CN116891604A - Thermoplastic polyester acid foamed product and preparation method thereof - Google Patents
Thermoplastic polyester acid foamed product and preparation method thereof Download PDFInfo
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- CN116891604A CN116891604A CN202310935196.2A CN202310935196A CN116891604A CN 116891604 A CN116891604 A CN 116891604A CN 202310935196 A CN202310935196 A CN 202310935196A CN 116891604 A CN116891604 A CN 116891604A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 28
- 239000002253 acid Substances 0.000 title claims abstract description 27
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 27
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 238000005187 foaming Methods 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 239000004088 foaming agent Substances 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
- 239000000806 elastomer Substances 0.000 claims abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 13
- 239000002667 nucleating agent Substances 0.000 claims abstract description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 10
- 238000003723 Smelting Methods 0.000 claims abstract description 8
- 239000002608 ionic liquid Substances 0.000 claims abstract description 6
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 43
- 238000010276 construction Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002042 Silver nanowire Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 239000002086 nanomaterial Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 239000003365 glass fiber Substances 0.000 abstract description 2
- 150000002500 ions Chemical class 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 235000021197 fiber intake Nutrition 0.000 abstract 1
- 230000004927 fusion Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 10
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K7/00—Use of ingredients characterised by shape
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a thermoplastic polyester acid foaming product and a preparation method thereof, and relates to the technical field of foaming product materials. The foaming product comprises the following raw materials: ethylene-propylene copolymers, propylene-based elastomers, two-dimensional lamellar nano-objects, one-dimensional fiber objects, catalysts, cross-linking agents, bridging agents, nucleating agents and foaming agents. The modified composite structure system mixture is matched with the fusion material to carry out mixed smelting, the quaternary phosphonium salt ionic liquid catalyst is used for carrying out material sheet separation, ions among materials are converted and intercalated, and meanwhile, the demolding mold product is prefabricated, so that the materials can be complementarily integrated together in the process of smelting and preparing the product, the glass fiber consumption of the traditional exterior trim part is reduced, the weight of the exterior trim part is reduced, and the thermoplastic polyester acid foamed product with good foaming effect, high foaming efficiency, uniform, small and compact foam holes, light weight, high strength and other excellent mechanical properties and service performance is formed.
Description
Technical Field
The invention relates to the technical field of foaming product materials, in particular to a thermoplastic polyester acid foaming product and a preparation method thereof.
Background
Thermoplastic Polyurethanes (TPU) are increasingly popular for their superior properties and environmental protection concept, with good mechanical properties, abrasion resistance, low temperature flexibility, and adhesion. TPU is a block copolymer with polyester or polyether as a soft segment and diisocyanate as a hard segment, is a type of high-elasticity thermoplastic elastomer, and the soft segment part of a molecular chain endows the TPU with excellent elasticity, and the hard segment part ensures that the TPU has high mechanical strength.
However, because of the large polarity in the molecule and the strong molecular force, the TPU has a short service life due to the large internal consumption, and because the thermoplastic polyurethane and the ethylene-vinyl acetate copolymer have poor compatibility, the thermoplastic polyurethane is directly used for blending and modifying the ethylene-vinyl acetate copolymer, microscopic phase separation can be generated, and the material performance is poor.
Disclosure of Invention
(one) solving the technical problems
Aiming at the defects of the prior art, the invention provides a thermoplastic polyester acid foaming product and a preparation method thereof, which solve the problems of short service life and poor material performance caused by traditional blending modification due to high internal polarity and high molecular acting force of TPU (thermoplastic polyurethane) of the traditional foaming product.
(II) technical scheme
In order to achieve the above purpose, the invention is realized by the following technical scheme: the thermoplastic polyester acid foamed product comprises the following raw materials: the ethylene-propylene copolymer, the propylene-based elastomer, the two-dimensional lamellar nano-object, the one-dimensional fiber object, the catalyst, the cross-linking agent, the bridging agent, the nucleating agent and the foaming agent are prepared by the mass ratio of 35-45 parts of ethylene-propylene copolymer, 15-30 parts of propylene-based elastomer, 10-25 parts of two-dimensional lamellar nano-object, 20-40 parts of one-dimensional fiber object, 0.5-2 parts of catalyst, 0.1-0.4 part of cross-linking agent, 0.7-1 part of bridging agent, 1.5-2 parts of nucleating agent and 3-4 parts of foaming agent.
Preferably, the two-dimensional lamellar nano-material is a material with two dimension sizes not between 0.1 and 100nm in three dimensions, and comprises one or two mixtures of graphene and derivatives thereof, hydrotalcite, black phosphorus nano-sheets and layered double hydroxides.
Preferably, the one-dimensional fiber is one of carbon nanofiber, carbon nanotube, silver nanowire and silicon dioxide nanowire.
Preferably, the catalyst is a quaternary phosphonium salt ionic liquid catalyst.
Preferably, the cross-linking agent is 1, 4-bis-butyl-peroxy isopropyl benzene, the bridging agent is DCP, and the foaming agent is one or more of cyclopentane and monofluoro-dichloroethane.
The preparation method of the thermoplastic polyester acid foaming product specifically comprises the following steps:
s1, modified lamellar polymer
Fully and uniformly mixing the two-dimensional lamellar nano-objects and the one-dimensional fiber objects in an internal mixer, adding the mixture into a container containing catalyst solution after mixing and cooling, stripping the structure by using a shearing force device, and completing the construction of a composite structure system by ultrasonic treatment;
s2, smelting the compound
Adding the ethylene-propylene copolymer and the propenyl elastomer into a double-screw extruder for mixing, and cooling for standby;
s3, mixing materials and mixing
Adding the mixture of which the construction of the composite structure system is completed in the step S1 and the mixture in the step S2 into an internal mixer for mixing, and adding a cross-linking agent, a bridging agent, a nucleating agent and a foaming agent into the internal mixer for mixing;
s4, tabletting and forming
Extruding and injecting the mixture obtained in the step S3 into a forming die, pressing the mixture into a sheet by an open type double-roller mixer after forming, cutting a size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out a pressure release test piece after gas saturation, and cutting the sample to obtain the thermoplastic polyester acid foaming product.
Preferably, the banburying temperature in the S1 step is 110-125 ℃, the banburying time is 10-15 min, the rotating speed is 35-50 rpm/min, and the mixing temperature of the double screw extruder in the S2 step is 110-115 ℃ and the mixing time is 5-10 min.
Preferably, the steam pressure in the forming die is 0.4-0.5 MPa, the temperature is 80-100 ℃, the foaming time in the step S4 is 5-6 min, and the temperature is 140-160 ℃.
(III) beneficial effects
The invention provides a thermoplastic polyester acid foaming product and a preparation method thereof. The beneficial effects are as follows:
1. the invention provides a thermoplastic polyester acid foaming product and a preparation method thereof, wherein the foaming product is prepared by mixing and fusing a plurality of materials with excellent flexibility, high rebound resilience, small density and light weight by a modified composite structure system mixture, carrying out mixed smelting, separating material sheets by a quaternary phosphonium salt ionic liquid catalyst, finishing conversion intercalation of ions among materials, and prefabricating a demolding mold product, so that the products can be complementarily integrated together in the process of smelting and preparing the products, the glass fiber dosage of the traditional exterior trim part is reduced, the weight of the exterior trim part is reduced, and the thermoplastic polyester acid foaming product with good foaming effect, high foaming efficiency, uniform, small and compact foam holes, light weight, high strength and other excellent mechanical properties and service performance is formed.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
the embodiment of the invention provides a thermoplastic polyester acid foaming product, which comprises the following raw materials: the ethylene-propylene copolymer, the propylene-based elastomer, the two-dimensional lamellar nano-substance, the one-dimensional fiber, the catalyst, the cross-linking agent, the bridging agent, the nucleating agent and the foaming agent are prepared by the mass ratio of 35 parts of ethylene-propylene copolymer, 15 parts of propylene-based elastomer, 10 parts of two-dimensional lamellar nano-substance, 20 parts of one-dimensional fiber, 0.5 part of catalyst, 0.1 part of cross-linking agent, 0.7 part of bridging agent, 1.5 parts of nucleating agent and 3 parts of foaming agent.
The preparation method of the thermoplastic polyester acid foaming product specifically comprises the following steps:
s1, modified lamellar polymer
Fully and uniformly mixing 10 parts of layered double hydroxide and 20 parts of carbon nano fibers in an internal mixer with the temperature of 110 ℃, the internal mixing time of 10min and the rotating speed of 35rpm/min, adding the mixture into a container containing 0.5 part of quaternary phosphonium salt ionic liquid catalyst solution after mixing and cooling, and performing structural stripping on the mixture by utilizing a shearing force device, and then completing the construction of a composite structural system by ultrasonic treatment, wherein the shearing force device consists of a mixing rotor comprising a rotor and a stator;
s2, smelting the compound
Adding 35 parts of ethylene-propylene copolymer and 15 parts of propylene-based elastomer into a double-screw extruder with the temperature of 110 ℃ and the mixing time of 5min for mixing, and cooling for standby;
s3, mixing materials and mixing
Mixing the mixture of the composite structure system construction in the step S1 and the mixing material in the step S2 in an internal mixer at 110 ℃ for 10min at 35rpm/min, and adding 0.1 part of cross-linking agent, 0.7 part of bridging agent, 1.5 parts of nucleating agent and 3 parts of foaming agent into the internal mixer for mixing;
s4, tabletting and forming
Extruding and injecting the mixture obtained in the step S3 into a forming die with steam pressure of 0.4MPa and temperature of 80 ℃, pressing the mixture into sheets by an open double-roller mixer after forming, cutting test pieces after the sheets are pressed into sheets, putting the sheets into a foaming kettle for foaming for 5min, taking out the pressure-relief test pieces after gas saturation at 140 ℃, and cutting the test pieces to obtain the thermoplastic polyester acid foaming product.
Table 1 shows the results of the examination of the examples of the present invention, examples one and comparative examples, using ethylene-vinyl acetate copolymer as a substitute blend:
| performance of | Standard (International) | Example 1 | Comparative example |
| Hardness (asker C) | J56 | 36.4 | 42 |
| Density (g/cm) 3 ) | J62 | 0.19 | 0.21 |
| Rebound resilience (%) | J86 | 53.2 | 51 |
| Tensile Strength (Mpa) | J57 | 3.2 | 2.7 |
| Heat shrinkage (%) | J64 | 2.1 | 3.8 |
| Compression set (%) | J59 | 21 | 28 |
| Elongation at break (%) | J57 | 284 | 360 |
| Tensile Strength (%) | ISO1798 | 2.76 | 2.5 |
TABLE 1
Embodiment two:
the thermoplastic polyester acid foamed product comprises the following raw materials: the ethylene-propylene copolymer, the propylene-based elastomer, the two-dimensional lamellar nano-substance, the one-dimensional fiber, the catalyst, the cross-linking agent, the bridging agent, the nucleating agent and the foaming agent are prepared by the mass ratio of 40 parts of ethylene-propylene copolymer, 20 parts of propylene-based elastomer, 15 parts of two-dimensional lamellar nano-substance, 30 parts of one-dimensional fiber, 1 part of catalyst, 0.2 part of cross-linking agent, 0.9 part of bridging agent, 1.5 parts of nucleating agent and 3 parts of foaming agent;
the preparation method of the thermoplastic polyester acid foaming product specifically comprises the following steps:
s1, modified lamellar polymer
Fully and uniformly mixing 15 parts of black phosphorus nano sheets and 30 parts of carbon nano fibers in an internal mixer with the temperature of 110 ℃, the internal mixing time of 10min and the rotating speed of 35rpm/min, adding the mixture into a container containing 1 part of quaternary phosphonium salt ionic liquid catalyst solution after mixing and cooling, and performing structural stripping on the mixture by utilizing a shearing force device, and then completing the construction of a composite structural system by ultrasonic treatment, wherein the shearing force device consists of a mixing rotor comprising a rotor and a stator;
s2, smelting the compound
Adding 40 parts of ethylene-propylene copolymer and 20 parts of propylene-based elastomer into a double-screw extruder with the temperature of 110 ℃ and the mixing time of 5min for mixing, and cooling for standby;
s3, mixing materials and mixing
Mixing the mixture of the composite structure system construction in the step S1 and the mixing material in the step S2 in an internal mixer at 110 ℃ for 10min at 35rpm/min, and adding 0.2 part of cross-linking agent, 0.9 part of bridging agent, 1.5 parts of nucleating agent and 3 parts of foaming agent into the internal mixer for mixing;
s4, tabletting and forming
Extruding and injecting the mixture obtained in the step S3 into a forming die with steam pressure of 0.5MPa and temperature of 90 ℃, pressing the mixture into sheets by an open double-roller mixer after forming, cutting test pieces after the sheets are pressed into sheets, putting the sheets into a foaming kettle for foaming for 6min, taking out the pressure-relief test pieces after gas saturation at 145 ℃, and cutting the test pieces to obtain the thermoplastic polyester acid foaming product. Table 2 shows the results of the examination of the present invention in examples two and comparative examples using ethylene-vinyl acetate copolymer as a substitute blend:
| performance of | Standard (International) | Example 1 | Comparative example |
| Hardness (asker C) | J56 | 37.2 | 42 |
| Density (g/cm) 3 ) | J62 | 0.2 | 0.21 |
| Rebound resilience (%) | J86 | 53.9 | 51 |
| Tensile Strength (Mpa) | J57 | 3.23 | 2.7 |
| Heat shrinkage (%) | J64 | 2.4 | 3.8 |
| Compression set (%) | J59 | 20 | 28 |
| Elongation at break (%) | J57 | 278 | 360 |
| Tensile Strength (%) | ISO1798 | 2.81 | 2.5 |
TABLE 2
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The thermoplastic polyester acid foaming product is characterized by comprising the following raw materials: the ethylene-propylene copolymer, the propylene-based elastomer, the two-dimensional lamellar nano-object, the one-dimensional fiber object, the catalyst, the cross-linking agent, the bridging agent, the nucleating agent and the foaming agent are prepared by the mass ratio of 35-45 parts of ethylene-propylene copolymer, 15-30 parts of propylene-based elastomer, 10-25 parts of two-dimensional lamellar nano-object, 20-40 parts of one-dimensional fiber object, 0.5-2 parts of catalyst, 0.1-0.4 part of cross-linking agent, 0.7-1 part of bridging agent, 1.5-2 parts of nucleating agent and 3-4 parts of foaming agent.
2. The thermoplastic polyester acid foamed article according to claim 1, wherein: the two-dimensional lamellar nano-material is a material with two dimension sizes not between 0.1 and 100nm in three dimensions and comprises graphene and derivatives thereof, hydrotalcite, black phosphorus nano-sheets and one or two mixtures of layered double hydroxides.
3. The thermoplastic polyester acid foamed article according to claim 1, wherein: the one-dimensional fiber is one of carbon nanofiber, carbon nanotube, silver nanowire and silicon dioxide nanowire.
4. The thermoplastic polyester acid foamed article according to claim 1, wherein: the catalyst is a quaternary phosphonium salt ionic liquid catalyst.
5. The thermoplastic polyester acid foamed article according to claim 1, wherein: the cross-linking agent is 1, 4-dibutyl peroxyisopropyl benzene, the bridging agent is DCP, and the foaming agent is one or more of cyclopentane and monofluoro-dichloroethane.
6. The preparation method of the thermoplastic polyester acid foaming product is characterized by comprising the following steps of:
s1, modified lamellar polymer
Fully and uniformly mixing the two-dimensional lamellar nano-objects and the one-dimensional fiber objects in an internal mixer, adding the mixture into a container containing catalyst solution after mixing and cooling, stripping the structure by using a shearing force device, and completing the construction of a composite structure system by ultrasonic treatment;
s2, smelting the compound
Adding the ethylene-propylene copolymer and the propenyl elastomer into a double-screw extruder for mixing, and cooling for standby;
s3, mixing materials and mixing
Adding the mixture of which the construction of the composite structure system is completed in the step S1 and the mixture in the step S2 into an internal mixer for mixing, and adding a catalyst, a cross-linking agent, a bridging agent, a nucleating agent and a foaming agent into the internal mixer for mixing;
s4, tabletting and forming
Extruding and injecting the mixture obtained in the step S3 into a forming die, pressing the mixture into a sheet by an open type double-roller mixer after forming, cutting a size test piece after tabletting, putting the test piece into a foaming kettle for foaming, taking out a pressure release test piece after gas saturation, and cutting the sample to obtain the thermoplastic polyester acid foaming product.
7. The method for producing a thermoplastic polyester acid foamed article according to claim 6, wherein: the banburying temperature in the S1 step is 110-125 ℃, the banburying time is 10-15 min, the rotating speed is 35-50 rpm/min, and the mixing temperature of the double-screw extruder in the S2 step is 110-115 ℃ and the mixing time is 5-10 min.
8. The method for producing a thermoplastic polyester acid foamed article according to claim 6, wherein: the steam pressure in the forming die is 0.4-0.5 MPa, the temperature is 80-100 ℃, the foaming time in the step S4 is 5-6 min, and the temperature is 140-160 ℃.
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| CN202310935196.2A CN116891604A (en) | 2023-07-28 | 2023-07-28 | Thermoplastic polyester acid foamed product and preparation method thereof |
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| CN202310935196.2A CN116891604A (en) | 2023-07-28 | 2023-07-28 | Thermoplastic polyester acid foamed product and preparation method thereof |
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