclave, and using CO with the pressure less than 1MPa 2 Purging the autoclave to remove air and moisture in the autoclave; then the temperature of the autoclave is raised to 110 ℃, the pressure is raised to 15MPa, and after the temperature and the pressure are reached, the temperature and the pressure are kept for 20min, so that the isotactic polybutene particles are obtainedPartially melting, and slowly releasing pressure at the speed of 0.3MPa/min to obtain a prefabricated product 1;
(2) Raising the temperature of the high-pressure kettle to 103 ℃ again, maintaining the pressure of the high-pressure kettle at 10MPa, and keeping the temperature and the pressure for 40min; the autoclave is decompressed controllably, and the decompression rate is 100MPa/s. And then placing the autoclave in a water bath for cooling, and taking out the polybutylene foaming material after cooling is finished, wherein the foaming ratio is between 15 and 25.
Example 3
(1) Putting experimental isotactic polybutene particles into an autoclave, and using CO with the pressure less than 1MPa 2 Purging the autoclave to remove air and moisture in the autoclave; then, the temperature of the high-pressure kettle is raised to 110 ℃, the pressure is raised to 15MPa, after the temperature and the pressure are reached, the temperature and the pressure are kept for 30min, the isotactic polybutene particles are partially melted, and the pressure is slowly released at the speed of 0.3MPa/min, so that a prefabricated product 1 is obtained;
(2) Raising the temperature of the high-pressure kettle to 109 ℃ again, maintaining the pressure of the high-pressure kettle at 10MPa, and keeping the temperature and the pressure for 40min; the autoclave is decompressed controllably, and the decompression speed is 100MPa/s. And then placing the high-pressure autoclave in a water bath for cooling, and taking out the polybutylene foaming material after cooling is finished, wherein the foaming ratio is between 30 and 35.
Example 4
(1) Putting experimental isotactic polybutene particles into an autoclave, and using CO with the pressure less than 1MPa 2 Purging the autoclave to remove air and moisture in the autoclave; then, the temperature of the high-pressure kettle is raised to 110 ℃, the pressure is raised to 15MPa, after the temperature and the pressure are reached, the temperature and the pressure are kept for 40min, the isotactic polybutylene particles are partially melted, and the pressure is slowly released at the speed of 0.3MPa/min, so that a prefabricated product 1 is obtained;
(2) Raising the temperature of the high-pressure kettle to 100 ℃ again, maintaining the pressure of the high-pressure kettle at 10MPa, and keeping the temperature and the pressure for 40min; the autoclave is decompressed controllably, and the decompression rate is 100MPa/s. And then placing the autoclave in a water bath for cooling, and taking out the polybutylene foaming material after cooling, wherein the foaming ratio is between 10 and 15.
Example 5
(1) Putting experimental isotactic polybutene particles into an autoclave, and using CO with the pressure less than 1MPa 2 Purging the autoclave to remove air and moisture in the autoclave; then, the temperature of the high-pressure kettle is raised to 110 ℃, the pressure is raised to 15MPa, after the temperature and the pressure are reached, the temperature and the pressure are kept for 50min, the isotactic polybutylene particles are partially melted, and the pressure is slowly released at the speed of 0.3MPa/min, so that a prefabricated product 1 is obtained;
(2) Raising the temperature of the high-pressure kettle to 109 ℃ again, maintaining the pressure of the high-pressure kettle at 10MPa, and keeping the temperature and the pressure for 60min; the autoclave is decompressed controllably, and the decompression rate is 100MPa/s. And then placing the high-pressure kettle in a water bath for cooling, and taking out the polybutylene foaming material after cooling is finished, wherein the foaming ratio is 25-30.
Example 6
(1) Placing the isotactic polybutylene particles for experiments in a double-screw extruder for melt extrusion to obtain polybutylene resin materials with a =5mm, b =5mm and c =2mm, and annealing at normal temperature and pressure for 24h to obtain a preform 2;
(2) The above samples were placed in an autoclave using CO at a pressure of less than 1MPa 2 Purging the autoclave for three times to remove air and moisture in the autoclave; and then raising the temperature of the high-pressure kettle to 100 ℃, raising the pressure to 15MPa, keeping the temperature and the pressure for 40min, relieving the pressure of the high-pressure kettle at the pressure relief rate of 100MPa/s, then placing the high-pressure kettle in a water bath for cooling, and taking out the polybutylene foaming material after cooling, wherein the foaming ratio is between 5 and 10.
Example 7
(1) Placing the isotactic polybutylene particles for experiments in a double-screw extruder for melt extrusion to obtain polybutylene resin materials with a =5mm, b =5mm and c =2mm, and annealing at normal temperature and pressure for 2h to obtain a preform 2;
(2) The above samples were placed in an autoclave using CO at a pressure of less than 1MPa 2 Purging the autoclave for three times to remove air and moisture in the autoclave; and then raising the temperature of the high-pressure kettle to 105 ℃, raising the pressure to 12.5MPa, keeping for 40min, then relieving the pressure of the high-pressure kettle at the pressure relief rate of 100MPa/s, then placing the high-pressure kettle in a water bath for cooling, and taking out the polybutylene foaming material after cooling, wherein the foaming ratio is 25-30.
Comparative example 1
Putting experimental isotactic polybutene particles into an autoclave, and using CO with the pressure less than 1MPa 2 Purging the autoclave to remove air and moisture in the autoclave; then raising the temperature of the autoclave to 110 ℃, raising the pressure to 15MPa, and keeping for 40min after the temperature and the pressure are reached to enable CO to be in contact with the atmosphere 2 Permeating into isotactic polybutene particle; after the pressure maintaining time is over, the pressure of the high-pressure kettle is controllably released, and the pressure releasing speed is 100MPa/s. And then placing the autoclave in a water bath for cooling, and taking out the polybutylene foaming material after cooling, wherein the foaming ratio is between 15 and 20.
Comparative example 2
(1) Putting polybutene alloy particles into an autoclave, and using CO with the pressure less than 1MPa 2 Purging the autoclave to remove air and moisture in the autoclave; then raising the temperature of the high-pressure kettle to 115 ℃, raising the pressure to 15MPa, keeping for 90min after the temperature and the pressure are reached, completely melting the polybutene alloy particles, and relieving the pressure at the rate of 0.3MPa/min to obtain a prefabricated product with a single crystal form;
(2) And raising the temperature of the high-pressure kettle to 97 ℃ again, raising the pressure to 10MPa, keeping for 40min after the temperature and the pressure are reached, and taking out the polybutylene foaming material after cooling is finished, wherein the foaming ratio is 25-30.
Effects of the embodiment
The polybutene foaming materials obtained in examples 1 to 7 and comparative examples 1 to 2 were electronically scanned by JSM-6360LV scanning electron microscope, and the scanning electron microscope images are shown in FIGS. 1 to 9. The cell size and cell structure of the polybutene foam were obtained from scanning electron micrographs, and the foaming ratio was obtained by Archimedes drainage method using ASTM D792-00, and the results are shown in Table 1.
TABLE 1
As can be seen from fig. 1 to 7 and fig. 8 to 9 and the data in the above table, the preparation method of the present invention can prepare the polybutene foam material having a bimodal cell structure with adjustable size by adjusting the annealing time.
Claims (19)
1. The preparation method of the polybutylene foam material is characterized by comprising the following steps:
(1) Annealing polybutene resin microparticles to obtain a preform;
the annealing treatment mode comprises supercritical CO 2 Annealing treatment or normal temperature and normal pressure annealing treatment;
when the annealing treatment mode is supercritical CO 2 During annealing treatment, the supercritical CO 2 The annealing treatment comprises the following steps: in supercritical CO 2 In the presence of the resin, carrying out heat preservation and pressure maintaining on the polybutylene resin particles to partially melt the polybutylene resin particles, and relieving pressure to obtain the polybutylene resin particles;
wherein the temperature for heat preservation and pressure maintaining is 80-140 ℃, and the pressure for heat preservation and pressure maintaining is 5 MPa-20MPa;
when the sizes of the polybutylene resin particles are that a is less than or equal to 5mm, b is less than or equal to 5mm, and c is less than or equal to 5mm, the heat preservation and pressure maintaining time is 5min to 85min; wherein a, b and c represent the maximum sizes of the polybutylene resin particles in the X-axis direction, the Y-axis direction and the Z-axis direction in a coordinate system;
the pressure relief rate is 0.1 to 1MPa/min;
when the annealing treatment mode is normal-temperature normal-pressure annealing treatment, the normal-temperature normal-pressure annealing treatment comprises the following steps: fusing polybutylene resin particles, and cooling at normal temperature and normal pressure to obtain the polybutylene resin particles;
(2) Foaming: in supercritical CO 2 In the presence of the pressure relief agent, performing heat preservation and pressure maintaining on the prefabricated product, and performing pressure relief to obtain the pressure relief agent; wherein the pressure of the heat preservation and pressure maintaining is 5MPa to 20MPa, the time of the heat preservation and pressure maintaining is 10min to 60min, the temperature of the heat preservation and pressure maintaining is 90 ℃ to 115 ℃, and the pressure relief rate is 5 to 300MPa/s.
2. The method for preparing polybutene foam according to claim 1, wherein in the step (1), the polybutene-based resin is one or more of isotactic polybutene, syndiotactic polybutene and polybutene alloy;
and/or the isotacticity of the polybutylene resin is 50 to 99 percent;
and/or the crystallinity of the polybutylene resin is 20 to 60 percent;
and/or the polybutylene resin has a melt index of 0.1g to 5g/10min;
and/or the polybutylene resin particle has a single crystal form or two crystal forms;
and/or the polybutylene resin particles are in the shape of granules or sheets.
3. The method for preparing polybutene foam according to claim 2, wherein the polybutene alloy is 1-butene/propylene copolymer;
and/or the isotacticity of the polybutene resin is 95%;
and/or the crystallinity of the polybutylene resin is 45%;
and/or the melt index of the polybutene resin is 0.5g/10min.
4. The method for producing polybutene foam according to claim 3, wherein the molecular weight distribution of the 1-butene/propylene copolymer is Mw/Mn =1 to 10.
5. The method for preparing polybutene foam according to claim 3 wherein the 1-butene/propylene copolymer has a 1-butene molar content of 70 to 99% and a propylene molar content of 1 to 30%.
6. The method for preparing polybutene foam according to claim 1 wherein in the step (1), when the annealing treatment is performed by supercritical CO 2 During annealing treatment, the sizes of the polybutylene resin particles are 1 mm-4 mm, 4m, 1 mm-4 m, cm, and the heat preservation and pressure maintaining time of the polybutylene resin particles is 10min to 80min.
7. The method of producing polybutene foam according to claim 1, wherein the size of the polybutene resin fine particles is a =2mm, b =2mm, c =2mm, and the heat and pressure retention time of the polybutene resin fine particles is from 20min to 60min.
8. The method of producing polybutene foam according to claim 1, wherein the size of the polybutene resin fine particles is a =2mm, b =2mm, c =2mm, and the heat and pressure retention time of the polybutene resin fine particles is 30min, 40min or 50min.
9. The method for preparing polybutene foam material as claimed in claim 1, wherein in the step (1), the temperature for maintaining the temperature and pressure is 90 ℃ to 120 ℃;
and/or in the step (1), the pressure for heat preservation and pressure maintaining is 6MPa to 18MPa;
and/or in the step (1), the pressure relief rate is 0.2 to 0.8MPa/min.
10. The method for preparing polybutene foam according to claim 1 wherein in the step (1), the temperature for keeping the temperature and pressure is 100 ℃, 105 ℃, 110 ℃ or 115 ℃;
and/or in the step (1), the pressure of heat preservation and pressure maintaining is 10MPa or 15MPa;
and/or in the step (1), the pressure relief rate is 0.3MPa/min.
11. The method for preparing polybutene foam according to claim 1, wherein when the annealing is performed at normal temperature and pressure, the cooling time in step (1) is 1h to 168h.
12. The method for preparing the polybutylene foam material according to claim 1, wherein when the annealing treatment is normal-temperature normal-pressure annealing treatment, the cooling time in the step (1) is 2h to 72h.
13. The method for preparing polybutene foam according to claim 1 wherein when the annealing is performed at normal temperature and pressure, the cooling time in step (1) is 24 hours.
14. The method for producing polybutene foam according to claim 1, wherein in the step (2), the pressure for keeping the temperature and pressure is 7MPa to 18MPa;
and/or in the step (2), keeping the temperature and the pressure for 20min to 50min;
and/or in the step (2), the temperature for heat preservation and pressure maintaining is 100-110 ℃;
and/or in the step (2), the pressure relief rate is 10 to 200MPa/s;
and/or in the step (2), the foaming multiplying power of the foaming is 6 to 32.
15. The method for preparing polybutene foam according to claim 1 wherein the pressure for holding the temperature and pressure is 10MPa;
and/or in the step (2), the heat preservation and pressure maintaining time is 40min;
and/or in the step (2), the temperature for heat preservation and pressure maintaining is 105 ℃;
and/or in the step (2), the pressure relief rate is 100 MPa/s;
and/or in the step (2), the foaming multiplying power of the foaming is 10 to 28.
16. The method for producing polybutene foam according to claim 1 wherein in the step (2), the expansion ratio of the foaming is 12.1, 15.3, 20.8, 27.6 or 27.7.
17. A polybutylene foam characterized by being produced by the method for producing a polybutylene foam according to any one of claims 1 to 16.
18. The polybutene foam according to claim 17 having a bimodal cell structure, wherein the large cells have an average diameter of 12 μm to 200 μm, and the small cells have an average diameter of 1.5 μm to 40 μm; the relative density of the nano-particles is 0.038g/cm 3 ~0.18 g/cm 3 。
19. Use of a polybutene foam according to claim 17 or 18 in the field of thermal insulation or sound absorption.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1219645A1 (en) * | 2000-12-26 | 2002-07-03 | Mitsui Chemicals, Inc. | Polybutene resin and pipe material and pipe comprising the same |
| CN101113201A (en) * | 2007-07-12 | 2008-01-30 | 华东理工大学 | Method for controlling conversion of isotactic polybutylene-1 crystal system two to crystal system one by carbon dioxide |
| CN103240884A (en) * | 2013-05-07 | 2013-08-14 | 西北工业大学 | Preparation method of polycarbonate microporous material with bimodal distribution |
| CN105670137A (en) * | 2016-02-06 | 2016-06-15 | 北京化工大学 | Polybutylene foam material and preparing method thereof |
| CN110183713A (en) * | 2019-06-25 | 2019-08-30 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of polybutene expanded bead (EPB) |
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- 2022-04-08 CN CN202210370127.7A patent/CN114702720B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1219645A1 (en) * | 2000-12-26 | 2002-07-03 | Mitsui Chemicals, Inc. | Polybutene resin and pipe material and pipe comprising the same |
| CN101113201A (en) * | 2007-07-12 | 2008-01-30 | 华东理工大学 | Method for controlling conversion of isotactic polybutylene-1 crystal system two to crystal system one by carbon dioxide |
| CN103240884A (en) * | 2013-05-07 | 2013-08-14 | 西北工业大学 | Preparation method of polycarbonate microporous material with bimodal distribution |
| CN105670137A (en) * | 2016-02-06 | 2016-06-15 | 北京化工大学 | Polybutylene foam material and preparing method thereof |
| CN110183713A (en) * | 2019-06-25 | 2019-08-30 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of polybutene expanded bead (EPB) |
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