CN113444359B - Compact thermoplastic polyurethane for preparing porous structure - Google Patents

Compact thermoplastic polyurethane for preparing porous structure Download PDF

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CN113444359B
CN113444359B CN202010221438.8A CN202010221438A CN113444359B CN 113444359 B CN113444359 B CN 113444359B CN 202010221438 A CN202010221438 A CN 202010221438A CN 113444359 B CN113444359 B CN 113444359B
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thermoplastic polyurethane
polyhydroxy
carbon
porous structure
compound
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CN113444359A (en
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陈光静
陈斌
林伟
陈敏
谭华锋
杨鹏洲
夏东
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Zhejiang Huafeng Thermoplastic Polyurethane Co ltd
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Zhejiang Huafeng Thermoplastic Polyurethane Co ltd
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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Abstract

The compact thermoplastic polyurethane for preparing the porous structure comprises thermoplastic polyurethane A and thermoplastic polyurethane B; wherein the mass of the thermoplastic polyurethane B is 0.5-10% of the total mass of the thermoplastic polyurethane A; the thermoplastic polyurethane A is obtained by polymerizing polyisocyanate A1, a polyhydroxy macromolecular compound A2 and a polyhydroxy micromolecular compound A3, and the mass of NCO in the polymerized thermoplastic polyurethane A is 0-0.1 wt% of the total mass; the thermoplastic polyurethane B is obtained by polymerizing polyisocyanate A1, polyhydroxy macromolecular compound B2 and polyhydroxy micromolecular compound A3, and the mass content of NCO in the polymerized thermoplastic polyurethane B is 1-15 wt% of the total mass of the thermoplastic polyurethane B. The thermoplastic polyurethane provided by the invention is used as a base material for preparing a porous structure forming body, can effectively stabilize the cellular structure of porous particles, has an outstanding welding forming effect, and is particularly suitable for a method for welding by adopting high-energy radiation.

Description

Compact thermoplastic polyurethane for preparing porous structure
Technical Field
The invention relates to a compact thermoplastic polyurethane for producing porous structures, and also relates to porous particles, shaped bodies and the use thereof which are obtained using said compact thermoplastic polyurethane.
Background
Thermoplastic polyurethane material is used as a thermoplastic forming high molecular polymer material, and is applied to the fields from daily life to industry due to excellent performance. According to the application field, the thermoplastic polyurethane can be processed into a sheet shape, a film shape, a porous shape and the like by various methods, wherein the thermoplastic polyurethane porous material has the characteristics of low density and high resilience by introducing gas into the thermoplastic polyurethane through physical or chemical foaming and forming a porous structure in the interior, and generally, the particles with the porous structure are formed by foaming the thermoplastic polyurethane firstly and then the surfaces of the particles are fused and bonded in a mould to form forming bodies with different shapes.
At present, the problems of difficult foaming, uneven foam holes, shrinkage after foaming or easy collapse of welding forming and the like generally exist in the process of preparing a porous structure forming body by thermoplastic polyurethane, and technical personnel pay more attention to the process improvement in the foaming and forming processes, but the research on the structural performance of the thermoplastic polyurethane is less.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide compact thermoplastic polyurethane for preparing a porous structure, and a molded body thereof and application of the molded body, wherein the thermoplastic polyurethane is used as a foaming base material to prepare porous structure particles. The thermoplastic polyurethane provided by the invention is used as a base material for preparing a porous structure forming body, the structural performance of the thermoplastic polyurethane has obvious influence on subsequent foaming and forming, the cellular structure of porous particles can be effectively stabilized, the welding forming effect of the forming body is outstanding, and the thermoplastic polyurethane is particularly suitable for a method for welding by adopting high-energy radiation.
The technical scheme is as follows: the compact thermoplastic polyurethane for preparing the porous structure comprises thermoplastic polyurethane A and thermoplastic polyurethane B;
wherein the mass of the thermoplastic polyurethane B is 0.5-10% of that of the thermoplastic polyurethane A;
the thermoplastic polyurethane A is obtained by polymerizing polyisocyanate A1, a polyhydroxy macromolecular compound A2 and a polyhydroxy micromolecular compound A3, and the mass content of NCO in the polymerized thermoplastic polyurethane A is 0-0.1 wt% of the total mass of the thermoplastic polyurethane A;
the thermoplastic polyurethane B is obtained by polymerizing polyisocyanate A1, polyhydroxy macromolecular compound B2 and polyhydroxy micromolecular compound A3, and the mass content of NCO in the polymerized thermoplastic polyurethane B is 1-15 wt% of the total mass of the thermoplastic polyurethane B.
Wherein:
the polyisocyanate A1 at least contains 2 isocyanate groups, and comprises one or more of p-phenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
The polyhydroxy compound A2 is a polymer of which the molecular chain end is hydroxyl and the repeating unit on the molecular main chain contains a carbon-carbon single bond and a carbon-oxygen single bond;
the number of carbon-carbon single bonds in a repeating unit on the molecular main chain of the polyhydroxy compound A2 is 1-6, and the number of carbon-oxygen single bonds is 1-2.
The number average molecular weight of the polyhydroxy compound A2 is 800-2000, preferably 800-1500.
The polyhydroxy small molecular compound A3 contains 2 terminal hydroxyl groups, and the number of carbon-carbon single bonds contained in a molecular chain is 1-5.
The polyhydroxy macromolecular compound B2 is a polymer of which the molecular chain end is hydroxyl and the repeating units on the molecular main chain contain carbon-carbon single bonds and carbon-oxygen single bonds and/or carbon-oxygen double bonds.
The number average molecular weight of the polyhydroxy compound B2 is 500-5000.
The polyhydroxy compound B2 is obtained by polymerization reaction of aliphatic dibasic acid containing 2-8 carbon atoms and dihydric alcohol containing 2-6 carbon atoms, or ring-opening polymerization of cyclic lactone containing 2-6 carbon atoms, or ring-opening polymerization of alkylene oxide containing 2-6 carbon atoms.
The Shore hardness of the thermoplastic polyurethane A is 70-98A, and the Shore hardness of the thermoplastic polyurethane B is 60-98A.
The preparation method of the compact thermoplastic polyurethane for preparing the porous structure comprises the following steps:
step 1: the preparation process of the thermoplastic polyurethane A comprises the following steps: adding polyisocyanate A1, a polyhydroxy compound A2 and a polyhydroxy micromolecule compound A3 into a reactor, controlling the reaction to be carried out above the melting point of the polymer A, cutting into particles after the reaction is finished, rapidly cooling to be below the melting point of the polymer A, controlling the mass content of NCO in the thermoplastic polyurethane A after polymerization to be 0-0.1 wt% of the total mass of the thermoplastic polyurethane A, and drying to obtain the thermoplastic polyurethane A;
step 2: the preparation process of the thermoplastic polyurethane B comprises the following steps: adding polyisocyanate A1, a polyhydroxy macromolecular compound B2 and a polyhydroxy micromolecular compound A3 into a reactor, controlling the reaction to be carried out above the melting point of a polymer B, cutting into granules and rapidly cooling to be below the melting point of the polymer B after the reaction is finished, controlling the mass content of NCO in the thermoplastic polyurethane B after polymerization to be 1-15 wt% of the total mass of the thermoplastic polyurethane B, drying to obtain the thermoplastic polyurethane B, and sealing and storing;
and 3, step 3: preparation of dense thermoplastic polyurethane particles of porous structure: adding thermoplastic polyurethane A and thermoplastic polyurethane B into an extruder, wherein the mass of the thermoplastic polyurethane B is 0.5-10% of that of the thermoplastic polyurethane A, simultaneously injecting supercritical gas into the extruder through injection ports, the addition amount of the supercritical gas is 1-2% of the total mass of the thermoplastic polyurethane A and the thermoplastic polyurethane B, plasticizing thermoplastic polyurethane elastomer particles into a melt in a screw, extruding the melt through a die head for pressure relief, carrying out granulation, and rapidly cooling to below normal temperature to obtain thermoplastic polyurethane particles with a porous structure;
and 4, step 4: preparation of a cellular thermoplastic polyurethane molded body: the obtained thermoplastic polyurethane particles of the porous structure are put into a mold, and the impregnated particles are irradiated with a substance having high energy radiation such as red radiation or microwave radiation, so that the surfaces of the particles melt and adhere together to obtain a molded body of the porous structure.
Has the advantages that: when the thermoplastic polyurethane particles for preparing the porous structure are expanded into the porous structure particles, the structural performance characteristics of the particles can effectively control the internal pore diameter after expansion to be uniform, the density of the porous particles is low, the foaming surface is smooth and bubble-free, and the particles cannot retract; particularly, the microwave radiation is adopted to prepare the formed body, and no polar substance is additionally added, so that the formed body which has no collapse, surface fusion bonding is close to integration, and the internal porous structure is kept complete can be obtained.
Drawings
FIG. 1 is a picture of the appearance of a porous thermoplastic polyurethane particle obtained in accordance with a preferred embodiment of the present invention.
FIG. 2 is a picture of the surface effect of the cellular structure thermoplastic polyurethane molded body obtained in the preferred embodiment of the present invention.
FIG. 3 is a sectional view of a cellular structure thermoplastic polyurethane molded body obtained in a preferred embodiment of the present invention.
Detailed Description
The invention provides compact thermoplastic polyurethane for preparing a porous structure, which comprises thermoplastic polyurethane A and thermoplastic polyurethane B;
wherein, the thermoplastic polyurethane B is 0.5 to 10 percent of the mass of the thermoplastic polyurethane A;
the thermoplastic polyurethane A is obtained by polymerizing polyisocyanate A1, a polyhydroxy compound A2 and a polyhydroxy micromolecule compound A3, and the NCO mass content in the polymerized thermoplastic polyurethane A is 0-0.1 wt% based on the total mass of the thermoplastic polyurethane A;
the thermoplastic polyurethane B is obtained by polymerizing polyisocyanate A1, a polyhydroxy macromolecular compound B2 and a polyhydroxy micromolecular compound A3, the NCO mass content in the polymerized thermoplastic polyurethane B is 1-15 wt%, and preferably, the NCO mass content in the polymerized thermoplastic polyurethane B is 5-10 wt% based on the total mass of the thermoplastic polyurethane B;
the Shore hardness of the thermoplastic polyurethane A is 70-98A, and the Shore hardness of the thermoplastic polyurethane B is 60-98A;
the polyisocyanate A1 at least contains 2 isocyanate groups, and comprises one or more of p-phenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate;
the polyhydroxy compound A2 is a polymer of which the molecular chain end is hydroxyl and the repeating unit on the molecular main chain contains a carbon-carbon single bond and a carbon-oxygen single bond;
the repeating units on the molecular main chain of the polyhydroxy compound A2 do not contain carbon-oxygen double bonds;
the number of carbon-carbon single bonds in a repeating unit on the molecular main chain of the polyhydroxy compound A2 is 1-6, and the number of carbon-oxygen single bonds is 1-2;
the number average molecular weight of the polyhydroxy compound A2 is 800-2000, preferably 800-1500, and particularly preferably 1000-1800;
the polyhydroxy small molecular compound A3 contains 2 terminal hydroxyl groups, and the number of carbon-carbon single bonds contained in a molecular chain is 1-5;
the polyhydroxy macromolecular compound B2 is a polymer of which the molecular chain end is hydroxyl and the repeating units on the molecular main chain contain carbon-carbon single bonds and carbon-oxygen single bonds and/or carbon-oxygen double bonds;
in some embodiments of the invention, the polyhydroxy compound B2 is obtained by polymerization reaction of aliphatic dibasic acid containing 2-8 carbon atoms and dihydric alcohol containing 2-6 carbon atoms, or ring-opening polymerization of cyclic lactone containing 2-6 carbon atoms, or ring-opening polymerization of alkylene oxide containing 2-6 carbon atoms;
in a particularly preferred embodiment of the invention, the polyhydroxy compound B2 is polyester diol obtained by polymerization reaction of 1, 6-adipic acid and diol with 2-6 carbon atoms or polyester diol obtained by ring-opening polymerization of caprolactone or polyether diol obtained by ring-opening polymerization of alkylene oxide with 2-4 carbon atoms;
the number average molecular weight of the polyhydroxy compound B2 is 500-5000;
the preparation method of the compact thermoplastic polyurethane for preparing the porous structure comprises the following steps:
step 1: the preparation process of the thermoplastic polyurethane A comprises the following steps: adding polyisocyanate A1, a polyhydroxy compound A2 and a polyhydroxy micromolecule compound A3 into a reactor, controlling the reaction to be carried out above the melting point of the polymer A, cutting into particles after the reaction is finished, rapidly cooling to be below the melting point of the polymer A, controlling the mass content of NCO in the thermoplastic polyurethane A after polymerization to be 0-0.1 wt% of the total mass of the thermoplastic polyurethane A, and drying to obtain the thermoplastic polyurethane A;
step 2: the preparation process of the thermoplastic polyurethane B comprises the following steps: adding polyisocyanate A1, a polyhydroxy macromolecular compound B2 and a polyhydroxy micromolecular compound A3 into a reactor, controlling the reaction to be carried out above the melting point of a polymer B, cutting into granules and rapidly cooling to be below the melting point of the polymer B after the reaction is finished, controlling the mass content of NCO in the thermoplastic polyurethane B after polymerization to be 1-15 wt% of the total mass of the thermoplastic polyurethane B, drying to obtain the thermoplastic polyurethane B, and sealing and storing;
and step 3: preparation of thermoplastic polyurethane particles of cellular structure: adding thermoplastic polyurethane A and thermoplastic polyurethane B into an extruder, wherein the mass of the thermoplastic polyurethane B is 0.5-10% of that of the thermoplastic polyurethane A, simultaneously injecting supercritical gas into the extruder through injection ports, the addition amount of the supercritical gas is 1-2% of the total mass of the thermoplastic polyurethane A and the thermoplastic polyurethane B, plasticizing thermoplastic polyurethane elastomer particles into a melt in a screw, extruding the melt through a die head for pressure relief, granulating, and rapidly cooling to below normal temperature to obtain thermoplastic polyurethane particles with a porous structure;
and 4, step 4: preparation of a cellular thermoplastic polyurethane molded body: the obtained thermoplastic polyurethane particles of the porous structure are put into a mold, and the impregnated particles are irradiated with a substance having high energy radiation such as red radiation or microwave radiation, so that the surfaces of the particles melt and adhere together to obtain a molded body of the porous structure.
The thermoplastic polyurethane moldings of cellular structure can be prepared by the known techniques, for example: adding the obtained thermoplastic polyurethane particles with porous structures into a mold, and irradiating the impregnated particles by a substance with high-energy radiation such as red radiation or microwave radiation to enable the surfaces of the particles to be fused and bonded together so as to obtain a molded body;
particularly preferably, the method adopts the high-energy radiation of 2000-8000MHz microwave to melt and bond the surfaces of the particles to prepare the molded body, and the radiation time is 30 s-3 min;
the molded body can be changed according to the shape change of the mold, and can be applied to the fields of soles, shoe marks, mattresses, ground mats, cushions, packaging materials, sports equipment and the like.
(1) Preparation of dense thermoplastic polyurethanes for the preparation of cellular structures:
the formulations of the components of the examples are shown in table 1 below:
TABLE 1
Figure BDA0002426211440000051
Wherein:
example 1
Thermoplastic polyurethane (a) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (A2) is polypropylene oxide dihydric alcohol (the number average molecular weight is 1500), and the polyhydroxy micromolecular compound (A3) is 1, 4-butanediol;
thermoplastic polyurethane (B) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (B2) is 1, 4-butanediol adipate (number average molecular weight of 2000), and the polyhydroxy micromolecular compound (A3) is 1, 4-butanediol;
example 2
Thermoplastic polyurethane (a) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (A2) is polyethylene oxide dihydric alcohol (the number average molecular weight is 800), and the polyhydroxy micromolecular compound (A3) is 1, 4-butanediol;
thermoplastic polyurethane (B) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (B2) is adipic acid-1, 2-hexanediol-1, 4-butanediol ester (the number average molecular weight is 500), and the polyhydroxy micromolecular compound (A3) is 1, 4-butanediol;
example 3
Thermoplastic polyurethane (a) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (A2) is polytetramethylene ether glycol (number average molecular weight is 1800), and the polyhydroxy micromolecular compound (A3) is ethylene glycol;
thermoplastic polyurethane (B) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (B2) is polytetramethylene ether glycol (number average molecular weight is 2000), and the polyhydroxy micromolecular compound (A3) is ethylene glycol;
example 4
Thermoplastic polyurethane (a) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (A2) is polypropylene oxide dihydric alcohol (the number average molecular weight is 1500), and the polyhydroxy micromolecular compound (A3) is ethylene glycol;
thermoplastic polyurethane (B) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (B2) is polycaprolactone diol (number average molecular weight is 3000), and the polyhydroxy micromolecular compound (A3) is ethylene glycol;
example 5
Thermoplastic polyurethane (a) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (A2) is polypropylene oxide dihydric alcohol (the number average molecular weight is 1500), and the polyhydroxy micromolecular compound (A3) is 1, 4-butanediol;
thermoplastic polyurethane (B) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (B2) is 1, 4-butanediol adipate (number average molecular weight of 2000), and the polyhydroxy micromolecular compound (A3) is 1, 4-butanediol;
the formulations of the components of the comparative examples are shown in table 2 below:
TABLE 2
Figure BDA0002426211440000061
Wherein:
comparative example 1
Thermoplastic polyurethane (a) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (A2) is polyethylene oxide dihydric alcohol (the number average molecular weight is 800), and the polyhydroxy micromolecular compound (A3) is 1, 4-butanediol;
comparative example 2
Thermoplastic polyurethane (a) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (A2) is polytetramethylene ether glycol (number average molecular weight is 1800), and the polyhydroxy micromolecular compound (A3) is ethylene glycol;
thermoplastic polyurethane (B) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (B2) is polytetramethylene ether glycol (number average molecular weight is 2000), and the polyhydroxy micromolecular compound (A3) is ethylene glycol;
comparative example 3
Thermoplastic polyurethane (a) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (A2) is 1, 4-butanediol adipate (number average molecular weight is 1500), and the polyhydroxy micromolecular compound (A3) is ethylene glycol;
thermoplastic polyurethane (B) wherein: the polyisocyanate (A1) is diphenylmethane diisocyanate, the polyhydroxy macromolecular compound (B2) is polycaprolactone diol (number average molecular weight is 3000), and the polyhydroxy micromolecular compound (A3) is ethylene glycol;
testing the hardness by using a Shore A durometer method specified in ASTM D2240, wherein the retention time of the spring test force is 1 s;
reacting-NCO groups contained in the prepared thermoplastic polyurethane (A) and thermoplastic polyurethane (B) with excessive di-n-butylamine to produce urea, and titrating the excessive di-n-butylamine with hydrochloric acid to quantitatively calculate the content of NCO;
the hardness and NCO content of the thermoplastic polyurethanes (A) and (B) obtained are shown in Table 3 below:
TABLE 3
Figure BDA0002426211440000071
(2) Preparation of thermoplastic polyurethane particles of cellular structure:
simultaneously adding thermoplastic polyurethane (A) and thermoplastic polyurethane (B) into a first-stage double-screw extruder, then obtaining thermoplastic polyurethane particles with a porous structure by referring to a preparation method disclosed in a patent CN 109501030A, wherein supercritical gas is used as a foaming agent, and the addition amount of the supercritical gas is 1-2% of the total mass of the thermoplastic polyurethane (A) and the thermoplastic polyurethane (B);
example 1, example 2 were prepared as follows:
the thermoplastic polyurethane (A) and the thermoplastic polyurethane (B) particles were fed into a first-stage twin-screw extruder according to the components and proportions of examples 1 and 2, and simultaneously 1.5% carbon dioxide, 0.3% nitrogen and 0.05% helium in a supercritical state were fed into the screw extruder through 3 feed ports, respectively, while maintaining a pressure of 10 mPa. The addition amount of carbon dioxide, nitrogen and helium in the supercritical state is calculated according to the total mass of the thermoplastic polyurethane. Plasticizing the thermoplastic polyurethane elastomer particles into a melt in a screw, extruding and releasing pressure through a die head, granulating and rapidly cooling to below normal temperature to obtain the thermoplastic polyurethane particles with the porous structure. Wherein the screw temperature is 200 ℃, the screw rotating speed is 800rpm, the retention time of the raw materials on the screw is 3min, and the rotating speed of the granulator is controlled at 4000 rpm;
examples 3 and 4 were prepared as follows:
the thermoplastic polyurethane (A) and the thermoplastic polyurethane (B) were fed into a first-stage twin-screw extruder according to the compositions and proportions of examples 3 and 4, respectively, and simultaneously 1.5% carbon dioxide and 0.3% nitrogen in a supercritical state were fed into the first-stage twin-screw extruder through 2 inlets, respectively, while maintaining a pressure of 10 mPa. The addition amount of carbon dioxide and nitrogen in the supercritical state is calculated according to the total mass of the thermoplastic polyurethane. And plasticizing the thermoplastic polyurethane elastomer particles into a melt in a screw, extruding and releasing pressure through a die head, granulating, and rapidly cooling to below normal temperature to obtain the thermoplastic polyurethane particles with the porous structure. Wherein the screw temperature is 200 ℃, the screw rotating speed is 800rpm, the retention time of the raw materials on the screw is 3min, and the rotating speed of the granulator is controlled at 4000 rpm;
example 5 was prepared as follows:
the thermoplastic polyurethane (a) and the thermoplastic polyurethane (B) particles were added to the first-stage twin-screw extruder according to the composition and ratio of example 5, and simultaneously 1.6% carbon dioxide in a supercritical state was injected into the screw extruder through the injection port, respectively, with a holding pressure of 10 mPa. The addition of carbon dioxide in the supercritical state is calculated according to the total mass of the thermoplastic polyurethane. Plasticizing the thermoplastic polyurethane elastomer particles into a melt in a screw, extruding the melt through a die head to release pressure, granulating the melt, and rapidly cooling the melt to below normal temperature to obtain the thermoplastic polyurethane particles with porous structures. Wherein the screw temperature is 200 ℃, the screw rotating speed is 800rpm, the retention time of the raw materials on the screw is 3min, and the rotating speed of the granulator is controlled at 4000 rpm;
comparative example 1 was prepared as follows:
the thermoplastic polyurethane (A) and the thermoplastic polyurethane (B) particles are respectively added into a first-stage double-screw extruder according to the components and the proportion of a comparative example 1 and a comparative example 2, and simultaneously 1.5 percent of carbon dioxide, 0.3 percent of nitrogen and 0.05 percent of helium in a supercritical state are respectively injected into the screw extruder through 3 injection ports, and the pressure is kept at 10mPa during injection. The addition amount of carbon dioxide, nitrogen and helium in the supercritical state is calculated according to the total mass of the thermoplastic polyurethane. Plasticizing the thermoplastic polyurethane elastomer particles into a melt in a screw, extruding and releasing pressure through a die head, granulating and rapidly cooling to below normal temperature to obtain the thermoplastic polyurethane particles with the porous structure. Wherein the screw temperature is 200 ℃, the screw rotating speed is 800rpm, the retention time of the raw materials on the screw is 3min, and the rotating speed of the granulator is controlled at 4000 rpm;
comparative examples 2 and 3 were prepared as follows:
the thermoplastic polyurethane (A) and the thermoplastic polyurethane (B) particles are added into a first-stage double-screw extruder according to the components and the proportion of a comparative example 2 and a comparative example 3, and simultaneously 1.5 percent of carbon dioxide and 0.3 percent of nitrogen in a supercritical state are respectively injected into the screw extruder through 2 injection ports, and the pressure is kept at 10mPa during injection. The addition amount of carbon dioxide and nitrogen in the supercritical state is calculated according to the total mass of the thermoplastic polyurethane. And plasticizing the thermoplastic polyurethane elastomer particles into a melt in a screw, extruding and releasing pressure through a die head, granulating, and rapidly cooling to below normal temperature to obtain the thermoplastic polyurethane particles with the porous structure. Wherein the screw temperature is 200 ℃, the screw rotating speed is 800rpm, the retention time of the raw materials on the screw is 3min, and the rotating speed of the granulator is controlled at 4000 rpm;
the properties of the thermoplastic polyurethane particles of cellular structure obtained are as follows 4:
TABLE 4
Figure BDA0002426211440000091
(3) Preparation of cellular thermoplastic polyurethane moldings:
weighing 25g of the obtained thermoplastic polyurethane particles with the porous structure, adding the weighed particles into a mold with an internal mold cavity specification of 10cm by 2cm by 5cm, placing the mold filled with the particles in a microwave radiation environment with 3000MHz, radiating for 30s, then placing the mold in the air, and cooling for 8 minutes to obtain the thermoplastic polyurethane forming body with the porous structure.
The properties of the cellular thermoplastic polyurethane moldings obtained are shown in Table 5 below:
testing the hardness by using a Shore C durometer method specified in ASTM D2240, wherein the retention time of the spring test force is 1 s;
TABLE 5
Figure BDA0002426211440000101
The performance data show that the compact thermoplastic polyurethane obtained by the invention is used for preparing the thermoplastic polyurethane particles with porous structures, and even under the condition of adopting different preparation methods, the particles have good surface skinning performance, smooth surface, no obvious large bubbles, no particle retraction phenomenon and small particle bulk density. The microwave radiation forming process does not need to add any polar substance, a good forming effect can be achieved after short-time microwave radiation, the surface of the formed body is flat and has no obvious granular sensation, the surface is close to integration, a welding interface between particles is difficult to see, porous particles in the formed body are tightly bonded, the porous structure of the porous particles is still well kept in the porous particles, the average density of the formed body is small, and the formed body shows excellent light texture.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A dense thermoplastic polyurethane for the preparation of cellular structures, characterized in that the dense thermoplastic polyurethane comprises a thermoplastic polyurethane a and a thermoplastic polyurethane B;
wherein the mass of the thermoplastic polyurethane B is 0.5-10% of the total mass of the thermoplastic polyurethane A;
the thermoplastic polyurethane A is obtained by polymerizing polyisocyanate A1, a polyhydroxy compound A2 and a polyhydroxy micromolecule compound A3, and the mass content of NCO in the polymerized thermoplastic polyurethane A is 0-0.1 wt% of the total mass of the thermoplastic polyurethane A;
the thermoplastic polyurethane B is obtained by polymerizing polyisocyanate A1, a polyhydroxy macromolecular compound B2 and a polyhydroxy micromolecular compound A3, and the mass content of NCO in the polymerized thermoplastic polyurethane B is 1-15 wt% of the total mass of the thermoplastic polyurethane B;
the repeating units on the molecular main chain of the polyhydroxy compound A2 do not contain carbon-oxygen double bonds.
2. The densified thermoplastic polyurethane according to claim 1, wherein the polyisocyanate A1 contains at least 2 isocyanate groups, and the isocyanate groups include one or more of p-phenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
3. The dense thermoplastic polyurethane for preparing porous structure according to claim 1, wherein said polyol A2 is a polymer having hydroxyl group at the molecular chain end and carbon-carbon single bond and carbon-oxygen single bond in the repeating unit in the molecular main chain; the number of carbon-carbon single bonds is 1-6, and the number of carbon-oxygen single bonds is 1-2.
4. The dense thermoplastic polyurethane for preparing cellular structures of claim 3, wherein said polyol A2 has a number average molecular weight of 800 to 2000.
5. The dense thermoplastic polyurethane for preparing porous structure of claim 1, wherein said polyhydroxy small molecule compound A3 contains 2 terminal hydroxyl groups and the number of carbon-carbon single bonds in the molecular chain is 1-5.
6. The densified thermoplastic polyurethane according to claim 1, for preparing a porous structure, characterized in that the polyhydroxylated macromolecular compound B2 is a polymer having hydroxyl groups at the ends of the molecular chain and containing carbon-carbon single bonds and carbon-oxygen single bonds and/or carbon-oxygen double bonds in the repeating units in the main molecular chain.
7. The densified thermoplastic polyurethane for preparing a porous structure according to claim 1, wherein the polyol B2 has a number average molecular weight of 500 to 5000.
8. The dense thermoplastic polyurethane for preparing porous structure of claim 1, wherein the polyol B2 is obtained by polymerization reaction of aliphatic dibasic acid containing 2-8 carbon atoms and dihydric alcohol containing 2-6 carbon atoms, or ring opening polymerization of cyclic lactone containing 2-6 carbon atoms, or ring opening polymerization of alkylene oxide containing 2-6 carbon atoms.
9. The dense thermoplastic polyurethane for preparing porous structure as claimed in claim 1, wherein the Shore A hardness of the thermoplastic polyurethane is 70-98A, and the Shore B hardness of the thermoplastic polyurethane is 60-98A.
10. A process for the preparation of a compact thermoplastic polyurethane for cellular structures according to claim 1, characterized in that:
step 1: the preparation process of the thermoplastic polyurethane A comprises the following steps: adding polyisocyanate A1, a polyhydroxy compound A2 and a polyhydroxy micromolecule compound A3 into a reactor, controlling the reaction to be carried out above the melting point of a polymer A, cutting into particles after the reaction is finished, rapidly cooling to be below the melting point of the polymer A, controlling the mass content of NCO in the thermoplastic polyurethane A after polymerization to be 0-0.1 wt% of the total mass of the thermoplastic polyurethane A, and drying to obtain the thermoplastic polyurethane A;
step 2: the preparation process of the thermoplastic polyurethane B comprises the following steps: adding polyisocyanate A1, a polyhydroxy macromolecular compound B2 and a polyhydroxy micromolecular compound A3 into a reactor, controlling the reaction to be carried out above the melting point of a polymer B, cutting into granules and rapidly cooling to be below the melting point of the polymer B after the reaction is finished, controlling the mass content of NCO in the thermoplastic polyurethane B after polymerization to be 1-15 wt% of the total mass of the thermoplastic polyurethane B, drying to obtain the thermoplastic polyurethane B, and sealing and storing;
and step 3: preparation of dense thermoplastic polyurethane particles of porous structure: adding thermoplastic polyurethane A and thermoplastic polyurethane B into an extruder, wherein the mass of the thermoplastic polyurethane B is 0.5-10% of that of the thermoplastic polyurethane A, simultaneously injecting supercritical gas into the extruder through injection ports respectively, wherein the addition amount of the supercritical gas is 1-2% of the total mass of the thermoplastic polyurethane A and the thermoplastic polyurethane B, plasticizing thermoplastic polyurethane elastomer particles into a melt in a screw, extruding and releasing pressure through a die head, granulating, and rapidly cooling to below normal temperature to obtain thermoplastic polyurethane particles with a porous structure;
and 4, step 4: preparation of a cellular thermoplastic polyurethane molded body: the obtained thermoplastic polyurethane particles of the porous structure are added into a mold, and the impregnated particles are irradiated by infrared radiation or microwave radiation, so that the surfaces of the particles are melt-bonded together to obtain a molded body of the porous structure.
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