TPE supercritical microcellular foam and preparation method thereof
阅读说明：本技术 一种tpe超临界微孔发泡物及其制备方法 (TPE supercritical microcellular foam and preparation method thereof ) 是由 胡志飞 郑孙兴 李图文 于 2021-07-16 设计创作，主要内容包括：本发明公开了一种TPE超临界微孔发泡物及其制备方法,涉及微孔发泡技术领域,其技术方案要点包括如下重量份的组分：热塑性弹性体54-82份；混合聚体16-20份；浸润剂6-8份；硅烷偶联剂2.2-2.6份；纳米氮化硼颗粒12-18份。本发明具有获得结构稳定、制备便捷且避免环境污染的TPE超临界微孔发泡物；其中,纳米氮化硼颗粒中的六方氮化硼颗粒、菱方氮化硼颗粒和立方氮化硼颗粒通过六方氮化硼颗粒的石墨型层状结构以及立方氮化硼颗粒的硬度结合作为填料,并在热塑性弹性体和混合聚体的共混下,使得该TPE超临界微孔发泡物具有结构强度大且稳定的效果,并有效避免污染物的使用。(The invention discloses a TPE supercritical microcellular foam and a preparation method thereof, relating to the technical field of microcellular foam, and the technical scheme is characterized by comprising the following components in parts by weight: 54-82 parts of thermoplastic elastomer; 16-20 parts of mixed polymer; 6-8 parts of a sizing agent; 2.2-2.6 parts of a silane coupling agent; 12-18 parts of nano boron nitride particles. The invention has the advantages that the TPE supercritical microcellular foam which has stable structure, convenient preparation and no environmental pollution is obtained; the hexagonal boron nitride particles, the rhombic boron nitride particles and the cubic boron nitride particles in the nano boron nitride particles are combined to be used as fillers through the graphite type layered structure of the hexagonal boron nitride particles and the hardness of the cubic boron nitride particles, and under the blending of the thermoplastic elastomer and the mixed polymer, the TPE supercritical microporous foam has the effects of high structural strength and stability, and the use of pollutants is effectively avoided.)
1. The TPE supercritical microcellular foam is characterized by comprising the following components in parts by weight:
54-82 parts of thermoplastic elastomer;
16-20 parts of mixed polymer;
6-8 parts of a sizing agent;
2.2-2.6 parts of a silane coupling agent;
12-18 parts of nano boron nitride particles;
wherein:
the mixed polymer consists of a polyvinylidene chloride homopolymer, an ethylene-vinyl ester copolymer saponified substance and acrylonitrile, wherein the ethylene-vinyl ester copolymer saponified substance is obtained by copolymerizing ethylene and a vinyl ester monomer and then saponifying;
the nanometer boron nitride particles comprise hexagonal boron nitride particles, rhombohedral boron nitride particles and cubic boron nitride particles, and the weight ratio of the hexagonal boron nitride particles to the rhombohedral boron nitride particles to the cubic boron nitride particles is 4:0.2-0.6: 0.8-1.2.
2. The TPE supercritical microcellular foam according to claim 1, wherein: the modified hollow glass bead is prepared from the following components in parts by weight:
s1, surface etching: placing hollow glass beads with the model number of K37, K38 or K46 into a closed stirrer for continuous stirring, introducing hydrofluoric acid gas into the stirrer, and ionizing the fluorine-containing gas in the stirrer to generate charged substances to react with the surfaces of the hollow glass beads, wherein the temperature in the stirrer is controlled to be 25-50 ℃;
s2, preparation for modification: taking NH3And heating to 35-40 ℃;
s3, surface modification: heating NH to 35-40 ℃3And (3) introducing the glass beads into a stirrer loaded with the hollow glass beads with the etched surfaces for activation, and obtaining the modified hollow glass beads after 2-6 hours.
3. The TPE supercritical microcellular foam according to claim 1, wherein: the thermoplastic elastomer is one or more of polycarbonate-ester amide, styrene block copolymer SBC and polyether ester thermoplastic elastomer Hytrel.
4. The TPE supercritical microcellular foam according to claim 1, wherein: the impregnating compound is one of polyvinyl acetate, acrylate emulsion, polyurethane emulsion and polyether polyol.
5. The TPE supercritical microcellular foam according to claim 1, wherein: the ratio of the hexagonal boron nitride particles to the rhombohedral boron nitride particles to the cubic boron nitride particles is 20:2:5 by weight.
6. A preparation method of TPE supercritical microcellular foam is characterized by comprising the following steps:
step 1, mixing: adding 54-82 parts by weight of thermoplastic elastomer, 16-20 parts by weight of mixed polymer, 6-8 parts by weight of impregnating compound, 2.2-2.6 parts by weight of silane coupling agent and 12-18 parts by weight of nano boron nitride particles into a mixer for mixing, and controlling the temperature of the mixer to be 40-60 ℃ to obtain a mixed material;
step 2, granulation: introducing the mixed material into a double-screw extruder to obtain particles A;
step 3, transformation: banburying and granulating the particles A and 10-12 parts by weight of modified hollow glass microspheres to obtain particles B;
step 4, tabletting: compacting the particles B in a vulcanizing press to obtain a flaky parison;
and 5, supercritical: carrying out high-pressure infiltration on the sheet-shaped blank by using a supercritical fluid, wherein the pressure of the high-pressure infiltration is 12MPa, and when the pressure reaches the maximum pressure, releasing the pressure to the normal pressure to obtain a supercritical foaming blank;
step 6, foaming: placing the supercritical foaming blank into a foaming device for foaming, releasing the pressure after the gas reaches the saturation required pressure of 20MPa, taking out the supercritical foaming blank and cutting the supercritical foaming blank to obtain a TPE (thermoplastic elastomer) supercritical microcellular foamed product finished product;
wherein the modified hollow glass bead is obtained by the following steps:
s1, surface etching: placing hollow glass beads with the model number of K37, K38 or K46 into a closed stirrer for continuous stirring, introducing hydrofluoric acid gas into the stirrer, and ionizing the fluorine-containing gas in the stirrer to generate charged substances to react with the surfaces of the hollow glass beads, wherein the temperature in the stirrer is controlled to be 25-50 ℃;
s2, preparation for modification: taking NH3And heating to 35-40 ℃;
s3, surface modification: heating NH to 35-40 ℃3And (3) introducing the glass beads into a stirrer loaded with the hollow glass beads with the etched surfaces for activation, and obtaining the modified hollow glass beads after 2-6 hours.
7. The method for preparing a TPE supercritical microcellular foam according to claim 6, wherein: the mixed polymer consists of a polyvinylidene chloride homopolymer, an ethylene-vinyl ester copolymer saponified substance and acrylonitrile, wherein the ethylene-vinyl ester copolymer saponified substance is obtained by copolymerizing ethylene and a vinyl ester monomer and then saponifying; the nanometer boron nitride particles comprise hexagonal boron nitride particles, rhombohedral boron nitride particles and cubic boron nitride particles, and the weight ratio of the hexagonal boron nitride particles to the rhombohedral boron nitride particles to the cubic boron nitride particles is 4:0.2-0.6: 0.8-1.2.
8. The method for preparing a TPE supercritical microcellular foam according to claim 6, wherein: the impregnating compound is one of polyvinyl acetate, acrylate emulsion, polyurethane emulsion and polyether polyol.
9. The method for preparing a TPE supercritical microcellular foam according to claim 6, wherein: the foaming device comprises a lower die and an upper die, wherein a lower side groove is formed in the upper side of the lower die, an upper side block is arranged on the lower side of the upper die, and the upper side block is inserted into the lower side cavity and forms a foaming inner cavity for foaming; the upper side of the lower die is also provided with a sealing ring groove positioned on one side of the periphery of the lower side type groove, a sealing gasket is arranged in the sealing ring groove, and the sealing gasket is used for abutting against the upper die and sealing a gap between the upper die and the lower die when the upper die and the lower die abut against each other; the upper die is provided with a plurality of ventilation cavities, and the ventilation cavities are communicated with the foaming inner cavity.
10. The method of claim 9, wherein the TPE supercritical microcellular foam comprises: vent holes which are sequentially communicated are formed among the vent cavities, a plurality of connecting holes which are respectively matched with the corresponding vent cavities are formed in the upper side of the upper die, a butt opening and closing table with the inner diameter smaller than that of the vent cavities is arranged on the lower side of the vent cavities, and a through groove with the inner diameter larger than that of the vent cavities is formed in the lower side of the butt opening and closing table; a movable opening and closing piece is inserted into the ventilation cavity, the movable opening and closing piece is sleeved with an elastic piece, the upper end of the elastic piece is abutted against the tail end of the movable opening and closing piece, and the lower end of the elastic piece is abutted against the upper side of the abutting opening and closing table; the movable opening and closing piece is provided with a sealing cover which is positioned on the lower side of the butt opening and closing platform and is used for being in butt joint with the butt opening and closing platform.
Technical Field
The invention relates to the technical field of microcellular foaming, in particular to a TPE supercritical microcellular foam and a preparation method thereof.
Background
The polymer microcellular foaming material means that the diameter of cells is less than 10 mu m, and the density of the cells is more than 109 cells/cm3The material has good impact toughness, fatigue resistance, heat resistance, low dielectric constant and conductivity, and can be used as insulating materials, separation media, adsorbents, packaging materials, biomedical materials, light pressure-resistant anti-seismic materials and the like. The teaching of n.p.suh of the american academy of labor for massages in 1980 was first proposed: when the cell size in the polymer is smaller than the internal defects of the material, the presence of the cells does not reduce the strength of the material, but instead the micropores can passivate the crack tips when the crack propagates under stress conditions, preventing further propagation of the crack and thus improving some of the properties of the material. The polymer cell morphology largely determines the properties and application areas of the foam.
The Chinese patent with the publication number of CN101508747B discloses a melamine modified polyvinyl formal foam material and a preparation method and application thereof, and the melamine modified polyvinyl formal foam material is characterized by being mainly prepared by mixing and reacting the following raw materials in parts by weight: 100 parts of polyvinyl alcohol, 0.1-20 parts of melamine, 20-100 parts of formaldehyde, 300-1200 parts of water, 0-80 parts of pore-forming agent, 0-10 parts of alkaline catalyst, 0.1-10 parts of emulsifier, 0-10 parts of foaming agent, 30-400 parts of acidic catalyst and 0-20 parts of auxiliary agent. Wherein the pore-forming agent comprises at least one of wheat starch, potato starch, corn starch and paste thereof.
Therefore, in the preparation process of the melamine modified polyvinyl formal foam material, the starch particles are used as the pore-forming agent, so that the step of cleaning the material is needed after the acetalization reaction of the material is completed, the step is difficult to remove the chemical residues in the material, the water consumption is high, the waste liquid is difficult to treat, the environmental protection is further influenced, the requirements of green and environmental protection are not met, and meanwhile, the potential safety hazard is easily brought to be improved.
Disclosure of Invention
In view of the defects in the prior art, the first object of the present invention is to provide a TPE supercritical microcellular foam, which has the effects of stable structure, convenient preparation and environmental pollution avoidance.
In order to achieve the purpose, the invention provides the following technical scheme:
the TPE supercritical microcellular foam comprises the following components in parts by weight:
54-82 parts of thermoplastic elastomer;
16-20 parts of mixed polymer;
6-8 parts of a sizing agent;
2.2-2.6 parts of a silane coupling agent;
12-18 parts of nano boron nitride particles;
wherein:
the mixed polymer consists of a polyvinylidene chloride homopolymer, an ethylene-vinyl ester copolymer saponified substance and acrylonitrile, wherein the ethylene-vinyl ester copolymer saponified substance is obtained by copolymerizing ethylene and a vinyl ester monomer and then saponifying;
the nanometer boron nitride particles comprise hexagonal boron nitride particles, rhombohedral boron nitride particles and cubic boron nitride particles, and the weight ratio of the hexagonal boron nitride particles to the rhombohedral boron nitride particles to the cubic boron nitride particles is 4:0.2-0.6: 0.8-1.2.
By adopting the technical scheme, the TPE supercritical microcellular foam which is stable in structure, convenient and fast to prepare and capable of avoiding environmental pollution is obtained; the hexagonal boron nitride particles, the rhombic boron nitride particles and the cubic boron nitride particles in the nano boron nitride particles are combined to be used as fillers through the graphite type layered structure of the hexagonal boron nitride particles and the hardness of the cubic boron nitride particles, and under the blending of the thermoplastic elastomer and the mixed polymer, the TPE supercritical microporous foam has the effects of high structural strength and stability, and the use of pollutants is effectively avoided.
The invention is further configured to: the modified hollow glass bead is prepared from the following components in parts by weight:
s1, surface etching: placing hollow glass beads with the model number of K37, K38 or K46 into a closed stirrer for continuous stirring, introducing hydrofluoric acid gas into the stirrer, and ionizing the fluorine-containing gas in the stirrer to generate charged substances to react with the surfaces of the hollow glass beads, wherein the temperature in the stirrer is controlled to be 25-50 ℃;
s2, preparation for modification: taking NH3And heating to 35-40 ℃;
s3, surface modification: heating NH to 35-40 ℃3And (3) introducing the glass beads into a stirrer loaded with the hollow glass beads with the etched surfaces for activation, and obtaining the modified hollow glass beads after 2-6 hours.
The invention is further configured to: the thermoplastic elastomer is one or more of polycarbonate-ester amide, styrene block copolymer SBC and polyether ester thermoplastic elastomer Hytrel.
The invention is further configured to: the impregnating compound is one of polyvinyl acetate, acrylate emulsion, polyurethane emulsion and polyether polyol.
The invention is further configured to: the ratio of the hexagonal boron nitride particles to the rhombohedral boron nitride particles to the cubic boron nitride particles is 20:2:5 by weight.
The second purpose of the invention is to provide a preparation method of TPE supercritical microcellular foam, which comprises the following steps:
step 1, mixing: adding 54-82 parts by weight of thermoplastic elastomer, 16-20 parts by weight of mixed polymer, 6-8 parts by weight of impregnating compound, 2.2-2.6 parts by weight of silane coupling agent and 12-18 parts by weight of nano boron nitride particles into a mixer for mixing, and controlling the temperature of the mixer to be 40-60 ℃ to obtain a mixed material;
step 2, granulation: introducing the mixed material into a double-screw extruder to obtain particles A;
step 3, transformation: banburying and granulating the particles A and 10-12 parts by weight of modified hollow glass microspheres to obtain particles B;
step 4, tabletting: compacting the particles B in a vulcanizing press to obtain a flaky parison;
and 5, supercritical: carrying out high-pressure infiltration on the sheet-shaped blank by using a supercritical fluid, wherein the pressure of the high-pressure infiltration is 12MPa, and when the pressure reaches the maximum pressure, releasing the pressure to the normal pressure to obtain a supercritical foaming blank;
step 6, foaming: placing the supercritical foaming blank into a foaming device for foaming, releasing the pressure after the gas reaches the saturation required pressure of 20MPa, taking out the supercritical foaming blank and cutting the supercritical foaming blank to obtain a TPE (thermoplastic elastomer) supercritical microcellular foamed product finished product;
wherein the modified hollow glass bead is obtained by the following steps:
s1, surface etching: placing hollow glass beads with the model number of K37, K38 or K46 into a closed stirrer for continuous stirring, introducing hydrofluoric acid gas into the stirrer, and ionizing the fluorine-containing gas in the stirrer to generate charged substances to react with the surfaces of the hollow glass beads, wherein the temperature in the stirrer is controlled to be 25-50 ℃;
s2, preparation for modification: taking NH3And heating to 35-40 ℃;
s3, surface modification: heating NH to 35-40 ℃3And (3) introducing the glass beads into a stirrer loaded with the hollow glass beads with the etched surfaces for activation, and obtaining the modified hollow glass beads after 2-6 hours.
The invention is further configured to: the mixed polymer consists of a polyvinylidene chloride homopolymer, an ethylene-vinyl ester copolymer saponified substance and acrylonitrile, wherein the ethylene-vinyl ester copolymer saponified substance is obtained by copolymerizing ethylene and a vinyl ester monomer and then saponifying; the nanometer boron nitride particles comprise hexagonal boron nitride particles, rhombohedral boron nitride particles and cubic boron nitride particles, and the weight ratio of the hexagonal boron nitride particles to the rhombohedral boron nitride particles to the cubic boron nitride particles is 4:0.2-0.6: 0.8-1.2.
The invention is further configured to: the impregnating compound is one of polyvinyl acetate, acrylate emulsion, polyurethane emulsion and polyether polyol.
The invention is further configured to: the foaming device comprises a lower die and an upper die, wherein a lower side groove is formed in the upper side of the lower die, an upper side block is arranged on the lower side of the upper die, and the upper side block is inserted into the lower side cavity and forms a foaming inner cavity for foaming; the upper side of the lower die is also provided with a sealing ring groove positioned on one side of the periphery of the lower side type groove, a sealing gasket is arranged in the sealing ring groove, and the sealing gasket is used for abutting against the upper die and sealing a gap between the upper die and the lower die when the upper die and the lower die abut against each other; the upper die is provided with a plurality of ventilation cavities, and the ventilation cavities are communicated with the foaming inner cavity.
By adopting the technical scheme, the upper die and the lower die are matched with each other to form a foaming inner cavity for preparing the TPE supercritical microcellular foam, and then the pressure of the supercritical fluid in the foaming inner cavity is increased through the ventilation cavity so as to complete convenient preparation of the TPE supercritical microcellular foam.
The invention is further configured to: vent holes which are sequentially communicated are formed among the vent cavities, a plurality of connecting holes which are respectively matched with the corresponding vent cavities are formed in the upper side of the upper die, a butt opening and closing table with the inner diameter smaller than that of the vent cavities is arranged on the lower side of the vent cavities, and a through groove with the inner diameter larger than that of the vent cavities is formed in the lower side of the butt opening and closing table; a movable opening and closing piece is inserted into the ventilation cavity, the movable opening and closing piece is sleeved with an elastic piece, the upper end of the elastic piece is abutted against the tail end of the movable opening and closing piece, and the lower end of the elastic piece is abutted against the upper side of the abutting opening and closing table; the movable opening and closing piece is provided with a sealing cover which is positioned on the lower side of the butt opening and closing platform and is used for being in butt joint with the butt opening and closing platform.
Through adopting above-mentioned technical scheme, the air vent communicates a plurality of air vent chamber in proper order, and then reaches the pressure of effective balanced foaming inner chamber to when rising the supercritical fluid's of foaming inner chamber pressure, the cooperation is removed and is opened and close the platform with the butt on the piece and realize effective control and regulation to pressure, further promotes the preparation convenience of this TPE supercritical micropore foaming thing.
In conclusion, the invention has the following beneficial effects: by optimizing the composition of the TPE supercritical microcellular foam, combining nano boron nitride particles comprising hexagonal boron nitride particles, rhombic boron nitride particles and cubic boron nitride particles in a set proportion with a thermoplastic elastomer, a mixed polymer and other additives, and sequentially carrying out mixing, granulation, transformation, tabletting, supercritical and foaming, the TPE supercritical microcellular foam which is stable in structure, convenient to prepare and capable of avoiding environmental pollution is obtained; meanwhile, the foaming device is optimized, and the purpose of effectively improving the preparation convenience of the TPE supercritical microcellular foam is achieved.
Drawings
FIG. 1 is a schematic structural view of the present embodiment;
fig. 2 is an enlarged schematic view of a portion a of fig. 1.
Description of reference numerals: 1. a lower die; 11. a lower side profiled groove; 12. sealing the ring groove; 2. an upper die; 21. an upper profile block; 22. a vent hole; 23. connecting holes; 24. a vent lumen; 25. an elastic member; 26. moving the opening and closing piece; 261. a sealing cover; 27. abutting against the opening and closing platform; 28. a through groove; 3. a gasket; 4. a foaming inner cavity.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present application, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The following is a detailed description of the TPE supercritical microcellular foam and the preparation method thereof according to the embodiment of the present invention:
the TPE supercritical microcellular foam comprises the following components in parts by weight:
54-82 parts of thermoplastic elastomer, 16-20 parts of mixed polymer, 10-12 parts of modified hollow glass microspheres, 6-8 parts of impregnating compound, 2.2-2.6 parts of silane coupling agent and 12-18 parts of nano boron nitride particles.
The thermoplastic elastomer is one or more of polycarbonate-ester amide, styrene block copolymer SBC and polyether ester thermoplastic elastomer Hytrel.
The mixed polymer consists of a polyvinylidene chloride homopolymer, an ethylene-vinyl ester copolymer saponified substance and acrylonitrile, wherein the ethylene-vinyl ester copolymer saponified substance is obtained by copolymerizing ethylene and a vinyl ester monomer and then saponifying.
The impregnating compound is one of polyvinyl acetate, acrylate emulsion, polyurethane emulsion and polyether polyol.
The nano boron nitride particles comprise hexagonal boron nitride particles, rhombohedral boron nitride particles and cubic boron nitride particles, and the weight ratio of the hexagonal boron nitride particles to the rhombohedral boron nitride particles to the cubic boron nitride particles is 4:0.2-0.6: 0.8-1.2.
Therefore, the TPE supercritical microcellular foam which has stable structure, convenient preparation and no environmental pollution is obtained. The hexagonal boron nitride particles, the rhombic boron nitride particles and the cubic boron nitride particles in the nano boron nitride particles are combined to be used as fillers through the graphite type layered structure of the hexagonal boron nitride particles and the hardness of the cubic boron nitride particles, and under the blending of the thermoplastic elastomer and the mixed polymer, the TPE supercritical microporous foam has the effects of high structural strength and stability, and the use of pollutants is effectively avoided.
It is to be mentioned that the modified hollow glass microspheres are obtained by the following steps:
s1, surface etching: placing hollow glass beads with the model number of K37, K38 or K46 into a closed stirrer for continuous stirring, introducing hydrofluoric acid gas into the stirrer, and ionizing the fluorine-containing gas in the stirrer to generate charged substances to react with the surfaces of the hollow glass beads, wherein the temperature in the stirrer is controlled to be 25-50 ℃;
s2, preparation for modification: taking NH3And heating to 35-40 ℃;
s3, surface modification: heating NH to 35-40 ℃3And (3) introducing the glass beads into a stirrer loaded with the hollow glass beads with the etched surfaces for activation, and obtaining the modified hollow glass beads after 2-6 hours.
A preparation method of TPE supercritical microcellular foam comprises the following steps:
step 1, mixing: adding 54-82 parts by weight of thermoplastic elastomer, 16-20 parts by weight of mixed polymer, 6-8 parts by weight of impregnating compound, 2.2-2.6 parts by weight of silane coupling agent and 12-18 parts by weight of nano boron nitride particles into a mixer for mixing, and controlling the temperature of the mixer to be 40-60 ℃ to obtain a mixed material;
step 2, granulation: introducing the mixed material into a double-screw extruder to obtain particles A;
step 3, transformation: banburying and granulating the particles A and 10-12 parts by weight of modified hollow glass microspheres to obtain particles B;
step 4, tabletting: compacting the particles B in a vulcanizing press to obtain a flaky parison;
and 5, supercritical: carrying out high-pressure infiltration on the sheet-shaped blank by using a supercritical fluid, wherein the pressure of the high-pressure infiltration is 12MPa, and when the pressure reaches the maximum pressure, releasing the pressure to the normal pressure to obtain a supercritical foaming blank;
step 6, foaming: placing the supercritical foaming blank into a foaming device for foaming, releasing the pressure after the gas reaches the saturation required pressure of 20MPa, taking out the supercritical foaming blank and cutting the supercritical foaming blank to obtain a TPE (thermoplastic elastomer) supercritical microcellular foamed product finished product;
as shown in fig. 1 and 2, the foaming device includes a lower die 1 and an upper die 2. The lower die 1 is provided with a lower profiled groove 11 on the upper side and an upper profiled block 21 on the lower side of the upper die 2. Wherein the upper mould block 21 is inserted into the lower mould cavity and forms a foaming cavity 4 for foaming. The upper side of the lower die 1 is also provided with a sealing ring groove 12 positioned on one side of the periphery of the lower side type groove 11. A sealing gasket 3 is arranged in the sealing ring groove 12, and the sealing gasket 3 is used for being abutted against the upper die 2 and sealing a gap between the upper die 2 and the lower die 1 when the upper die 2 is abutted against the lower die 1. Meanwhile, a plurality of vent chambers 24 are provided in the upper die 2. The ventilation cavity 24 is communicated with the foaming inner cavity 4, so that when the upper die 2 and the lower die 1 are matched with each other and form the foaming inner cavity 4 for preparing the TPE supercritical microcellular foam, the pressure of the supercritical fluid in the foaming inner cavity 4 is increased through the ventilation cavity 24, and the convenient preparation of the TPE supercritical microcellular foam is completed. It should be mentioned that the plurality of vent chambers 24 are provided with vent holes 22 communicating in sequence therebetween, and the upper mold 2 is provided at the upper side thereof with a plurality of connection holes 23 respectively matching with the respective vent chambers 24.
As shown in fig. 2, an abutment opening/closing table 27 having an inner diameter smaller than that of the vent chamber 24 is provided below the vent chamber 24, and a through groove 28 having an inner diameter larger than that of the vent chamber 24 is provided below the abutment opening/closing table 27. A moving shutter 26 is inserted in the vent lumen 24. The movable shutter 26 is fitted with an elastic member 25, and the upper end of the elastic member 25 abuts against the rear end of the movable shutter 26 and the lower end abuts against the upper side of the abutting opening/closing table 27. The elastic member 25 is an elastic object, and a spring is generally used to reduce the cost. The movable shutter 26 is provided with a seal cover 261 which is located below the abutment opening/closing table 27 and abuts against the abutment opening/closing table 27. Therefore, the vent holes 22 are sequentially communicated with the plurality of vent cavities 24, so that the pressure in the foaming inner cavity 4 is effectively balanced, when the pressure of the supercritical fluid in the foaming inner cavity 4 is increased, the sealing cover 261 on the opening and closing piece 26 is moved in a matched manner, and the opening and closing table 27 is abutted to realize effective control and adjustment of the pressure, so that the preparation convenience of the TPE supercritical microcellular foam is further improved.
Example one
The TPE supercritical microcellular foam comprises the following components in parts by weight:
54 parts of polycarbonate-ester amide, 16 parts of polyvinylidene chloride homopolymer, ethylene-vinyl ester copolymer saponified product and acrylonitrile in a weight part ratio of 1:1:1, 10 parts of modified hollow glass beads, 6 parts of acrylate emulsion, 2.2 parts of silane coupling agent, 12 parts of hexagonal boron nitride particles, rhombic boron nitride particles and cubic boron nitride particles in a weight part ratio of 20:1: 4.
Therefore, the TPE supercritical microcellular foam which has stable structure, convenient preparation and no environmental pollution is obtained. The hexagonal boron nitride particles, the rhombic boron nitride particles and the cubic boron nitride particles in the nano boron nitride particles are combined to be used as fillers through the graphite type layered structure of the hexagonal boron nitride particles and the hardness of the cubic boron nitride particles, and under the blending of the thermoplastic elastomer and the mixed polymer, the TPE supercritical microporous foam has the effects of high structural strength and stability, and the use of pollutants is effectively avoided.
It is to be mentioned that the modified hollow glass microspheres are obtained by the following steps:
s1, surface etching: putting hollow glass beads with the model number of K37 into a closed stirrer for continuous stirring, introducing hydrofluoric acid gas into the stirrer, ionizing the fluorine-containing gas in the stirrer to generate charged substances to react with the surfaces of the hollow glass beads, wherein the temperature in the stirrer is controlled to be 25 ℃;
s2, preparation for modification: taking NH3And heated to 35 ℃;
s3, surface modification: heating to 35 ℃ NH3And (3) introducing the glass beads into a stirrer loaded with the hollow glass beads with the etched surfaces for activation, and obtaining the modified hollow glass beads after 6 hours.
A preparation method of TPE supercritical microcellular foam comprises the following steps:
step 1, mixing: 54 parts of polycarbonate-ester amide, 16 parts of polyvinylidene chloride homopolymer, ethylene-vinyl ester copolymer saponified substance and acrylonitrile in a weight ratio of 1:1:1, 6 parts of wetting agent, 2.2 parts of silane coupling agent, and 12 parts of hexagonal boron nitride particles, rhombic boron nitride particles and cubic boron nitride particles in a weight ratio of 20:1:4 are added into a mixer to be mixed, and the temperature of the mixer is controlled at 40 ℃ to obtain a mixed material;
step 2, granulation: introducing the mixed material into a double-screw extruder to obtain particles A;
step 3, transformation: banburying and granulating the particles A and 10 parts by weight of modified hollow glass beads to obtain particles B;
step 4, tabletting: compacting the particles B in a vulcanizing press to obtain a flaky parison;
and 5, supercritical: carrying out high-pressure infiltration on the sheet-shaped blank by using a supercritical fluid, wherein the pressure of the high-pressure infiltration is 12MPa, and when the pressure reaches the maximum pressure, releasing the pressure to the normal pressure to obtain a supercritical foaming blank;
step 6, foaming: placing the supercritical foaming blank into a foaming device for foaming, releasing the pressure after the gas reaches the saturation required pressure of 20MPa, taking out the supercritical foaming blank and cutting the supercritical foaming blank to obtain a TPE (thermoplastic elastomer) supercritical microcellular foamed product finished product;
as shown in fig. 1 and 2, the foaming device includes a lower die 1 and an upper die 2. The lower die 1 is provided with a lower profiled groove 11 on the upper side and an upper profiled block 21 on the lower side of the upper die 2. Wherein the upper mould block 21 is inserted into the lower mould cavity and forms a foaming cavity 4 for foaming. The upper side of the lower die 1 is also provided with a sealing ring groove 12 positioned on one side of the periphery of the lower side type groove 11. A sealing gasket 3 is arranged in the sealing ring groove 12, and the sealing gasket 3 is used for being abutted against the upper die 2 and sealing a gap between the upper die 2 and the lower die 1 when the upper die 2 is abutted against the lower die 1. Meanwhile, a plurality of vent chambers 24 are provided in the upper die 2. The ventilation cavity 24 is communicated with the foaming inner cavity 4, so that when the upper die 2 and the lower die 1 are matched with each other and form the foaming inner cavity 4 for preparing the TPE supercritical microcellular foam, the pressure of the supercritical fluid in the foaming inner cavity 4 is increased through the ventilation cavity 24, and the convenient preparation of the TPE supercritical microcellular foam is completed. It should be mentioned that the plurality of vent chambers 24 are provided with vent holes 22 communicating in sequence therebetween, and the upper mold 2 is provided at the upper side thereof with a plurality of connection holes 23 respectively matching with the respective vent chambers 24.
As shown in fig. 2, an abutment opening/closing table 27 having an inner diameter smaller than that of the vent chamber 24 is provided below the vent chamber 24, and a through groove 28 having an inner diameter larger than that of the vent chamber 24 is provided below the abutment opening/closing table 27. A moving shutter 26 is inserted in the vent lumen 24. The movable shutter 26 is fitted with an elastic member 25, and the upper end of the elastic member 25 abuts against the rear end of the movable shutter 26 and the lower end abuts against the upper side of the abutting opening/closing table 27. The elastic member 25 is an elastic object, and a spring is generally used to reduce the cost. The movable shutter 26 is provided with a seal cover 261 which is located below the abutment opening/closing table 27 and abuts against the abutment opening/closing table 27. Therefore, the vent holes 22 are sequentially communicated with the plurality of vent cavities 24, so that the pressure in the foaming inner cavity 4 is effectively balanced, when the pressure of the supercritical fluid in the foaming inner cavity 4 is increased, the sealing cover 261 on the opening and closing piece 26 is moved in a matched manner, and the opening and closing table 27 is abutted to realize effective control and adjustment of the pressure, so that the preparation convenience of the TPE supercritical microcellular foam is further improved.
Example two
The TPE supercritical microcellular foam comprises the following components in parts by weight:
68 parts of polyether ester thermoplastic elastomer Hytrel, 18 parts of polyvinylidene chloride homopolymer, ethylene-vinyl ester copolymer saponified product and acrylonitrile in a weight part ratio of 1:1:1, 11 parts of modified hollow glass microspheres, 7 parts of polyether polyol, 2.4 parts of silane coupling agent, 15 parts of hexagonal boron nitride particles, rhombic boron nitride particles and cubic boron nitride particles in a weight part ratio of 20:2: 5.
Therefore, the TPE supercritical microcellular foam which has stable structure, convenient preparation and no environmental pollution is obtained. The hexagonal boron nitride particles, the rhombic boron nitride particles and the cubic boron nitride particles in the nano boron nitride particles are combined to be used as fillers through the graphite type layered structure of the hexagonal boron nitride particles and the hardness of the cubic boron nitride particles, and under the blending of the thermoplastic elastomer and the mixed polymer, the TPE supercritical microporous foam has the effects of high structural strength and stability, and the use of pollutants is effectively avoided.
It is to be mentioned that the modified hollow glass microspheres are obtained by the following steps:
s1, surface etching: putting hollow glass beads with the model number of K38 into a closed stirrer for continuous stirring, introducing hydrofluoric acid gas into the stirrer, and ionizing the fluorine-containing gas in the stirrer to generate charged substances to react with the surfaces of the hollow glass beads, wherein the temperature in the stirrer is controlled to be 38 ℃;
s2, preparation for modification: taking NH3And heated to 38 ℃;
s3, surface modification: heating NH to 38 DEG C3And (4) introducing the glass beads into a stirrer loaded with the hollow glass beads with the etched surfaces for activation, and obtaining the modified hollow glass beads after 4 hours.
A preparation method of TPE supercritical microcellular foam comprises the following steps:
step 1, mixing: taking polyether ester thermoplastic elastomer Hytrel68 parts by weight, polyvinylidene chloride homopolymer, ethylene-vinyl ester copolymer saponified product and acrylonitrile 18 parts by weight, polyether polyol 7 parts by weight, silane coupling agent 2.4 parts by weight, and hexagonal boron nitride particles, rhombic boron nitride particles and cubic boron nitride particles 15 parts by weight in a ratio of 20:2:5, adding into a mixer, and mixing at 50 ℃ to obtain a mixed material;
step 2, granulation: introducing the mixed material into a double-screw extruder to obtain particles A;
step 3, transformation: banburying and granulating the particles A and 11 parts by weight of modified hollow glass beads to obtain particles B;
step 4, tabletting: compacting the particles B in a vulcanizing press to obtain a flaky parison;
and 5, supercritical: carrying out high-pressure infiltration on the sheet-shaped blank by using a supercritical fluid, wherein the pressure of the high-pressure infiltration is 12MPa, and when the pressure reaches the maximum pressure, releasing the pressure to the normal pressure to obtain a supercritical foaming blank;
step 6, foaming: placing the supercritical foaming blank into a foaming device for foaming, releasing the pressure after the gas reaches the saturation required pressure of 20MPa, taking out the supercritical foaming blank and cutting the supercritical foaming blank to obtain a TPE (thermoplastic elastomer) supercritical microcellular foamed product finished product;
as shown in fig. 1 and 2, the foaming device includes a lower die 1 and an upper die 2. The lower die 1 is provided with a lower profiled groove 11 on the upper side and an upper profiled block 21 on the lower side of the upper die 2. Wherein the upper mould block 21 is inserted into the lower mould cavity and forms a foaming cavity 4 for foaming. The upper side of the lower die 1 is also provided with a sealing ring groove 12 positioned on one side of the periphery of the lower side type groove 11. A sealing gasket 3 is arranged in the sealing ring groove 12, and the sealing gasket 3 is used for being abutted against the upper die 2 and sealing a gap between the upper die 2 and the lower die 1 when the upper die 2 is abutted against the lower die 1. Meanwhile, a plurality of vent chambers 24 are provided in the upper die 2. The ventilation cavity 24 is communicated with the foaming inner cavity 4, so that when the upper die 2 and the lower die 1 are matched with each other and form the foaming inner cavity 4 for preparing the TPE supercritical microcellular foam, the pressure of the supercritical fluid in the foaming inner cavity 4 is increased through the ventilation cavity 24, and the convenient preparation of the TPE supercritical microcellular foam is completed. It should be mentioned that the plurality of vent chambers 24 are provided with vent holes 22 communicating in sequence therebetween, and the upper mold 2 is provided at the upper side thereof with a plurality of connection holes 23 respectively matching with the respective vent chambers 24.
As shown in fig. 2, an abutment opening/closing table 27 having an inner diameter smaller than that of the vent chamber 24 is provided below the vent chamber 24, and a through groove 28 having an inner diameter larger than that of the vent chamber 24 is provided below the abutment opening/closing table 27. A moving shutter 26 is inserted in the vent lumen 24. The movable shutter 26 is fitted with an elastic member 25, and the upper end of the elastic member 25 abuts against the rear end of the movable shutter 26 and the lower end abuts against the upper side of the abutting opening/closing table 27. The elastic member 25 is an elastic object, and a spring is generally used to reduce the cost. The movable shutter 26 is provided with a seal cover 261 which is located below the abutment opening/closing table 27 and abuts against the abutment opening/closing table 27. Therefore, the vent holes 22 are sequentially communicated with the plurality of vent cavities 24, so that the pressure in the foaming inner cavity 4 is effectively balanced, when the pressure of the supercritical fluid in the foaming inner cavity 4 is increased, the sealing cover 261 on the opening and closing piece 26 is moved in a matched manner, and the opening and closing table 27 is abutted to realize effective control and adjustment of the pressure, so that the preparation convenience of the TPE supercritical microcellular foam is further improved.
EXAMPLE III
The TPE supercritical microcellular foam comprises the following components in parts by weight:
82 parts of styrene-based block copolymer SBC, 20 parts of polyvinylidene chloride homopolymer, ethylene-vinyl ester copolymer saponified substance and acrylonitrile according to the weight part ratio of 2:1:1, 12 parts of modified hollow glass microspheres, 8 parts of acrylate emulsion, 2.6 parts of silane coupling agent, 18 parts of hexagonal boron nitride particles, rhombic boron nitride particles and cubic boron nitride particles according to the weight part ratio of 20:3: 6.
Therefore, the TPE supercritical microcellular foam which has stable structure, convenient preparation and no environmental pollution is obtained. The hexagonal boron nitride particles, the rhombic boron nitride particles and the cubic boron nitride particles in the nano boron nitride particles are combined to be used as fillers through the graphite type layered structure of the hexagonal boron nitride particles and the hardness of the cubic boron nitride particles, and under the blending of the thermoplastic elastomer and the mixed polymer, the TPE supercritical microporous foam has the effects of high structural strength and stability, and the use of pollutants is effectively avoided.
It is to be mentioned that the modified hollow glass microspheres are obtained by the following steps:
s1, surface etching: putting hollow glass beads with the model number of K46 into a closed stirrer for continuous stirring, introducing hydrofluoric acid gas into the stirrer, ionizing the fluorine-containing gas in the stirrer to generate charged substances to react with the surfaces of the hollow glass beads, wherein the temperature in the stirrer is controlled to be 50 ℃;
s2, preparation for modification: taking NH3And heating to 40 ℃;
s3, surface modification: heating to 40 ℃ NH3And (3) introducing the glass beads into a stirrer loaded with the hollow glass beads with the etched surfaces for activation, and obtaining the modified hollow glass beads after 2 hours.
A preparation method of TPE supercritical microcellular foam comprises the following steps:
step 1, mixing: adding 82 parts of styrene-based block copolymer SBC, 20 parts of polyvinylidene chloride homopolymer, ethylene-vinyl ester copolymer saponified substance and acrylonitrile, 8 parts of acrylic ester emulsion, 2.6 parts of silane coupling agent and 18 parts of hexagonal boron nitride particles, rhombic boron nitride particles and cubic boron nitride particles in a weight ratio of 20:3:6 into a mixer for mixing, and controlling the temperature of the mixer to be 60 ℃ to obtain a mixed material;
step 2, granulation: introducing the mixed material into a double-screw extruder to obtain particles A;
step 3, transformation: banburying and granulating the particles A and 12 parts by weight of modified hollow glass beads to obtain particles B;
step 4, tabletting: compacting the particles B in a vulcanizing press to obtain a flaky parison;
and 5, supercritical: carrying out high-pressure infiltration on the sheet-shaped blank by using a supercritical fluid, wherein the pressure of the high-pressure infiltration is 12MPa, and when the pressure reaches the maximum pressure, releasing the pressure to the normal pressure to obtain a supercritical foaming blank;
step 6, foaming: placing the supercritical foaming blank into a foaming device for foaming, releasing the pressure after the gas reaches the saturation required pressure of 20MPa, taking out the supercritical foaming blank and cutting the supercritical foaming blank to obtain a TPE (thermoplastic elastomer) supercritical microcellular foamed product finished product;
as shown in fig. 1 and 2, the foaming device includes a lower die 1 and an upper die 2. The lower die 1 is provided with a lower profiled groove 11 on the upper side and an upper profiled block 21 on the lower side of the upper die 2. Wherein the upper mould block 21 is inserted into the lower mould cavity and forms a foaming cavity 4 for foaming. The upper side of the lower die 1 is also provided with a sealing ring groove 12 positioned on one side of the periphery of the lower side type groove 11. A sealing gasket 3 is arranged in the sealing ring groove 12, and the sealing gasket 3 is used for being abutted against the upper die 2 and sealing a gap between the upper die 2 and the lower die 1 when the upper die 2 is abutted against the lower die 1. Meanwhile, a plurality of vent chambers 24 are provided in the upper die 2. The ventilation cavity 24 is communicated with the foaming inner cavity 4, so that when the upper die 2 and the lower die 1 are matched with each other and form the foaming inner cavity 4 for preparing the TPE supercritical microcellular foam, the pressure of the supercritical fluid in the foaming inner cavity 4 is increased through the ventilation cavity 24, and the convenient preparation of the TPE supercritical microcellular foam is completed. It should be mentioned that the plurality of vent chambers 24 are provided with vent holes 22 communicating in sequence therebetween, and the upper mold 2 is provided at the upper side thereof with a plurality of connection holes 23 respectively matching with the respective vent chambers 24.
As shown in fig. 2, an abutment opening/closing table 27 having an inner diameter smaller than that of the vent chamber 24 is provided below the vent chamber 24, and a through groove 28 having an inner diameter larger than that of the vent chamber 24 is provided below the abutment opening/closing table 27. A moving shutter 26 is inserted in the vent lumen 24. The movable shutter 26 is fitted with an elastic member 25, and the upper end of the elastic member 25 abuts against the rear end of the movable shutter 26 and the lower end abuts against the upper side of the abutting opening/closing table 27. The elastic member 25 is an elastic object, and a spring is generally used to reduce the cost. The movable shutter 26 is provided with a seal cover 261 which is located below the abutment opening/closing table 27 and abuts against the abutment opening/closing table 27. Therefore, the vent holes 22 are sequentially communicated with the plurality of vent cavities 24, so that the pressure in the foaming inner cavity 4 is effectively balanced, when the pressure of the supercritical fluid in the foaming inner cavity 4 is increased, the sealing cover 261 on the opening and closing piece 26 is moved in a matched manner, and the opening and closing table 27 is abutted to realize effective control and adjustment of the pressure, so that the preparation convenience of the TPE supercritical microcellular foam is further improved.
Example four
Example four differs from example one in that the thermoplastic elastomer in example four is a polycarbonate-ester amide and polyether ester thermoplastic elastomer Hytrel. The wetting agent is polyvinyl acetate and polyether glycol.
EXAMPLE five
Example five differs from example one in that the thermoplastic elastomer in example five is a styrenic block copolymer SBC and a polyether ester thermoplastic elastomer Hytrel. The impregnating compound is polyurethane emulsion and polyether glycol.
EXAMPLE six
The difference between the sixth embodiment and the first embodiment is that the thermoplastic elastomer in the sixth embodiment is a polyether ester thermoplastic elastomer Hytrel. The impregnating compound is polyvinyl acetate and polyurethane emulsion.
Comparative example 1
The difference between the first comparative example and the second comparative example is that the modified hollow glass beads are not added in the first comparative example, and the hollow glass beads of K38 are added.
Comparative example No. two
Comparative example two differs from example two in that no mixed polymer is added in comparative example two.
Comparative example No. three
The difference between the third comparative example and the second example is that the nano boron nitride particles are not added in the third comparative example.
Test and test:
1. testing according to ASTM D1622- -Density;
2. testing according to GB/T1453-2005-compressive strength;
table one examples one to three and comparative examples one to three test results
Density (kg/m)3)
Compressive Strength (MPa)
Example one
86
0.85
Example two
82
0.95
EXAMPLE III
88
0.90
Comparative example 1
112
0.99
Comparative example No. two
107
0.86
Comparative example No. three
84
0.68
In summary, the composition of the TPE supercritical microcellular foam is optimized, nanometer boron nitride particles comprising hexagonal boron nitride particles, rhombic boron nitride particles and cubic boron nitride particles in a set proportion, a thermoplastic elastomer, a mixed polymer and other additives are combined, and the TPE supercritical microcellular foam which is stable in structure, convenient to prepare and capable of avoiding environmental pollution is obtained after mixing, granulating, reforming, tabletting, supercritical and foaming are sequentially carried out; meanwhile, the foaming device is optimized, and the purpose of effectively improving the preparation convenience of the TPE supercritical microcellular foam is achieved.
References in this application to "first," "second," "third," "fourth," etc., if any, are intended to distinguish between similar elements and not necessarily to describe a particular order or sequence. It will be appreciated that the data so used may be interchanged under appropriate circumstances such that the embodiments described herein may be practiced otherwise than as specifically illustrated or described herein. Furthermore, the terms "comprises" and "comprising," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, or apparatus.
It should be noted that the descriptions in this application referring to "first", "second", etc. are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present application.
The principle and the implementation of the present application are explained herein by applying specific examples, and the above description of the embodiments is only used to help understand the method and the core idea of the present application; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.