CN115160766A - High-resilience low-shrinkage polyurethane foaming bead and preparation method thereof - Google Patents
High-resilience low-shrinkage polyurethane foaming bead and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-resilience low-shrinkage polyurethane foaming bead and a preparation method thereof, belonging to the technical field of new materials. The high-resilience low-shrinkage polyurethane foaming bead is prepared from polyurethane particles; the polyurethane particle comprises the following components in parts by weight: 80 to 100 parts; nucleating agent: 0.1 to 2 parts; a compatilizer: 2~5 parts; filling: 5 to 10 parts; the TPU has the following structure:
(ii) a Wherein m, n and p are positive integers, and the hard segment content is 50-70%; and the melt flow rate of the TPU is 15 to 25g/10min at 190 ℃ under the condition of 5kg of load. The high-resilience low-shrinkage polyurethane foaming bead disclosed by the invention is high in foaming multiplying power, and has higher resilience and smaller shrinkage.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to high-resilience low-shrinkage polyurethane foam beads and a preparation method thereof.
Background
Thermoplastic Polyurethane (TPU) as a thermoplastic elastomer has excellent performances such as low density and wear resistance, and is widely applied to various industries such as shoe materials, aerospace, automobiles, sports and the like. The TPU foam material can be made lightweight while maintaining its original excellent properties, and is endowed with new functions, and has become a research focus in recent years.
However, the molecular chain of TPU has a linear structure and has low crystallinity. TPU's have low stiffness at room temperature, make it difficult to obtain high resilience articles and suffer from severe shrinkage after foaming.
Therefore, how to modify TPU to overcome the above problems of TPU foaming materials to broaden the application depth and width of thermoplastic elastomers is a technical problem to be solved.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the problems of poor resilience and serious shrinkage of the existing TPU foaming material, and provides the high-resilience low-shrinkage polyurethane foaming bead and the preparation method thereof.
In order to solve the technical problem, the invention adopts the following technical scheme:
the high-resilience low-shrinkage polyurethane foaming bead is prepared from polyurethane particles; the polyurethane particle comprises the following components in parts by weight,
TPU:80 to 100 parts;
nucleating agent: 0.1 to 2 parts;
a compatilizer: 2~5 parts;
filling: 5 to 10 parts;
wherein the TPU comprises the structure:
wherein m, n and p are positive integers, and the hard segment content is 50-70%; and the melt flow rate of the TPU is 15 to 25g/10min at 190 ℃ under the condition of 5kg of load.
The TPU with the hard segment content of 50-70% is adopted, the hard segment content is high, the melt strength can be improved, and the TPU has better shrinkage resistance in the foaming process.
Preferably, the composition also comprises the following components in parts by weight,
hydrolysis resistance agent: 1~6 parts;
antistatic agent: 1~3 parts;
antioxidant: 0.2 to 1 part.
Preferably, the filler comprises one or more of ABS, AS, talc, barium sulfate and silica micropowder.
Preferably, the nucleating agent comprises GMS, tiO 2 And CaCO 3 And the grain diameter of the nucleating agent is 50 to 100nm.
Preferably, the compatibilizer comprises ABS-g-MAH and/or DCP.
Preferably, the hydrolysis resistance agent comprises polycarbodiimide and/or epoxy compounds.
Preferably, the antistatic agent is a compound containing quaternary ammonium salt as a main component, including TXP-10, FA14 or M550.
Preferably, the antioxidant comprises antioxidant 1010 and/or antioxidant 168.
Preferably, the preparation method of the polyurethane particles comprises,
putting the TPU, the nucleating agent, the compatilizer and the filler into an oven at the temperature of 80-90 ℃ and drying for 4-6 h;
putting the dried TPU, the nucleating agent, the compatilizer and the filler into a color mixer, and mixing for 5-10 min at the rotating speed of 50-100r/min to obtain a uniformly dispersed mixture;
extruding the mixture by a double-screw extruder, and carrying out underwater grain cutting by a grain cutter to obtain the polyurethane particles; wherein the feeding rotating speed of the double-screw extruder is 35 to 40r/min, and the rotating speed of the double-screw host is 150 to 220r/min; the temperature of a feeding section of the screw is 170 to 200 ℃, the temperature of a melting section is 190 to 210 ℃, the temperature of a metering section is 170 to 200 ℃, and the rotating speed of a melt pump is 10 to 25 r/min; the temperature of a screen changer, a melt pump, a start valve and a die head of the double-screw extruder is 200 to 220 ℃; the rotating speed of the granulator is 1000 to 2000r/min; the temperature of the circulating cooling water is 5 to 20 ℃.
The invention also provides a preparation method of the high-resilience low-shrinkage polyurethane foaming bead, which comprises the following steps,
putting the polyurethane particles into a reaction kettle with constant temperature T, and filling supercritical CO 2 Performing permeation and swelling to reach an equilibrium state to form a polymer-supercritical fluid homogeneous phase system; wherein the temperature is set to be 90 to 120 ℃ by taking water as a medium, and CO is used 2 The pressure of the mixture is 9 to 12Mpa, CO is in a pressure range of 9 to 12Mpa 2 The infiltration time of (a) is 0.5 to 2h;
and (3) carrying out pressure relief foaming at the speed of 5-10Mpa/s to obtain the high-resilience low-shrinkage polyurethane foaming bead of 8-20 times.
Compared with the prior art, the invention has the following advantages:
1. the high-resilience low-shrinkage polyurethane foaming bead provided by the invention has the advantages that the content of the hard segment of the adopted TPU is 50-70%, the melt strength is higher, and the shrinkage resistance is strong in the foaming process. By adding the nucleating agent, the crystallization of TPU particles can be promoted on the one hand, and the heterogeneous nucleation efficiency can be improved on the other hand. By adding the nucleating agent, more crystal nuclei can be generated in the matrix and uniformly dispersed in the system, so that more cells can be generated in the foaming process, thereby improving the resilience of the polyurethane foaming bead. By adding the filler, the melt strength of the polyurethane particles can be improved, and the shrinkage rate of the high-resilience low-shrinkage polyurethane foaming bead in the pressure-maintaining curing process can be reduced. By adding the compatilizer, the blending performance of the material can be improved, the surface of the expanded bead is smooth and mellow, and the value of the expanded bead as an industrial product is improved.
2. The preparation method provided by the invention has the advantages of simple and convenient manufacturing process and stable product quality, and can realize high-automation production and application.
3. The high-resilience low-shrinkage polyurethane foaming bead provided by the invention is a high-resilience low-shrinkage foaming thermoplastic polyurethane bead, has higher resilience and smaller shrinkage rate, and has high foaming multiplying power. The foaming multiplying power is 18 to 40 times, the shrinkage rate after pressure maintaining and curing is 5 to 15 percent, and the rebound resilience is 55 to 70 percent. The high-resilience low-shrinkage polyurethane foaming bead has a good application prospect, and the application field of the polyurethane foaming material is widened.
Drawings
FIG. 1 is a SEM image of a section of expanded beads prepared in example 2 of the present invention.
FIG. 2 is a sectional SEM photograph of expanded beads prepared in comparative example 2 of the present invention.
Detailed Description
Example 1
The high-resilience low-shrinkage polyurethane foaming bead is prepared from polyurethane particles. The polyurethane particles include: 9kg of TPU (HF-4085) and 70g of nucleating agent (CaCO) 3 ) 500g of filler (ABS, tianjin staphylol DG-417), 300g of compatibilizer (ABS-g-MAH, nantongming Yang Sujiao).
The preparation method of the high-resilience low-shrinkage polyurethane foaming bead comprises the following steps:
putting the TPU, the nucleating agent, the filler and the compatilizer into an oven at 80 ℃ for drying for 4 hours, then adding the TPU, the nucleating agent, the filler, the compatilizer, the hydrolysis resistance agent, the antistatic agent and the antioxidant into a color mixer, and mixing for 10 minutes at the rotating speed of 60r/min to obtain a uniformly dispersed mixed material.
And extruding the mixture by a double-screw extruder, and carrying out underwater grain cutting by a grain cutter to obtain the polyurethane particles. Wherein the feeding rotating speed of the double-screw extruder is 30r/min. The rotating speed of the double-screw main machine is 200r/min. The temperature of the screw feeding section is 160 ℃; the temperature of the melting section is 180 ℃; the metering section temperature was 175 ℃. The melt pump speed was 12 r/min. The screen changer, the melt pump, the start valve and the die head of the double-screw extruder are at 180 ℃. The rotating speed of the granulator is 1300r/min, and the temperature of circulating cooling water is 18 ℃.
Putting polyurethane particles into a reaction kettle with constant temperature T, and filling supercritical CO 2 Performing permeation and swelling to reach an equilibrium state to form a polymer-supercritical fluid homogeneous phase system; wherein water is used as medium, temperature T is set to 115 ℃, and CO is added 2 The pressure of (A) was 10MPa, and CO was adjusted to 2 The soaking time of (2) was 0.5h.
The foaming was carried out at a rate of 5MPa/s under pressure, giving 18 times the weight of the polyurethane expanded beads.
Example 2
The high-resilience low-shrinkage polyurethane foaming bead is prepared from polyurethane particles. The polyurethane particles include: 9kg of TPU (HF-4085), 70g of nucleating agent (CaCO) 3 ) 500g of filler (ABS, tianjin staphyl DG-417), 300g of compatibilizer (ABS-g-MAH, nantong ming Yang Sujiao), 100g of anti-hydrolysis agent (Shanghai Langii, hyMax 1010), 100g of antistatic agent (M550, teng chemical industry) and 20g of antioxidant (1010, BASF).
The preparation method of the high-resilience low-shrinkage polyurethane foaming bead comprises the following steps:
putting the TPU, the nucleating agent, the filler and the compatilizer into an oven at 80 ℃ for drying for 4 hours, then adding the TPU, the nucleating agent, the filler, the compatilizer, the hydrolysis resistance agent, the antistatic agent and the antioxidant into a color mixer, and mixing for 10 minutes at the rotating speed of 60r/min to obtain a uniformly dispersed mixed material.
And extruding the mixture by a double-screw extruder, and carrying out underwater grain cutting by a grain cutting machine to obtain the polyurethane particles. Wherein the feeding rotating speed of the double-screw extruder is 30r/min. The rotating speed of the double-screw main machine is 200r/min. The temperature of the screw feeding section is 160 ℃; the temperature of the melting section is 180 ℃; the metering section temperature was 175 ℃. The melt pump speed was 12 r/min. The screen changer, the melt pump, the start valve and the die head of the double-screw extruder are at 180 ℃. The rotating speed of the granulator is 1300r/min, and the temperature of circulating cooling water is 18 ℃.
Putting polyurethane particles into a reaction kettle with constant temperature T, and filling supercritical CO 2 Performing permeation and swelling to reach an equilibrium state to form a polymer-supercritical fluid homogeneous phase system; wherein water is used as medium, temperature T is set to 117 ℃, and CO is added 2 The pressure of (A) is 10.6MPa, CO 2 The soaking time of (2) was 0.5h.
The foaming was carried out at a rate of 5MPa/s by depressurization to give 20-fold foamed polyurethane beads. A section SEM image of the expanded bead is shown in FIG. 1, and it can be seen from FIG. 1 that the expanded bead has a uniform pore size distribution of 50 to 80 μm. As the pore diameter is larger, more gas is contained in the middle of the foam pores, most of the gas can be left after exchanging with air in the pressure maintaining process, so that the anti-shrinkage performance of the material is improved, and the prepared foam material has good resilience and high shrinkage rate.
Example 3
The high-resilience low-shrinkage polyurethane foaming bead is prepared from polyurethane particles; the polyurethane particles include: 8.5kg TPU (HF-4085), 70g nucleating agent (CaCO) 3 ) 1kg of filler (ABS, tianjin staphylol DG-417), 300g of compatibilizer (ABS-g-MAH, nantongming Yang Sujiao), 100g of hydrolysis resistant agent (Shanghai Langyi, hyMax 1010), 100g of antistatic agent (M550, tenmozaar chemical) and 20g of antioxidant (1010, BASF).
The preparation method of the high-resilience low-shrinkage polyurethane foaming bead comprises the following steps:
putting the TPU, the nucleating agent, the filler and the compatilizer into an oven at 80 ℃ for drying for 4 hours, then adding the TPU, the nucleating agent, the filler, the compatilizer, the hydrolysis resistance agent, the antistatic agent and the antioxidant into a color mixer, and mixing for 10 minutes at the rotating speed of 60r/min to obtain a uniformly dispersed mixed material.
And extruding the mixture by a double-screw extruder, and carrying out underwater grain cutting by a grain cutter to obtain the polyurethane particles. Wherein the feeding rotating speed of the double-screw extruder is 30r/min, and the rotating speed of the double-screw main machine is 200r/min. The temperature of the screw feeding section is 160 ℃; the temperature of the melting section is 180 ℃; the metering section temperature was 175 ℃. The melt pump speed was 12 r/min. The screen changer, the melt pump, the start valve and the die head of the double-screw extruder are at 180 ℃. The rotating speed of the granulator is 1300r/min, and the temperature of circulating cooling water is 18 ℃.
Putting the polyurethane particles into a reaction kettle with constant temperature T, and filling supercritical CO 2 Performing permeation and swelling to reach an equilibrium state to form a polymer-supercritical fluid homogeneous phase system; wherein water is used as medium, the temperature is set to be 115 ℃, and CO is adopted 2 The pressure of (A) was 10MPa, and CO was adjusted to 2 The soaking time of (2) was 0.5h.
The foaming was carried out at a rate of 6MPa/s, giving 20 times the weight of the polyurethane expanded beads.
Comparative example 1
The high resilience low shrinkage polyurethane expanded beads of comparative example 1, which used polyurethane particles different from those of example 2, did not include a nucleating agent and the other ingredients were unchanged. The method comprises the following steps: 9kg of TPU (HF-4085), 500g of filler (ABS, tianjin staphylol DG-417), 300g of compatibilizer (ABS-g-MAH, nantongming Yang Sujiao), 100g of hydrolysis resistant agent (Shanghai Langyi, hyMax 1010), 100g of antistatic agent (M550, tenmoya chemical industry) and 20g of antioxidant (1010, BASF).
The preparation method is the same as that of example 1.
The SEM image of the cross section of the expanded beads prepared in comparative example 1 is shown in FIG. 2, and it can be seen from FIG. 2 that the pore size of the expanded beads is about 10 μm. The prepared foaming bead has small aperture, less gas is contained in the middle of the foam hole, and only a small part of gas can be remained after the gas is exchanged with air in the pressure maintaining process, so that the foaming material prepared by the bead has poor resilience and high shrinkage.
Comparative example 2
The high resilience low shrinkage polyurethane expanded bead of comparative example 2, which employs polyurethane particles comprising: 8.5kg TPU (HF-4085), 70g nucleating agent (CaCO) 3 ) 300g of compatibilizer (ABS-g-MAH, nantong Ming Yang Sujiao), 100g of hydrolysis resistant agent (Shanghai Langyi, hyMax 1010), 100g of antistatic agent (M550, tenmoya chemical industry) and 20g of antioxidant (1010, BASF).
The preparation method is the same as in example 2.
The properties of the high resilience low shrinkage polyurethane expanded beads prepared in example 1~3 and comparative example 1~2 are shown in table 1. Wherein the melt flow rate of the polyurethane particles at 190 ℃ under a load of 5kg was measured by the method in ASTM D1238. The compression set was tested using the method of GB/T6669-2008.
TABLE 1 Performance data for example 1~3 and comparative example 1~2
As can be seen from Table 1, compared with the rebound resilience of the comparative example of 46 to 56%, the rebound resilience of the high-rebound and low-shrinkage polyurethane foam bead provided by the invention is 59 to 62%, and the rebound resilience is obviously improved. Meanwhile, the shrinkage rate of the comparative example is 9 to 20 percent, while the shrinkage rate of the high-resilience low-shrinkage polyurethane foaming bead provided by the invention is 5~9 percent, and the shrinkage rate is obviously reduced. The melt index of the polyurethane particles of the comparative examples is 16 to 20, while the melt index of the polyurethane particles of the present invention is 11 to 12. The polyurethane particle polymer with low melt index has high melt strength, and can better support a foam cell structure in the foaming process, so that the prepared foaming material has low shrinkage. Therefore, the high-resilience low-shrinkage polyurethane foaming bead provided by the invention has good resilience and low shrinkage, and the application field of the high-resilience low-shrinkage polyurethane foaming bead is widened.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. The high-resilience low-shrinkage polyurethane foamed bead is characterized by being prepared from polyurethane particles; the polyurethane particle comprises the following components in parts by weight,
TPU:80 to 100 parts;
nucleating agent: 0.1 to 2 parts;
a compatilizer: 2~5 parts;
filling: 5 to 10 parts;
wherein the TPU comprises the structure:
wherein m, n and p are positive integers, and the hard segment content is 50-70%; and the melt flow rate of the TPU is 15 to 25g/10min at 190 ℃ under the condition of 5kg of load.
2. The high resilience low shrinkage polyurethane expanded bead according to claim 1, further comprising the following components in parts by weight,
hydrolysis resistance agent: 1~6 parts;
antistatic agent: 1~3 parts;
antioxidant: 0.2 to 1 part.
3. The high resilience low shrinkage polyurethane expanded bead according to claim 1, wherein the filler comprises one or more of POE, ABS, AS, talc, barium sulfate and silica micropowder.
4. The high resilience low shrinkage polyurethane expanded bead according to claim 1, wherein the nucleating agent comprises GMS, tiO 2 And CaCO 3 And the grain diameter of the nucleating agent is 50 to 100nm.
5. The high resilience low shrinkage polyurethane expanded beads according to claim 1, wherein the compatibilizer comprises ABS-g-MAH and/or DCP.
6. The high resilience low shrinkage polyurethane expanded bead according to claim 1, wherein the hydrolysis resistance agent comprises polycarbodiimide and/or epoxy compound.
7. The high resilience low shrinkage polyurethane expanded bead as claimed in claim 1, wherein the antistatic agent is a compound containing a quaternary ammonium salt as a main component, including TXP-10, FA14 or M550.
8. The high resilience low shrinkage polyurethane expanded bead according to claim 1, wherein the antioxidant comprises antioxidant 1010 and/or antioxidant 168.
9. The high resilience low shrinkage polyurethane expanded bead according to claim 1, wherein the polyurethane particles are prepared by a method comprising,
putting the TPU, the nucleating agent, the compatilizer and the filler into an oven at the temperature of 80-90 ℃ and drying for 4-6 h;
putting the dried TPU, the nucleating agent, the compatilizer and the filler into a color mixer, and mixing for 5-10 min at the rotating speed of 50-100r/min to obtain a uniformly dispersed mixture;
extruding the mixture by a double-screw extruder, and carrying out underwater grain cutting by a grain cutter to obtain the polyurethane particles; wherein the feeding rotating speed of the double-screw extruder is 35 to 40r/min, and the rotating speed of the double-screw host is 150 to 220r/min; the temperature of a feeding section of the screw is 170 to 200 ℃, the temperature of a melting section is 190 to 210 ℃, the temperature of a metering section is 170 to 200 ℃, and the rotating speed of a melt pump is 10 to 25 r/min; the temperature of a screen changer, a melt pump, a start valve and a die head of the double-screw extruder is 200 to 220 ℃; the rotating speed of the granulator is 1000 to 2000r/min; the temperature of the circulating cooling water is 5 to 20 ℃.
10. A preparation method of high-resilience low-shrinkage polyurethane foaming beads is characterized by comprising the following steps,
the polyurethane particles according to claim 1 are put into a reaction vessel with a constant temperature T, and supercritical CO is charged 2 Performing permeation and swelling to reach an equilibrium state to form a polymer-supercritical fluid homogeneous phase system; wherein the temperature is set to be 90 to 120 ℃ by taking water as a medium, and CO is added 2 The pressure of the mixture is 9 to 12Mpa 2 The infiltration time of (a) is 0.5 to 2h;
and (3) carrying out pressure relief foaming at the speed of 5-10Mpa/s to obtain the high-resilience low-shrinkage polyurethane foaming bead of 8-20 times.
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