CN114395161B - Foamable thermoplastic polyurethane elastomer and preparation method and application thereof - Google Patents
Foamable thermoplastic polyurethane elastomer and preparation method and application thereof Download PDFInfo
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- CN114395161B CN114395161B CN202210077383.7A CN202210077383A CN114395161B CN 114395161 B CN114395161 B CN 114395161B CN 202210077383 A CN202210077383 A CN 202210077383A CN 114395161 B CN114395161 B CN 114395161B
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- 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
- C08J9/14—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 organic
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Abstract
The invention discloses a foamable thermoplastic polyurethane elastomer and a preparation method and application thereof. The preparation method comprises the following steps: (1) Adding a thermoplastic polyurethane elastomer with a crystallization temperature of not less than 70 ℃ and a Shore hardness of 70A-85D and a foaming agent into a first-stage double-screw extruder according to a mass ratio of 0.1-10, and melting and mixing; the foaming agent is one or a mixture of more of butane, isobutane, pentane, pentafluoropropane and acetone; (2) Feeding the material extruded by the double-screw extruder in the step (1) into a second-stage single-screw extruder for cooling treatment, extruding the material through a die head, and carrying out underwater pelletizing to obtain a foamable thermoplastic polyurethane elastomer; the water pressure of underwater pelletizing is 5-30bar. The foamable thermoplastic polyurethane elastomer has good foamability and mouldable fusion molding performance and high stability.
Description
Technical Field
The invention relates to the field of thermoplastic polyurethane elastomers, in particular to a foamable thermoplastic polyurethane elastomer and a preparation method and application thereof.
Background
The thermoplastic polyurethane elastomer (TPU) not only has a wider hardness range, but also has the advantages of excellent wear resistance, mechanical strength, water resistance, oil resistance, chemical corrosion resistance, mildew resistance, environmental friendliness, recyclability and the like. And filling a large number of bubbles into the TPU beads by using the TPU resin beads as a matrix through an extrusion foaming granulation or autoclave foaming method to obtain the foamed TPU beads. The foamed TPU bead molded product has a series of advantages of low density, heat and sound insulation, high specific strength, high elasticity, buffering and the like, so the foamed TPU bead molded product is widely applied to the fields of packaging industry, agriculture, transportation industry, military industry, aerospace industry, daily necessities and the like.
Chinese patent CN104364304B discloses a method for preparing expanded particles from a thermoplastic polyurethane melt containing a foaming agent, which is to extrude and cut the thermoplastic polyurethane melt containing supercritical carbon dioxide and/or nitrogen through a hole plate to prepare expanded thermoplastic polyurethane beads, wherein the bulk density of the expanded particles is 30-250g/L.
Chinese patent CN107383854B discloses a preparation method of a thermoplastic polyurethane micro-airbag elastomer material, which comprises the steps of preparing a thermoplastic polyurethane melt by adopting liquid raw material polymerization reaction, adding a polymer auxiliary material with low molecular weight, a foaming agent and a nucleating agent into the thermoplastic polyurethane melt, finally extruding and granulating, and realizing step-by-step pressure reduction by adjusting the water pressure of the granulated water, thereby preparing the thermoplastic polyurethane micro-airbag elastomer material with a certain open pore structure.
Chinese patent CN109501030B discloses a foaming thermoplastic elastomer and a preparation method and a device thereof, which are characterized in that supercritical CO is firstly extruded by a first-stage extruder 2 、N 2 And inert gas are added into the thermoplastic polyurethane melt, and then CO is continuously added into the second-stage extruder 2 And N 2 Finally, the foamed thermoplastic elastomer beads with the bulk density of 60-300g/L are prepared by extrusion through a die head.
Disclosure of Invention
The invention provides a preparation method of a foamable thermoplastic polyurethane elastomer, and the foamable thermoplastic polyurethane elastomer prepared by the method has excellent foamable performance and moldability and welding molding performance. The foaming thermoplastic polyurethane elastomer prepared by the invention compresses the foaming agent in the foaming thermoplastic polyurethane elastomer, has high stability, can keep the internal foaming agent stably existing for a long time without escaping, has large bulk density, small volume and small occupied area, is suitable for storage and transportation, and greatly saves the transportation and storage cost compared with foaming thermoplastic polyurethane beads.
A method for preparing a foamable thermoplastic polyurethane elastomer, comprising the steps of:
(1) Adding a thermoplastic polyurethane elastomer with a crystallization temperature of not less than 70 ℃ and a Shore hardness of 70A-85D (preferably 80A-85D) and a foaming agent into a first-stage double-screw extruder according to a mass ratio of 100.1-10 for melt mixing;
the foaming agent is one or a mixture of more of butane, isobutane, pentane, pentafluoropropane and acetone;
(2) Feeding the material extruded by the double-screw extruder in the step (1) into a second-stage single-screw extruder for cooling treatment, extruding the material through a die head, and carrying out underwater pelletizing to obtain a foamable thermoplastic polyurethane elastomer; the water pressure of the underwater pelletizing is 5-30bar, preferably 10-30bar, and more preferably 15-30bar.
In order to prepare the foamable thermoplastic polyurethane elastomer meeting the requirements of the invention, the preparation method of the invention is mainly comprehensively and cooperatively controlled through the following aspects:
1) Controlling the crystallization temperature and the Shore hardness of the raw material of the thermoplastic polyurethane elastomer to ensure that the thermoplastic polyurethane elastomer has enough capacity to compress a foaming agent in the thermoplastic polyurethane elastomer;
2) Controlling the proportion of the foaming agent in the thermoplastic polyurethane elastomer;
3) The variety of the foaming agent is controlled, the foaming agents such as supercritical carbon dioxide and the like are easy to escape, and the long-acting stable foamable thermoplastic polyurethane elastomer is difficult to prepare;
4) A two-stage extrusion process of a double-screw extruder and a single-screw extruder is adopted, and the single-screw extruder is used for fully cooling materials;
5) The water pressure in the underwater pelletizing process is controlled to ensure that the foaming agent can be well compressed in the thermoplastic polyurethane elastomer.
In the present invention, the crystallization temperature of the thermoplastic polyurethane elastomer can be obtained by Differential Scanning Calorimetry (DSC) test, for example, by means of a model DSC 1 manufactured by METTLER corporation, using STARe software for data analysis, more specifically: heating 5-10mg of thermoplastic polyurethane elastomer beads from-90 ℃ to 250 ℃ at a heating rate of 20 ℃/min, keeping the temperature for 2 minutes, then cooling from 250 ℃ to-90 ℃ at a speed of 10 ℃/min, finally heating from-90 ℃ to 250 ℃ at a speed of 20 ℃/min, and taking the DSC enthalpy absorption peak-to-peak temperature in the cooling process as the crystallization temperature of the thermoplastic polyurethane elastomer beads.
In the present invention, the Shore hardness of the thermoplastic polyurethane elastomer may be according to ASTM D2240-15el.
In a preferable example, in the preparation method of the foamable thermoplastic polyurethane elastomer, in the step (1), the thermoplastic polyurethane elastomer is added at a main feed inlet of the twin-screw extruder, and the foaming agent is added at a position 2/3 of the screw length away from the main feed inlet of the twin-screw extruder.
In the preparation method of the foamable thermoplastic polyurethane elastomer, in the step (1), a nucleating agent can be added from the main feed inlet of the double-screw extruder.
The mass ratio of the nucleating agent to the thermoplastic polyurethane elastomer is preferably 0.1 to 1.
The nucleating agent is preferably one or a mixture of more of talcum powder, silicon dioxide, calcium carbonate, titanium dioxide, zinc oxide, calcium oxide, montmorillonite, sodium benzoate and diatomite.
In a preferred example, in the preparation method of the foamable thermoplastic polyurethane elastomer, in the step (2), the water temperature of the underwater cutting is 0-90 ℃.
The invention also provides the foamable thermoplastic polyurethane elastomer prepared by the preparation method.
In a preferred embodiment, the particle size of the foamable thermoplastic polyurethane elastomer is 0.5-6mm.
In a preferred embodiment, the density of the foamable thermoplastic polyurethane elastomer is 0.7 to 1.3g/cm 3 。
As a general inventive concept, the present invention also provides a method of preparing expanded thermoplastic polyurethane elastomer beads, comprising: and (3) foaming the foamable thermoplastic polyurethane elastomer on a reaction kettle or a fluidized bed by using steam, hot air or microwave radiation to obtain foamed thermoplastic polyurethane elastomer beads.
The invention also provides the foamed thermoplastic polyurethane elastomer bead prepared by the method.
The present invention also provides a process for preparing a thermoplastic polyurethane foam article comprising: and (3) foaming and welding the foamable thermoplastic polyurethane elastomer or the foamed thermoplastic polyurethane elastomer beads in a mould by using steam or microwave radiation to obtain a thermoplastic polyurethane foam product.
The invention also provides a thermoplastic polyurethane foam product prepared by the method.
The invention also provides the use of said thermoplastic polyurethane foam articles as shoe soles, tires, bicycle seats, upholstery, cushioning, sound insulation mats, children's toys, ground coverings.
Compared with the prior art, the invention has the main advantages that:
1. the foamable thermoplastic polyurethane elastomer prepared by the invention has excellent foamable performance and weldable molding performance, can be used for preparing a thermoplastic polyurethane foam product after foaming, or directly preparing the thermoplastic polyurethane foam product in one step, and greatly saves the transportation and storage cost compared with foamed thermoplastic polyurethane elastomer beads.
2. The foamable thermoplastic polyurethane elastomer prepared by the invention has good storage stability, the elasticity of the thermoplastic polyurethane with high crystallization temperature has the capability of rapid shaping, and the soft and hard sections of the molecular weight chain section can realize rapid separation, so that the elastic crystal of the thermoplastic polyurethane is more compact, and the foaming agent in the prepared foamable thermoplastic polyurethane elastomer is difficult to escape.
3. The thermoplastic polyurethane foam products prepared from the foamable thermoplastic polyurethane elastomer of the present invention can be used as shoe soles, tires, bicycle seats, upholstery, cushioning, sound insulation mats, children's toys, and floor coverings.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
Thermoplastic polyurethane elastomer beads (selected from new Merrill Co., ltd., trade name) having a Shore hardness of 88A and a crystallization temperature of 90 deg.C
M88) and 2500-mesh talcum powder and butane are respectively added into a first-stage double-screw extruder according to 100kg/h, 0.3kg/h and 2kg/h for melt mixing, wherein thermoplastic polyurethane elastomer beads and talcum powder are measured by a weightless scale, the butane is added at a position 2/3 of the length of a screw from a main feeding port of the double-screw extruder, a flow meter is used for measuring the plasticizing area temperature of the double-screw extruder to be 180-200 ℃, the conveying section temperature is set to be 140-160 ℃, then the materials are conveyed into a second-stage single-screw extruder through a connector for cooling treatment, the temperature of the single-screw extruder is set to be 150 ℃, finally the materials are extruded through a die head and cut into granules under water, the water pressure is controlled to be 15bar by a high-pressure water pump, the water temperature is 30 ℃, and the density is 1.1g/cm 3 The expandable thermoplastic polyurethane elastomer beads of (1).
Example 2
Thermoplastic polyurethane elastomer beads (selected from new Merrill Co., ltd., trade name) having a Shore hardness of 70A and a crystallization temperature of 75 deg.C
M70), 2000-mesh silicon dioxide and pentafluoropropane are added into a first-stage double-screw extruder according to 100kg/h, 0.1kg/h and 10kg/h respectively for melt mixing, wherein thermoplastic polyurethane elastomer beads and the silicon dioxide are measured by weight loss scale, and the pentafluoropropane is added from the main part of the double-screw extruderAdding a material port at a position 2/3 of the length of a screw, metering by a flowmeter, setting the temperature of a plasticizing area of a double-screw extruder to be 160-180 ℃, setting the temperature of a conveying section to be 120-140 ℃, then sending the material into a second-stage single-screw extruder through a connector for cooling treatment, setting the temperature of the single-screw extruder to be 135 ℃, finally extruding through a die head, carrying out underwater granulation, controlling the water pressure of granulation water to be 20bar and the water temperature to be 0 ℃ through a high-pressure water pump, and obtaining the material with the density of 1.02g/cm 3 The expandable thermoplastic polyurethane elastomer beads of (1).
Example 3
Thermoplastic polyurethane elastomer beads (selected from new Merrill Co., ltd., brand number) with Shore hardness of 55D and crystallization temperature of 118 deg.C
E155D), adding 2000-mesh diatomite and acetone into a first-stage double-screw extruder according to 100kg/h, 1kg/h and 0.1kg/h respectively for melting and mixing, wherein thermoplastic polyurethane elastomer beads and diatomite are measured by a weightlessness scale, the acetone is added at a position 2/3 screw length away from a main feed inlet of the double-screw extruder, the acetone is measured by a flowmeter, the temperature of a plasticizing area of the double-screw extruder is 190-210 ℃, the temperature of a conveying section is set to be 140-160 ℃, then the materials are conveyed into a second-stage single-screw extruder through a connector for cooling treatment, the temperature of the single-screw extruder is set to be 160 ℃, finally the materials are extruded through a die head and cut into granules under water, the water pressure of the cut granules is controlled to be 30bar by a high-pressure water pump, and the water temperature is 50 ℃, so that the density of 1.3g/cm is obtained 3 The expandable thermoplastic polyurethane elastomer beads of (1).
Example 4
Thermoplastic polyurethane elastomer beads (selected from new Merrill materials, inc., trade name) having a Shore hardness of 75D and a crystallization temperature of 133 deg.C
E175D), adding talcum powder and pentane of 5000 meshes into a first-stage double-screw extruder according to the proportion of 100kg/h, 0.2kg/h and 4kg/h respectively for melting and mixing, wherein the thermoplastic polyurethane elastomer beads and the talcum powder are measured by weight loss scales,adding pentane at a position 2/3 of the length of a screw from a main feed inlet of the double-screw extruder, metering by a flow meter, setting the temperature of a plasticizing area of the double-screw extruder to be 200-220 ℃ and the temperature of a conveying section to be 160-180 ℃, then sending the materials into a second-stage single-screw extruder through a connector for cooling treatment, setting the temperature of the single-screw extruder to be 170 ℃, finally extruding the materials through a die head, granulating the materials underwater, controlling the water pressure of granulating water to be 20bar and the water temperature to be 25 ℃ through a high-pressure water pump, and obtaining the product with the density of 1.15g/cm 3 The expandable thermoplastic polyurethane elastomer beads of (1).
Example 5
Thermoplastic polyurethane elastomer beads (selected from new Merrill materials Co., ltd., trade name) having a Shore hardness of 90A and a crystallization temperature of 95 deg.C
E190 100kg/h, 0.25kg/h and 6kg/h of talcum powder and acetone are respectively added into a first-stage double-screw extruder for melting and mixing, wherein thermoplastic polyurethane elastomer beads and talcum powder are measured by a weightless scale, the acetone is added at a position 2/3 of the length of a screw rod from a main feeding port of the double-screw extruder, the acetone is measured by a flow meter, the temperature of a plasticizing area of the double-screw extruder is 170-190 ℃, the temperature of a conveying section is set to be 140-150 ℃, then the materials are conveyed into a second-stage single-screw extruder through a connector for cooling treatment, the temperature of the single-screw extruder is set to be 145 ℃, finally the materials are extruded through a die head, underwater grain cutting is carried out, the water pressure of the grain cutting water pump is controlled to be 18bar, the water temperature is 15 ℃, and the density is 1.25g/cm 3 The expandable thermoplastic polyurethane elastomer beads of (1).
Comparative example 1
Thermoplastic polyurethane elastomer beads (selected from new Merrill materials Co., ltd., trade name) having a Shore hardness of 80A and a crystallization temperature of 58 deg.C
M80), 2500 mesh talc powder and butane were added to a first stage twin-screw extruder at 100 kg/hr, 0.3 kg/hr and 2 kg/hr, respectively, to melt-mix them, wherein the thermoplastic polyurethane elastomer beads wereAnd talcum powder is measured by a weightlessness scale, butane is added at the position 2/3 of the length of a screw rod from a main feeding port of the double-screw extruder, the butane is measured by a flowmeter, the temperature of a plasticizing area of the double-screw extruder is 160-180 ℃, the temperature of a conveying section is set to be 130-150 ℃, then the material is conveyed into a second-stage single-screw extruder through a connector for cooling treatment, the temperature of the single-screw extruder is set to be 130 ℃, finally the material is extruded through a die head and cut into particles underwater, the water pressure of cutting water is controlled to be 15bar through a high-pressure water pump, the water temperature is 30 ℃, and the density is 1.05g/cm 3 The expandable thermoplastic polyurethane elastomer beads of (1).
The expandable thermoplastic polyurethane elastomer beads of examples 1 to 5 and comparative example 1 were expanded in a reaction vessel into which high-pressure steam was introduced to obtain thermoplastic polyurethane elastomer beads. The method comprises the following specific steps: firstly weighing 1kg of foamable thermoplastic polyurethane elastomer beads, putting the foamable thermoplastic polyurethane elastomer beads into a reaction kettle, introducing water vapor with certain steam pressure into the reaction kettle to heat the foamable thermoplastic polyurethane elastomer beads, heating for a certain time, opening the reaction kettle to take out materials, naturally cooling to room temperature to obtain the foamed thermoplastic polyurethane elastomer beads, wherein the steam pressure and the heating time adopted in examples 1-5 and comparative example 1, and the density and the average cell size of the obtained foamed thermoplastic polyurethane elastomer beads are shown in Table 1.
TABLE 1
Production of thermoplastic polyurethane foam boards:
the expanded thermoplastic polyurethane elastomer beads obtained after the expansion of the expandable thermoplastic polyurethane elastomer beads of examples 1 to 5 and comparative example 1 were filled in a mold 300mm in length x 250mm in width x 20mm in thickness. The particles were bonded by 10% compression in the thickness direction of the mold using water vapor at a pressure (shown in table 2) to give molded thermoplastic polyurethane foam boards, which were then oven dried at 70 ℃ for 6 hours and then allowed to stand at room temperature for 2 hours to evaluate their properties, as shown in the data in table 2.
The expandable thermoplastic polyurethane elastomer beads of example 5 were directly filled into a mold 300mm long by 250mm wide by 20mm thick. The particles were bonded by 10% compression in the thickness direction of the mold using water vapor under a pressure (shown in Table 2) to give a molded thermoplastic polyurethane foam board, which was then oven-dried at 70 ℃ for 6 hours and then allowed to stand at room temperature for 2 hours to evaluate the properties, as shown in the data of Table 2, which is reported as example 6.
TABLE 2
Remarking: examples 1 to 5 and comparative example 1 in Table 2 represent thermoplastic polyurethane foam boards obtained by bonding the expanded thermoplastic polyurethane elastomer beads of examples 1 to 5 and comparative example 1, respectively, and example 6 represents a thermoplastic polyurethane foam board obtained by directly welding the expandable thermoplastic polyurethane elastomer beads of example 5.
The expandable thermoplastic polyurethane elastomer beads of example 1 and comparative example 1, which were stored for different periods of time, were expanded in a reaction vessel into which high-pressure steam was introduced to obtain thermoplastic polyurethane elastomer beads. The method comprises the following specific steps: firstly weighing 1kg of foamable thermoplastic polyurethane elastomer beads, putting the 1kg of foamable thermoplastic polyurethane elastomer beads into a reaction kettle, introducing water vapor with certain steam pressure into the reaction kettle, heating the foamable thermoplastic polyurethane elastomer beads for a certain time, opening the reaction kettle, taking out the material, and naturally cooling the material to room temperature to obtain the foamed thermoplastic polyurethane elastomer beads, wherein the steam pressure and the heating time adopted in the embodiment 1 and the comparative example 1, and the density of the obtained foamed thermoplastic polyurethane elastomer beads are shown in a table 3.
TABLE 3
The data in the table 1 show that the foamable thermoplastic polyurethane elastomer bead prepared by the invention has excellent foamable performance, and the prepared foamable thermoplastic polyurethane elastomer bead has low density and fine foam pores; from the data in table 2, it can be seen that the foamed thermoplastic polyurethane foam products having excellent appearance, light weight, high resilience and high strength can be obtained from both the foamed thermoplastic polyurethane foam products formed by foaming the expandable thermoplastic polyurethane elastomer beads of the present invention and the foamed thermoplastic polyurethane foam products formed by directly molding the expandable thermoplastic polyurethane elastomer beads of the present invention; from the data in table 3, we can see that the expandable thermoplastic polyurethane elastomer bead prepared by the invention has the property of good storage stability; in conclusion, the foamable thermoplastic polyurethane elastomer bead prepared by the invention has wide application prospects in the fields of soles, tires, bicycle seats, interior ornaments, buffer pads, sound insulation pads, children toys, ground coverings and the like.
Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention defined by the appended claims.
Claims (10)
1. A method for preparing a foamable thermoplastic polyurethane elastomer is characterized by comprising the following steps:
(1) Adding a thermoplastic polyurethane elastomer with a crystallization temperature of not less than 70 ℃ and a Shore hardness of 70A-85D and a foaming agent into a first-stage double-screw extruder according to a mass ratio of 100.1-10 for melt mixing;
the foaming agent is one or a mixture of more of butane, isobutane, pentane, pentafluoropropane and acetone;
(2) Feeding the material extruded by the double-screw extruder in the step (1) into a second-stage single-screw extruder for cooling treatment, extruding the material through a die head, and carrying out underwater pelletizing to obtain a foamable thermoplastic polyurethane elastomer; the water pressure of the underwater granulating is 5-30bar.
2. The preparation method according to claim 1, wherein in the step (1), the shore hardness of the thermoplastic polyurethane elastomer is 80A-85D.
3. The production method according to claim 1, wherein in the step (1), the thermoplastic polyurethane elastomer is fed at a main feed port of the twin-screw extruder, and the foaming agent is fed at a position 2/3 of the screw length from the main feed port of the twin-screw extruder.
4. The method according to claim 1, wherein in the step (2), the water temperature of the underwater pellets is 0-90 ℃.
5. The production method according to claim 1, wherein in the step (2), the water pressure of the underwater pellets is 10 to 30bar.
6. The production method according to claim 5, wherein in the step (2), the water pressure of the underwater pellets is 15 to 30bar.
7. The foamable thermoplastic polyurethane elastomer prepared by the preparation process according to any one of claims 1 to 6.
8. The foamable thermoplastic polyurethane elastomer according to claim 7, wherein the foamable thermoplastic polyurethane elastomer has a particle diameter of 0.5 to 6mm and a density of 0.7 to 1.3g/cm 3 。
9. A process for preparing expanded thermoplastic polyurethane elastomer beads, comprising: foaming the foamable thermoplastic polyurethane elastomer of claim 7 or 8 on a reaction kettle or fluidized bed with steam, hot air or microwave radiation to obtain foamed thermoplastic polyurethane elastomer beads.
10. A method of making a thermoplastic polyurethane foam article comprising: the foamable thermoplastic polyurethane elastomer of claim 7 or 8 is foamed and welded in a mold with steam or microwave radiation to obtain a thermoplastic polyurethane foam article.
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