CN115124834A - Thermoplastic polyamide elastomer blending foaming material and preparation method thereof - Google Patents
Thermoplastic polyamide elastomer blending foaming material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thermoplastic polyamide elastomer blending foaming material and a preparation method thereof. The thermoplastic polyamide elastomer blending foaming material is prepared by foaming a thermoplastic polyamide elastomer composition, wherein the thermoplastic polyamide elastomer composition is prepared from the following raw materials in parts by weight: 5-95 parts of thermoplastic polyamide elastomer, 5-15 parts of polyamide, 0.5-2 parts of chain extender, 0.05-0.3 part of antioxidant, 0-5 parts of nucleating agent and 0-5 parts of lubricant, wherein the complex viscosity of the thermoplastic polyamide elastomer composition is in the range of 5000 Pa.s-10000 Pa.s, and the loss tangent value is in the range of 0.8-2. The invention solves the problems of low foaming multiplying power, serious volume shrinkage, poor restorability and collapse and rupture of cells of the foaming material of the thermoplastic polyamide elastomer material caused by low melt strength and matrix modulus and low linear molecular chain strength and elasticity of the thermoplastic polyamide elastomer material.
Description
Technical Field
The invention belongs to the field of foaming materials, and particularly relates to a thermoplastic polyamide elastomer blending foaming material and a preparation method thereof.
Background
The polyamide elastomer is a nylon-type thermoplastic elastomer (TPE) material with soft segments and hard segments which are alternately segmented, the hard segments are high-crystallinity polyamide (nylon 6, nylon 66, nylon 12 and the like), and the soft segments are polyether, polyester or polycarbonate. Due to its excellent mechanical and chemical properties, polyamide elastomer foams have more excellent properties in terms of resilience, compression resistance, heat insulation, shock absorption, etc. than other thermoplastic elastomer foams. At present, the polyamide elastomer foaming material is researched less in China, most of the polyamide elastomer foaming material is in the research and development stage, and the polyamide elastomer foaming material has sufficient development space.
As with other thermoplastic elastomers, in the physical foaming process, the polyamide elastomer is foamedThere is significant volume shrinkage behavior of the material. The polyamide elastomer foam material just prepared has the characteristics of high foaming ratio and high elasticity, but the elastomer foam material has serious contraction phenomena in the process of replacing the foaming agent and air in the foam holes, which are shown as rapid volume contraction, foam hole collapse and fracture and serious performance reduction. The shrinkage phenomenon is mainly caused by the defects of low melt strength and modulus, low linear molecular chain rigidity, low elasticity, high gas diffusion and the like of the polyamide elastomer material, and CO is used 2 When used as a physical blowing agent, CO is added after the foaming is completed 2 The air in the environment has no time to diffuse into the interior of the foam hole, the pressure in the foam hole is lower than the atmospheric pressure in the environment, and the air negative pressure can cause the polyamide elastomer foam material to generate a remarkable volume shrinkage phenomenon. As air is gradually diffused into the foam holes, the pressure in the air bubbles is gradually increased until the internal pressure and the external pressure are equal, the pressure borne by the polyamide elastomer molecular chain segment and the matrix is gradually reduced, and the polyamide elastomer molecular chain segment and the matrix are gradually stretched and recovered due to the elasticity of the polyamide elastomer molecular chain segment and the matrix, but the polyamide elastomer matrix has low modulus and linear molecular chains and low strength and elasticity, and is subjected to plastic deformation after being compressed, so that the volume of the polyamide elastomer foam after being contracted can only be partially recovered or even can not be recovered.
Chinese patent CN 201810077608.2 discloses a preparation method of block polyether amide elastomer (Pebax) and TPU blended foaming material, the formula of the material is: the weight ratio of Pebax to TPU is 10: 90-90:10, the preparation method is that Pebax and TPU are mixed by a double screw extruder and then granulated, and a physical foaming agent N is used by a batch foaming method 2 The invention improves the water resistance and weather resistance of the product, but does not effectively improve the viscoelasticity and modulus of the material, so that the product is easy to shrink in the foaming process.
Chinese patent CN109943079A discloses a polyamide elastomer foam material and a preparation method thereof. The preparation method comprises the steps of uniformly mixing the polyamide elastomer, the melt viscosity regulator, the foam cell nucleating agent and the foaming auxiliary agent, and extruding and molding to prepare the foaming precursor meeting the requirements; and then preparing the polyamide elastomer foaming material by a physical foaming method, wherein the invention prepares the foam with light weight, good flexibility, uniform cell size and low density, and introduces a melt viscosity regulator to regulate and control the melt viscosity and strength, but the patent method does not provide an effective scheme for the problem of foaming material shrinkage.
Chinese patent CN201810077522.X discloses a thermoplastic elastomer and a foaming material thereof, which are prepared by blending polyether amide elastomer (Pebax) with one or more of EVA, POE and OBC, then carrying out chemical or physical crosslinking to obtain a new thermoplastic elastomer material, and then carrying out supercritical foaming on the crosslinked material to obtain the foaming material. The patent method adopts two or more polymers with different phases to blend, and has the defects of insufficient mixing, easy phase separation, interface combination and the like, and further causes the defects of uneven size, easy shrinkage and the like of the foaming material.
Therefore, the problem of shrinkage of the thermoplastic polyamide elastomer foam material needs to be further researched and solved.
Disclosure of Invention
The invention provides a thermoplastic polyamide elastomer blending foaming material and a preparation method thereof, which solve the problems of low foaming multiplying power, serious volume shrinkage, poor restorability and collapse and rupture of cells of the foaming material caused by low melt strength and matrix modulus and low linear molecular chain strength and elasticity of the thermoplastic polyamide elastomer material.
According to a first aspect of the present invention, there is provided a thermoplastic polyamide elastomer blended foamed material, which is prepared by foaming a thermoplastic polyamide elastomer composition, wherein the thermoplastic polyamide elastomer composition is formed from the following raw materials by weight: 85-95 parts of thermoplastic polyamide elastomer, 5-15 parts of polyamide, 0.5-2 parts of chain extender, 0.05-0.3 part of antioxidant, 0-5 parts of nucleating agent and 0-5 parts of lubricant, wherein the complex viscosity of the thermoplastic polyamide elastomer composition is within the range of 5000 Pa.s-10000 Pa.s, and the loss tangent value is within the range of 0.8-2.
Preferably, in the thermoplastic polyamide elastomer blended foaming material, the thermoplastic polyamide elastomer is a nylon-type thermoplastic elastomer material with soft blocks and hard blocks alternating with each other, wherein the hard blocks comprise at least one of polyamide 6, polyamide 12 and polyamide 66, and the soft blocks comprise at least one of polyether and polyester.
Preferably, in the thermoplastic polyamide elastomer blend foam material, the melting point of the Polyamide (PA) is not higher than the melting temperature of the thermoplastic polyamide elastomer by 30 ℃ or more, and the relative viscosity of the Polyamide (PA) is 2.8 or more.
Preferably, in the thermoplastic polyamide elastomer blended foam material, the chain extender is at least one of a random copolymer (SMA) of styrene and maleic anhydride or a multifunctional epoxy compound.
Preferably, in the thermoplastic polyamide elastomer blended foaming material, the chain extender is 0.5-1 part, the nucleating agent is 0.5-3 parts, and the lubricant is 1-3 parts.
Preferably, in the thermoplastic polyamide elastomer blended foam material, the apparent density of the thermoplastic polyamide elastomer blended foam material is 0.08-0.5g/cm 3 Within the range, the crystallinity is not more than 26%.
According to a second aspect of the present invention, there is provided a method for preparing the thermoplastic polyamide elastomer blended foam material, comprising the following steps: s1, extruding and granulating the thermoplastic polyamide elastomer, polyamide, a chain extender, an antioxidant, a nucleating agent and a lubricant through an extruder to obtain the thermoplastic polyamide elastomer composition, wherein the temperature of the extruder is set at 220-240 ℃; s2, placing the thermoplastic polyamide elastomer composition into a mould pressing foaming machine, setting the temperature of the mould pressing foaming machine between 200 ℃ and 230 ℃, and introducing CO 2 、N 2 One or two of the components are saturated for 0.5 to 2 hours under the saturation pressure of 10 to 20MPa, and then the mixture is decompressed and foamed to obtain the thermoplastic polyamide elastomer blended foaming material.
According to a third aspect of the present invention, there is provided a method for preparing the thermoplastic polyamide elastomer blended foam material, comprising the following steps: s1, extruding and granulating the thermoplastic polyamide elastomer, the polyamide, the chain extender, the antioxidant, the nucleating agent and the lubricant through an extruder to obtain the thermoplastic polyimideAmine elastomer composition, wherein the extruder temperature is set at 220-240 ℃; s2, adding the thermoplastic polyamide elastomer composition into a double-stage extrusion foaming system, wherein the temperature of a first-stage extruder of the double-stage extrusion foaming system is between 220 ℃ and 230 ℃, introducing a foaming agent into the molten polymer melt, and uniformly mixing the foaming agent with the molten polymer melt to obtain the gas-containing polymer melt, wherein the foaming agent is CO 2 、N 2 One or two of them; and cooling the gas-containing polymer melt to 200-220 ℃ by using a second-stage single-screw extruder or a melt cooler of a two-stage extrusion foaming system to enable the pressure of a machine head to be more than 10MPa, and extruding by using the machine head to obtain the thermoplastic polyamide elastomer blending foaming material.
According to a fourth aspect of the present invention, there is provided a method for preparing the thermoplastic polyamide elastomer blended foam material, comprising the following steps: s1, extruding and granulating the thermoplastic polyamide elastomer, polyamide, a chain extender, an antioxidant, a nucleating agent and a lubricant through an extruder to obtain the thermoplastic polyamide elastomer composition, wherein the temperature of the extruder is set at 220-240 ℃; s2, adding the thermoplastic polyamide elastomer composition into an injection molding machine, wherein the temperature of the injection molding machine is between 220 ℃ and 230 ℃, and adding N 2 Introducing the gas-containing polymer melt into the molten polymer melt, uniformly mixing the gas-containing polymer melt with the molten polymer melt to obtain a gas-containing polymer melt, and injecting the gas-containing polymer melt into a mold at an injection pressure of more than or equal to 100MPa to obtain the thermoplastic polyamide elastomer blended foaming material.
According to a fifth aspect of the present invention, there is provided a method for preparing the thermoplastic polyamide elastomer blended foam material, comprising the following steps: s1, putting a thermoplastic polyamide elastomer, polyamide, an antioxidant, a nucleating agent and a lubricant into a Haake internal mixer together, blending at 220-240 ℃, adding a chain extender, continuing to blend to obtain an internal mixing product, pressing the internal mixing product into sheets with consistent thickness by using a mould press, and cutting; s2, adopting a cooling foaming process, putting the pressed sheet into a mould pressing kettle at the temperature of between 220 and 240 ℃, and introducing 10-20MPa of CO 2 After melting and plasticizing, reducing the temperature of the mould pressing kettle to a foaming temperature of between 200 and 220 ℃, and continuously maintaining the pressure for 0.5 to 2 hoursAnd then, quickly decompressing to obtain the thermoplastic polyamide elastomer blending foaming material.
The invention has the beneficial effects that:
the method is simple and easy to operate, and effectively solves the problems of low foaming multiplying power, serious volume shrinkage, poor restorability, collapse and fracture of cells and the like of the thermoplastic elastomer foaming material.
Drawings
In order to more clearly illustrate the detailed description of the invention or the technical solutions in the prior art, the drawings that are needed in the detailed description of the invention or the prior art will be briefly described below.
FIG. 1 is a flow chart of the process for preparing the thermoplastic polyamide elastomer blended foam of the present invention.
FIG. 2 is a complex viscosity plot of the products of examples 1, 2 of the present invention and comparative examples 1, 2.
FIG. 3 is a graph showing the loss tangent tan. delta. of the products of examples 1 and 2 of the present invention and comparative examples 1 and 2.
FIG. 4 is a graph showing the elastic modulus curves of the products of examples 1 and 2 of the present invention and comparative examples 1 and 2.
FIG. 5 is a graph showing the expansion ratio with time of the products of examples 1 and 2 of the present invention and comparative examples 1 and 2.
FIG. 6 is a scanning electron micrograph of the product of example 1 of the present invention.
FIG. 7 is a scanning electron micrograph of the foaming of the product of comparative example 1.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods in the following examples are all conventional methods unless otherwise specified; reagents and materials, unless otherwise specified, are conventionally obtained commercially or prepared by conventional methods.
The thermoplastic polyamide elastomer blended foaming material is prepared by foaming a thermoplastic polyamide elastomer composition, wherein the thermoplastic polyamide elastomer composition is prepared from the following raw materials in parts by weight: 85-95 parts of thermoplastic polyamide elastomer, 5-15 parts of polyamide, 0.5-2 parts of chain extender, 0.05-0.3 part of antioxidant, 0-5 parts of nucleating agent and 0-5 parts of lubricant, wherein the complex viscosity of the thermoplastic polyamide elastomer composition is within the range of 5000 Pa.s-10000 Pa.s, and the loss tangent value is within the range of 0.8-2. Preferably, the chain extender is 0.5-1 part, the antioxidant is 0.05-0.1 part, the nucleating agent is 0-3 parts, and the lubricant is 1-3 parts. The thermoplastic polyamide elastomer blended foaming material has the weight percentage of 0.08-0.5g/cm 3 Apparent density within the range and a crystallinity of not more than 26%. The thermoplastic polyamide elastomer blended foaming material has good foaming performance, can recover quickly after shrinkage, and has high recovery rate.
The thermoplastic polyamide elastomer is a nylon-type thermoplastic elastomer material with soft segments and hard segments which are alternately segmented, wherein the hard segments are high-crystallinity polyamide, preferably at least one of polyamide 6, polyamide 12 and polyamide 66, and the soft segments comprise at least one of polyether and polyester.
The polyamide comprises at least one of polyamide 6, polyamide 12 and polyamide 66, the melting point of the Polyamide (PA) is not higher than the melting temperature of the thermoplastic polyamide elastomer by more than 30 ℃, and the relative viscosity of the Polyamide (PA) is greater than or equal to 2.8.
The chain extender is at least one of a random copolymer (SMA) of styrene and maleic anhydride or a polyfunctional epoxy compound. The antioxidant is at least one of antioxidant 168 and antioxidant 1098. The nucleating agent is at least one of talcum powder, calcium carbonate and nano silicon dioxide. The lubricant is at least one of stearic acid amide and monoglyceride stearate.
The preparation method of the thermoplastic polyamide elastomer blended foaming material comprises the following steps:
s1, melting and blending a thermoplastic polyamide elastomer, polyamide, a chain extender, an antioxidant, a nucleating agent and a lubricant at a temperature of 220-240 ℃ in proportion, and then performing extrusion granulation or tabletting to prepare a thermoplastic polyamide elastomer composition;
in this step, in a preferred embodiment, the raw materials are proportionally fed into an extruder, the temperature of the extruder is set to 220 ℃ and 240 ℃, and the thermoplastic polyamide elastomer composition is prepared by extrusion granulation; in another preferred embodiment, the thermoplastic polyamide elastomer composition sheet is prepared by melt blending the raw materials in proportions in an internal mixer set to a temperature of 220-240 ℃ and then pressing the mixture into a sheet by a molding press.
In the step, a polyamide elastomer is used as a raw material, a certain amount of chain extender SMA is added for carrying out melting chain extension modification, so that the polyamide elastomer has a branched structure, and polyamide with good compatibility with the polyamide elastomer is added, and the three react with each other, thereby not only improving the branching degree and strength of a molecular chain of the polyamide elastomer, but also enhancing the melt strength and matrix modulus of the polyamide elastomer.
S2, preparing the thermoplastic polyamide elastomer blending foaming material from the thermoplastic polyamide elastomer composition through a foaming process.
In this step, in a preferred embodiment, the thermoplastic polyamide elastomer composition is placed in a molding machine set at a temperature between 200 ℃ and 230 ℃ and CO is introduced 2 、N 2 One or two of the components are saturated for 0.5 to 2 hours under the saturation pressure of 10 to 20MPa, and then the mixture is decompressed and foamed to obtain the thermoplastic polyamide elastomer blended foaming material.
In another preferred embodiment, the thermoplastic polyamide elastomer composition is added to a two-stage extrusion foaming system, the first stageThe temperature of the extruder is between 220 ℃ and 230 ℃, 0.1-2 parts of foaming agent is introduced into the molten polymer melt and is uniformly mixed with the molten polymer melt to obtain the gas-containing polymer melt, wherein the foaming agent is CO 2 、N 2 Or a foaming agent capable of releasing CO after decomposition by heating 2 And/or N 2 (ii) a And cooling the gas-containing polymer melt to 200-220 ℃ by using a second-stage single-screw extruder or a melt cooler, adjusting the feeding amount and the extrusion process parameters to enable the head pressure to be greater than 10MPa, and extruding by using a head to obtain the thermoplastic polyamide elastomer blending foaming material.
In yet another preferred embodiment, the thermoplastic polyamide elastomer composition is introduced into an injection molding machine at a temperature between 220 ℃ and 230 ℃ and 0.1 to 1 part N is added 2 And introducing the mixture into a molten polymer melt, wherein the plasticizing length of the screw is 50-70% of that of full injection, uniformly mixing the mixture with the molten polymer to obtain a gas-containing polymer melt, and injecting the gas-containing polymer melt into a mold at an injection pressure of more than or equal to 100MPa to obtain the thermoplastic polyamide elastomer blending foaming material.
In yet another preferred embodiment, the thermoplastic polyamide elastomer composition obtained in step S1 is placed in a mold pressing kettle at a temperature between 220 ℃ and 240 ℃ by a cooling foaming process, and is introduced with 10-20MPa of CO 2 And after melting and plasticizing, cooling the mould pressing kettle to the foaming temperature of 200-220 ℃, keeping the pressure for 0.5-2 hours, and quickly releasing the pressure to obtain the thermoplastic polyamide elastomer blending foaming material.
The method has simple process and easy operation, and effectively solves the defects of low foaming ratio, serious volume shrinkage, poor recovery, collapse and rupture of cells and the like of the thermoplastic elastomer foaming material.
Example 1:
raw materials: 85 parts of thermoplastic polyamide elastomer (TPAE), 15 parts of polyamide 6(PA6) with the relative viscosity of 2.8 and the melting point of 220 ℃, 1 parts of chain extender SMA, and 0.1 part and 0.2 part of antioxidant 168 and 1098 respectively.
The preparation method comprises the following steps:
s1, melt blending: firstly, putting the polyamide elastomer, the polyamide and the antioxidant into a Haake internal mixer together, blending for 1min at the temperature of 225 ℃ and the rotating speed of 60rpm, then adding a chain extender SMA, and continuing blending for 10min to obtain an internal mixing product; tabletting: and pressing the obtained banburying product into sheets with consistent thickness by using a molding press, and cutting to prepare the thermoplastic polyamide elastomer composition.
S2, supercritical foaming: adopting a cooling foaming process, putting the pressed sheet (thermoplastic polyamide elastomer composition) into a mould pressing kettle at the temperature of 240 ℃, and introducing 12MPa of CO 2 And after 30min of melting and plasticizing, reducing the temperature of the mould pressing kettle to the foaming temperature of 220 ℃, keeping the pressure for 30min, and quickly releasing the pressure to obtain the thermoplastic polyamide elastomer blending foaming material.
And (3) performance characterization:
(1) and (3) rheological property testing: and carrying out dynamic frequency scanning test on the blend by using a HAAKE flat plate rotating rheometer, wherein the type of a rotor of the rheometer is P20TiL, the diameter of a flat plate is 20mm, a test gap is 1.0mm, a measurement mode is set to be a fixed strain 1%, the test temperature is 225 ℃, and the test is carried out under the nitrogen environment of 0.2MPa in order to prevent oxidative degradation. Frequency scanning test: setting the frequency range as 100-0.1rad/s, and testing from high frequency to low frequency to obtain the storage modulus (G'), complex viscosity (| eta |) * |) changes in viscoelastic performance parameters with frequency. Fig. 2 and fig. 3 are graphs of storage modulus and complex viscosity of TPAE and TPAE after chain extension and blending, respectively.
(2) And (3) testing the crystallinity: the crystallinity of the blend is defined by the hard segment content of the polyamide elastomer material and the content of the added polyamide:
wherein Δ H m Is the enthalpy of fusion, Δ H, of the blended material 1 Is the melting enthalpy, Δ H, of the polyamide elastomer hard segment material 2 Is the melting enthalpy, W, of the polyamide material added H Is the hard segment content, W, of the polyamide elastomer material f Is the weight fraction of the polyamide elastomer material.
(3) Relative viscosity test: dissolving polyamide in a solvent, and measuring the viscosity of the polyamide solution and the viscosity of a pure solvent by using a capillary viscometer, wherein the ratio of the viscosity of the polyamide solution to the viscosity of the pure solvent is the relative viscosity of the polyamide.
(4) And (3) testing the foaming ratio: after removal from the autoclave, the foamed article was tested for apparent density using an analytical balance according to standard GB 1033-86. The ratio of the density of the blended sample before foaming to the density after foaming is the foaming multiplying power. Fig. 5 is a graph showing the change of the expansion ratio of each foamed sample with time.
(5) And (3) shrinkage testing: shrinkage Q of foamed sample i Initial expansion ratio of sample
Foaming rate of sample with time
Calculated, the calculation formula is as follows:
table 1 reports the expansion ratio and shrinkage ratio of each foamed sample.
(6) Cutting the foamed sample into strip-shaped samples by using an ultrathin blade, quenching the strip-shaped samples in liquid nitrogen, then carrying out metal spraying treatment to enhance the conductivity, observing the section shape by using a scanning electron microscope, and obtaining SEM images.
After testing and calculation, example 1 had a crystallinity of 22.86%, a complex viscosity (ω ═ 0.628rad/s) of 8900pa · s, a loss tangent tan δ of 0.8, and an elastic modulus of 4300 pa.
Example 2:
raw materials: 90 parts of thermoplastic polyamide elastomer (TPAE), 10 parts of polyamide 6(PA6) with the relative viscosity of 3.9 and the melting point of 220 ℃, 1 parts of chain extender SMA, and 0.1 part and 0.2 part of antioxidant 168 and 1098 respectively.
The rest of the procedure was the same as in example 1.
After testing and calculation, example 2 had a crystallinity of 25.21%, a complex viscosity (ω: 0.628rad/s) of 5700pa · s, a loss tangent tan δ of 1, and an elastic modulus of 2200 pa.
Comparative example 1:
the pure material thermoplastic polyamide elastomer (TPAE) is pressed and cut by a mould press, then supercritical foaming is carried out, a cooling foaming method is also adopted, the melting plasticizing temperature is 220 ℃, the foaming temperature is 190 ℃, and the rest conditions and the performance characterization are the same as those of the example 1.
After testing and calculation, comparative example 1 had a crystallinity of 29.33%, a complex viscosity (ω 0.628rad/s) of 2173pa · s, a loss tangent tan δ of 6, and an elastic modulus of 222.3 pa.
Comparative example 2:
raw materials: 100 parts of thermoplastic polyamide elastomer (TPAE), 1 parts of chain extender SMA1 parts, and 0.1 part and 0.2 part of antioxidant 168 and 1098 parts respectively.
The preparation method comprises the following steps:
s1, melt blending: firstly, putting the polyamide elastomer antioxidant into a Haake internal mixer together, blending for 1min at the temperature of 225 ℃ and the rotating speed of 60rpm, then adding a chain extender SMA, and continuing blending for 10min to obtain an internal mixing product; tabletting: and pressing the obtained banburying product into sheets with consistent thickness by using a molding press, and cutting.
S2, supercritical foaming: adopting a cooling foaming process, putting the pressed sheet into a mould pressing kettle at the temperature of 230 ℃, and introducing 12MPa of CO 2 And after 30min of melting and plasticizing, reducing the temperature of the mould pressing kettle to the foaming temperature of 205 ℃, keeping the pressure for 30min, and quickly relieving the pressure to obtain the thermoplastic polyamide elastomer blending foaming material.
After testing and calculation, comparative example 2 has a crystallinity of 29.23%, a complex viscosity (ω ═ 0.628rad/s) of 2158pa · s, a loss tangent tan δ of 3.26, and an elastic modulus of 397.3 pa.
Table 1 shows the expansion ratio and shrinkage ratio data of the foams prepared in examples 1 and 2 and comparative examples 1 and 2:
| initial expansion ratio | Foaming ratio after 24h | Apparent density (g/cm) after 24h 3 ) | Shrinkage rate | |
| Example 1 | 13.72 | 11.89 | 0.090 | 13.34％ |
| Example 2 | 14.31 | 11.50 | 0.093 | 19.64％ |
| Comparative example 1 | 14.20 | 5.73 | 0.187 | 59.65％ |
| Comparative example 2 | 12.15 | 7.64 | 0.140 | 37.12％ |
As can be seen from Table 1, the initial foaming ratio of the TPAE + SMA + PA6 blended elastomer material is almost the same as that of the pure TPAE material, which indicates that the foaming performance of the elastomer material after blending is not greatly affected. But the expansion ratio after shrinkage is very different, the expansion ratio after blending the elastomer material for 24 hours is far larger than that of a pure TPAE material, and the shrinkage rate is far lower than that of the pure TPAE foam material. Fig. 5 shows the relationship between the expansion ratio and time in the above examples, and it can be seen that the pure TPAE material shrinks seriously after being foamed and hardly recovers the volume with the increase of time, while the blended elastomer material recovers quickly after shrinking and the recovery rate is extremely high.
In the foaming process, cell nucleation and growth are induced after rapid pressure relief. At this stage, when the cell size is increased, the soft segment and the hard segment in the TPAE molecular chain are subjected to bidirectional stretching force, and as TPAE has the defects of low melt strength and modulus, low rigidity and elasticity of a linear molecular chain and the like, the cell structure and the molecular chain can be damaged, so that the cell structure and the molecular chain can be completely failed, and the shrinkage phenomenon occurs under the condition of negative pressure, so that irreversible deformation is caused. As can be seen from fig. 2 to 4, the complex viscosity and the elastic modulus of the TPAE blended foaming material of the invention are greatly improved, and the loss tangent value is smaller, compared with a pure TPAE material, which indicates that the melt strength and the matrix modulus of the material are improved, and the molecular chain branching and even the cross-linking structure is higher, so that the material can bear bidirectional stretching force and negative pressure in the foaming process, and prevent the molecular chain and the cell structure from completely losing and deforming, after air permeates into the cells, the negative pressure in the cells is gradually reduced, the pressure of the molecular chain segment is gradually reduced, and the self elasticity is gradually extended and recovered, so that the foaming ratio is gradually recovered and improved, and therefore, the recovery after the foam shrinkage and the maintenance of the cell structure can be effectively improved.
The comparison of the cell morphologies of the products of example 1 and comparative example 1, shown in FIGS. 6 and 7, further demonstrates the effectiveness and effectiveness of the process of the present invention.
In examples 1 and 2 of the present invention, melt blending and foaming are performed by an internal mixer and a molding press, and a cooling foaming process is used for foaming, but other melt blending and foaming processes can be used in the present invention, such as the following examples 3 to 5.
Example 3:
raw materials: 95 parts of thermoplastic polyamide elastomer (TPAE), 15 parts of polyamide 6(PA6) with the relative viscosity of 2.8 and the melting point of 220 ℃, 0.5 part of chain extender SMA, 0.02 part and 0.03 part of antioxidant 168 and 1098 respectively, 5 parts of nucleating agent and 1 part of lubricant.
The preparation method comprises the following steps:
s1, weighing the raw materials in proportion, adding the raw materials into an extruder, setting the temperature of the extruder to 240 ℃, and preparing a thermoplastic polyamide elastomer composition through extrusion granulation;
s2, placing the thermoplastic polyamide elastomer composition prepared in the step 1 into a mould pressing foaming machine, setting the temperature of the mould pressing machine at 210 ℃, and introducing CO 2 、N 2 And one or two of the components are mixed, the saturation pressure is 15MPa, the saturation time is 1 hour, and then the pressure is released for foaming to obtain the thermoplastic polyamide elastomer blended foaming material.
After testing and calculation, example 3 had a crystallinity of 21.73%, a complex viscosity (ω -0.628 rad/s) of 9200pa · s, a loss tangent tan δ of 0.75, and an elastic modulus of 4600 pa.
Example 4:
raw materials: 88 parts of thermoplastic polyamide elastomer (TPAE), 5 parts of polyamide 6(PA6) with the relative viscosity of 3.9 and the melting point of 220 ℃, 0.1 part and 0.2 part of chain extender SMA2 parts, 0.1 part and 0.2 part of antioxidant 168 and 1098 parts respectively, 3 parts of nucleating agent and 3 parts of lubricant.
The preparation method comprises the following steps:
s1, weighing the raw materials in proportion, adding the raw materials into an extruder, setting the temperature of the extruder to be 220 ℃, and preparing a thermoplastic polyamide elastomer composition through extrusion granulation;
s2, adding the thermoplastic polyamide elastomer composition prepared in the step S1 into a double-stage extrusion foaming system, wherein the temperature of a first-stage extruder is 230 ℃, introducing 2 parts of foaming agent into the molten polymer melt, and uniformly mixing the foaming agent and the molten polymer melt to obtain the gas-containing polymer melt, wherein the foaming agent is CO 2 (ii) a Cooling the gas-containing polymer melt to 220 ℃ by a second-stage single-screw extruder or a melt cooler, adjusting the feeding amount and the extrusion process parameters to ensure that the head pressure is more than 10MPa, and passing the machineAnd (4) after head extrusion, obtaining the thermoplastic polyamide elastomer blending foaming material.
After testing and calculation, example 4 had a crystallinity of 25.43%, a complex viscosity (ω ═ 0.628rad/s) of 5200pa · s, a loss tangent tan δ of 1.25, and an elastic modulus of 2100 pa.
Example 5:
raw materials: 85 parts of thermoplastic polyamide elastomer (TPAE), 10 parts of polyamide 6(PA6) with the relative viscosity of 3.9 and the melting point of 220 ℃, 1 parts of chain extender SMA, 0.5 part and 0.5 part of antioxidants 168 and 1098, 0.5 part of nucleating agent and 5 parts of lubricant.
The preparation method comprises the following steps:
s1, weighing the raw materials in proportion, adding the raw materials into an extruder, setting the temperature of the extruder at 230 ℃, and preparing a thermoplastic polyamide elastomer composition through extrusion granulation;
s2, adding the thermoplastic polyamide elastomer composition prepared in the step S1 into an injection molding machine, setting the temperature of the injection molding machine at 220 ℃, and adding 1 part of N 2 Introducing the gas-containing melt into a molten polymer melt, uniformly mixing the gas-containing melt with the molten polymer melt, and injecting the gas-containing melt into a mold to obtain the polyamide thermoplastic elastomer foaming material.
After testing and calculation, example 4 had a crystallinity of 25.23%, a complex viscosity (ω ═ 0.628rad/s) of 5604pa · s, a loss tangent tan δ of 1.15, and an elastic modulus of 2150 pa.
Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that: any person skilled in the art can modify or easily conceive the technical solutions described in the foregoing embodiments or equivalent substitutes for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A thermoplastic polyamide elastomer blending foaming material is characterized by being prepared by foaming a thermoplastic polyamide elastomer composition, wherein the thermoplastic polyamide elastomer composition is formed by the following raw materials in parts by weight: 85-95 parts of thermoplastic polyamide elastomer, 5-15 parts of polyamide, 0.5-2 parts of chain extender, 0.05-0.3 part of antioxidant, 0-5 parts of nucleating agent and 0-5 parts of lubricant, wherein the complex viscosity of the thermoplastic polyamide elastomer composition is within the range of 5000 Pa.s-10000 Pa.s, and the loss tangent value is within the range of 0.8-2.
2. The thermoplastic polyamide elastomer blend foam material as claimed in claim 1, wherein the thermoplastic polyamide elastomer is a nylon-type thermoplastic elastomer material with soft segments and hard segments alternating with each other, wherein the hard segments comprise at least one of polyamide 6, polyamide 12 and polyamide 66, and the soft segments comprise at least one of polyether and polyester.
3. The thermoplastic polyamide elastomer blend foam material as claimed in claim 1, wherein the melting point of the Polyamide (PA) is not higher than the melting temperature of the thermoplastic polyamide elastomer by more than 30 ℃, and the relative viscosity of the Polyamide (PA) is 2.8 or more.
4. The thermoplastic polyamide elastomer blend foam material as claimed in claim 1, wherein the chain extender is at least one of a random copolymer of Styrene and Maleic Anhydride (SMA) or a multifunctional epoxy compound.
5. The thermoplastic polyamide elastomer blended foaming material as claimed in claim 1, wherein the chain extender is 0.5-1 part, the nucleating agent is 0.5-3 parts, and the lubricant is 1-3 parts.
6. According to claimThe thermoplastic polyamide elastomer blended foam material as claimed in claim 1, wherein the apparent density of the thermoplastic polyamide elastomer blended foam material is 0.08-0.5g/cm 3 Within the range, the crystallinity is not more than 26%.
7. The method for preparing the thermoplastic polyamide elastomer blended foam material as claimed in any one of claims 1 to 6, comprising the steps of:
s1, extruding and granulating the thermoplastic polyamide elastomer, polyamide, a chain extender, an antioxidant, a nucleating agent and a lubricant through an extruder to obtain a thermoplastic polyamide elastomer composition, wherein the temperature of the extruder is set to be 220-240 ℃;
s2, placing the thermoplastic polyamide elastomer composition into a mould pressing foaming machine, wherein the temperature of the mould pressing foaming machine is set between 200 ℃ and 230 ℃, and introducing CO 2 、N 2 One or two of the components are saturated for 0.5 to 2 hours under the saturation pressure of 10 to 20MPa, and then the mixture is decompressed and foamed to obtain the thermoplastic polyamide elastomer blended foaming material.
8. The method for preparing the thermoplastic polyamide elastomer blended foaming material according to any one of the claims 1 to 6, characterized by comprising the following steps:
s1, extruding and granulating the thermoplastic polyamide elastomer, polyamide, a chain extender, an antioxidant, a nucleating agent and a lubricant through an extruder to obtain a thermoplastic polyamide elastomer composition, wherein the temperature of the extruder is set to be 220-240 ℃;
s2, adding the thermoplastic polyamide elastomer composition into a double-stage extrusion foaming system, wherein the temperature of a first-stage extruder of the double-stage extrusion foaming system is between 220 ℃ and 230 ℃, introducing a foaming agent into the molten polymer melt, and uniformly mixing the foaming agent with the molten polymer melt to obtain the gas-containing polymer melt, wherein the foaming agent is CO 2 、N 2 One or two of (a) and (b); cooling the gas-containing polymer melt to 200E, E through a second-stage single-screw extruder or melt cooler of the two-stage extrusion foaming systemAnd (3) at 220 ℃, enabling the pressure of a machine head to be more than 10MPa, and extruding by the machine head to obtain the thermoplastic polyamide elastomer blending foaming material.
9. The method for preparing the thermoplastic polyamide elastomer blended foaming material according to any one of the claims 1 to 6, characterized by comprising the following steps:
s1, extruding and granulating thermoplastic polyamide elastomer, polyamide, a chain extender, an antioxidant, a nucleating agent and a lubricant through an extruder to obtain a thermoplastic polyamide elastomer composition, wherein the temperature of the extruder is set at 220-240 ℃;
s2, adding the thermoplastic polyamide elastomer composition into an injection molding machine, wherein the temperature of the injection molding machine is between 220 ℃ and 230 ℃, and adding N 2 And introducing the gas-containing polymer melt into the molten polymer melt, uniformly mixing the gas-containing polymer melt with the molten polymer melt to obtain a gas-containing polymer melt, and injecting the gas-containing polymer melt into a mold at an injection pressure of more than or equal to 100MPa to obtain the thermoplastic polyamide elastomer blended foaming material.
10. The method for preparing the thermoplastic polyamide elastomer blended foaming material according to any one of the claims 1 to 6, characterized by comprising the following steps:
s1, putting a thermoplastic polyamide elastomer, polyamide, an antioxidant, a nucleating agent and a lubricant into a Haake internal mixer together, blending at the temperature of 220-240 ℃, adding a chain extender, continuing to blend to obtain an internal mixing product, pressing the internal mixing product into sheets with consistent thickness by using a molding press, and cutting;
s2, adopting a cooling foaming process, putting the pressed sheet into a mould pressing kettle at the temperature of between 220 and 240 ℃, and introducing 10-20MPa of CO 2 And after melting and plasticizing, reducing the temperature of the mould pressing kettle to a foaming temperature of 200-220 ℃, keeping the pressure for 0.5-2 hours, and quickly releasing the pressure to obtain the thermoplastic polyamide elastomer blending foaming material.
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