CN115418070A - TPE material and preparation method and application thereof - Google Patents

TPE material and preparation method and application thereof Download PDF

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CN115418070A
CN115418070A CN202211201637.8A CN202211201637A CN115418070A CN 115418070 A CN115418070 A CN 115418070A CN 202211201637 A CN202211201637 A CN 202211201637A CN 115418070 A CN115418070 A CN 115418070A
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tpe material
screw machine
tpe
temperature
elastomer
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具嘉峻
贺热民
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Midea Group Co Ltd
Guangdong Midea White Goods Technology Innovation Center Co Ltd
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Midea Group Co Ltd
Guangdong Midea White Goods Technology Innovation Center Co Ltd
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • 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
    • C08J9/0066—Use of inorganic compounding ingredients
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/02—Doors; Covers
    • F25D23/028—Details
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2203/00—Foams characterized by the expanding agent
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    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—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
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes

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Abstract

The invention discloses a TPE material and a preparation method and application thereof, wherein the TPE material comprises the following preparation raw materials in parts by weight: 20-60 parts of SEBS elastomer; 10-40 parts of POE elastomer; 5-25 parts of polyolefin; 5-40 parts of lubricating oil. The TPE material provided by the invention has excellent low-temperature resistance, and has better heat preservation and heat insulation performance when being used as a door seal. The invention also provides a preparation method and application of the TPE material.

Description

TPE material and preparation method and application thereof
Technical Field
The invention relates to the technical field of thermoplastic materials, in particular to a TPE material and a preparation method and application thereof.
Background
With the improvement of living standard, freezing/refrigerating equipment (such as refrigerator) has become an essential household appliance in the home of people, and the requirement of cooling efficiency of the equipment is higher and higher for the purpose of energy saving and fresh keeping. One of the main causes of hindering the cooling efficiency in the refrigerator is heat entering from a gap between the main body storage room and the door. Generally, a method of effectively improving cooling efficiency is to provide a seal at a peripheral edge portion of a refrigerator door and to close a gap between opening edge portions of the refrigerator door to suppress heat from entering.
TPE (Thermoplastic Elastomer ) is a commonly used material for door seals for refrigeration/freezer equipment. However, the traditional TPE material has the defects of poor low temperature resistance, high K value, unfavorable heat preservation and insulation and the like.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a TPE material which has excellent low-temperature resistance and has better heat preservation and heat insulation performance when being used as a door seal.
The invention also provides a preparation method of the TPE material.
The invention also provides a door seal, and the preparation raw materials of the door seal comprise the TPE material.
The invention also provides an application of the door seal in refrigeration equipment.
According to the embodiment of the first aspect of the invention, the TPE material is prepared from the following raw materials in parts by weight:
Figure BDA0003872608900000011
the TPE material provided by the embodiment of the invention has at least the following beneficial effects:
(1) The invention combines two elastomers, improves the low-temperature impact resistance of the obtained TPE material, does not harden under the low-temperature condition, and still keeps good elasticity.
(2) In the traditional technology, a small molecular plasticizer, such as dibasic acid esters, phthalic acid esters (including phthalic acid esters and terephthalic acid esters), benzene polycarboxylic acid esters, benzoic acid esters, polyol esters, chlorinated hydrocarbons, epoxies, citric acid esters, polyesters and the like, is generally required to be added for preparing a TPE material for refrigeration equipment, and the plasticizer is similar to an environmental hormone, so that the environmental and human body are negatively influenced by excessive industrial use; the plasticizer can also inhibit the uniformity and controllability of foaming in the preparation process of the TPE material, and in addition, the foaming agent can be separated out at low temperature, so that when the TPE material is used for a door seal of freezing/refrigerating equipment, not only can serious harm be caused to the environment, but also mildew can grow on the TPE material, and further, substances stored in the freezing/refrigerating equipment can be polluted.
(3) The preparation raw materials of the TPE material comprise polyolefin, and the price of the polyolefin is usually lower than that of SEBS elastomer (styrene elastomer) and POE elastomer (polyolefin elastomer), so that the preparation price of the TPE material can be reduced to a certain extent;
in addition, the polyolefin can also adjust the hardness and melt index of the TPE material, and improve the processability and moldability of the whole formulation system, which may cause difficulty in molding the TPE material if no polyolefin or the polyolefin content is not within the range required by the present invention.
And the invention adopts the combination of two elastomers and polyolefin, and the mutual matching of the dosage, thus reducing the dosage of micromolecule plasticizer, even avoiding the use of micromolecule plasticizer, and simultaneously ensuring the plasticity of the obtained TPE material to meet the use requirement of the door seal of the refrigeration equipment.
(4) According to the invention, the lubricating oil is included in the TPE preparation raw material, so that the compatibility among the SEBS elastomer, the POE elastomer and the polyolefin can be improved, and the apparent property of the obtained TPE material can be improved.
According to some embodiments of the invention, the SEBS elastomer is a block copolymer of styrene and at least one of butadiene and isoprene.
According to some embodiments of the present invention, the mass content of the styrene segment in the SEBS elastomer is between 20 and 35 wt%.
According to some preferred embodiments of the present invention, the mass content of the styrene segment in the SEBS elastomer is between 30 and 33 wt%.
According to some embodiments of the invention, the SEBS elastomer has a shore a hardness of between 50 and 80.
According to some preferred embodiments of the present invention, the shore a hardness of the SEBS elastomer is between 70 and 75.
According to some embodiments of the invention, the SEBS elastomer may be selected from at least one of bamlin petrochemical SEBS YH-503T, kraton 601, kraton G1633, kraton G1651, kraton G1654, kraton G1650, kraton G1652, and kraton G1653.
According to some preferred embodiments of the present invention, said SEBS elastomer is selected from SEBS YH-503T.
According to some embodiments of the invention, the POE elastomer has a shore a hardness of 60 to 64.
According to some embodiments of the invention, the POE elastomer is prepared from monomers comprising ethylene and octene.
According to some embodiments of the invention, the POE elastomer is at least one of POE7447 dow and DF610 mitsui.
According to some embodiments of the invention, the POE elastomer is a mixture of american dow POE7447 and mitsui chemical DF 610.
According to some embodiments of the invention, the POE elastomer has a mass ratio of POE7447, dow, usa to DF610, about 1.5.
According to some embodiments of the present invention, in the TPE material, the weight ratio of SEBS elastomer to POE elastomer is 1 to 2.
According to some preferred embodiments of the present invention, in the TPE material, a weight ratio of SEBS elastomer to POE elastomer is: 1.2-1.6. For example, specifically 1.28.
According to some embodiments of the invention, the polyolefin has a melt index between 0.8 and 1.0g/10min at 190 ℃ under 2.16kg test conditions.
According to some embodiments of the invention, the polyolefin is selected from at least one of PP (polypropylene), LDPE (low density polyethylene), LLDPE (linear low density polyethylene) and HDPE (high density polyethylene).
According to some embodiments of the invention, the polyolefin is selected from at least one of LDPE 8784ML and HDPE8318ML of exxonmobil.
According to some preferred embodiments of the invention, the polyolefin is selected from LDPE.
According to some further preferred embodiments of the present invention, the polyolefin is specifically selected from LDPE 8784ML, exxon meifu.
Therefore, the density of the polyolefin with lower density can be further reduced on the basis of ensuring the forming performance of the TPE material.
According to some embodiments of the invention, the mass ratio of the SEBS elastomer to the polyolefin in the TPE material is 1.5 to 4.
According to some preferred embodiments of the present invention, the mass ratio of the SEBS elastomer to the polyolefin in the TPE material is about 1.56.
According to some embodiments of the invention, the lubricating oil is selected from at least one of white mineral oil, paraffinic oil, aromatic oil, and naphthenic oil.
According to some preferred embodiments of the invention, the white mineral oil may be number 10 white mineral oil (white mineral oil # 10).
Therefore, in the TPE material, the added lubricating oil has higher compatibility with the SEBS elastomer, the POE elastomer and the polyolefin, so that the texture uniformity of the obtained TPE material is finally improved.
According to some embodiments of the invention, the mass ratio of the SEBS elastomer to the lubricating oil in the TPE material is 2-6.
According to some preferred embodiments of the present invention, the mass ratio of the SEBS elastomer to the lubricating oil in the TPE material is 2.5 to 2.8.
According to some embodiments of the invention, the mass ratio of the SEBS elastomer to the lubricating oil in the TPE material is 3.5 to 3.6.
According to some embodiments of the invention, the raw materials for preparing the TPE material further comprises at least one of an inorganic filler, an antioxidant, a lubricant, and a dispersant.
According to some embodiments of the invention, the raw materials from which the TPE material is made further comprise an inorganic filler.
According to some embodiments of the present invention, the weight ratio of the SEBS elastomer to the inorganic filler in the TPE material is 0.5 to 6.
According to some preferred embodiments of the present invention, the weight ratio of the SEBS elastomer to the inorganic filler in the TPE material is 20 to 60.
According to some preferred embodiments of the present invention, in the TPE material, the weight ratio of the SEBS elastomer to the inorganic filler is 1-1.5.
According to some preferred embodiments of the present invention, in the TPE material, a weight ratio of SEBS elastomer to the inorganic filler is 1.33 to 1.34.
According to some preferred embodiments of the present invention, in the TPE material, a weight ratio of the SEBS elastomer to the inorganic filler is 1.24 to 1.25.
According to some preferred embodiments of the present invention, in the TPE material, a weight ratio of the SEBS elastomer to the inorganic filler is 1.15 to 1.16.
According to some preferred embodiments of the present invention, the weight ratio of the SEBS elastomer to the inorganic filler in the TPE material is 1.45-1.46.
According to some embodiments of the invention, the inorganic filler is selected from at least one of calcium carbonate, barium sulfate, talc, silica, titanium dioxide and montmorillonite.
According to some preferred embodiments of the present invention, the silica is at least one of a crystalline fine silica powder (fine silica powder) and a non-crystalline fine silica powder.
According to some embodiments of the invention, the inorganic filler is selected from at least two of calcium carbonate, barium sulfate and silica micropowder.
According to some preferred embodiments of the present invention, the inorganic filler is a mixture of calcium carbonate and fine silica powder; the mass ratio of the two is 7-9; for example, it may be specifically about 8.
According to some preferred embodiments of the present invention, the inorganic filler is a mixture of barium sulfate and fine silica powder; the mass ratio of the two is 7-10; for example, it may be specifically about 7.67.
By adding the inorganic filler into the raw materials for preparing the TPE material, the putting-in elasticity and the forming property of the TPE material can be improved, so that the TPE material is more suitable for preparing the door seal.
According to some embodiments of the present invention, the raw material for preparing the TPE material further comprises an antioxidant.
According to some embodiments of the invention, the weight ratio of the SEBS elastomer to the antioxidant in the TPE material is 10-200.
According to some embodiments of the invention, the weight ratio of the SEBS elastomer to the antioxidant in the TPE material is 30 to 40.
According to some embodiments of the invention, the weight ratio of the SEBS elastomer to the antioxidant in the TPE material is 35-37.5.
According to some embodiments of the invention, the antioxidant is selected from at least one of antioxidant 1010 (CAS: 6683-19-8), antioxidant 168 (CAS: 31570-04-4), and DSTDP (CAS: 693-36-7).
According to some embodiments of the invention, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168.
According to some embodiments of the present invention, the weight ratio of the antioxidant 1010 and the antioxidant 168 in the antioxidant is 1 to 5.
According to some embodiments of the present invention, the weight ratio of the antioxidant 1010 to the antioxidant 168 in the antioxidant is 1.8 to 3.
The antioxidant is added, so that the aging resistance of the obtained TPE material can be optimized, the service life of the TPE material is prolonged, and the appearance performance of the extruded surface of the obtained TPE material can be improved.
According to some embodiments of the invention, the raw materials from which the TPE material is made further comprise a lubricant.
According to some embodiments of the present invention, the weight ratio of the SEBS elastomer to the lubricant in the TPE material is 2 to 60.
According to some embodiments of the present invention, the weight ratio of the SEBS elastomer to the lubricant in the TPE material is 9 to 20, and may be, for example, about 9.33.
According to some embodiments of the invention, the lubricant is selected from at least one of polyethylene wax (CAS: 9002-88-4), palmitamide (CAS: 629-54-9), oleamide (CAS: 301-02-0), erucamide (CAS: 112-84-5), and ethylene bisstearamide (CAS: 110-30-5).
According to some preferred embodiments of the present invention, the polyethylene wax (PE wax) may be AC-6A from Hall Winnie.
According to some preferred embodiments of the invention, the lubricant is selected from AC-6A from Hall Winnie.
The lubricant can reduce the friction force between the TPE material and a preparation instrument on one hand, and can improve the compatibility among various preparation raw materials of the TPE material on the other hand, so that the appearance performance of the TPE material is finally improved; because the texture is uniform and the surface has no cracks, the mechanical property of the TPE material is finally improved.
If the proportion of the raw materials for preparing the TPE material is very reasonable, the lubricant is not added, so that the composition of the TPE material can be simplified.
According to some embodiments of the invention, the raw materials for preparing the TPE material further comprise a dispersant.
According to some embodiments of the invention, the weight ratio of the SEBS elastomer to the dispersant in the TPE material is 100-150.
According to some embodiments of the invention, the weight ratio of the SEBS elastomer to the dispersant in the TPE material is 106-140; for example, it may be specifically about 106.7.
According to some embodiments of the invention, the dispersant is selected from KY-220 (also known as EBS 220) of cencino, a specialized dispersant for EBS elastomers.
The dispersant can effectively reduce the operation difficulty in the preparation process of the TPE material.
According to some preferred embodiments of the present invention, the TPE material is prepared from the following raw materials in parts by weight:
Figure BDA0003872608900000061
according to some embodiments of the invention, the thermal conductivity of the TPE material is between 148 and 181 mW/(m · K).
According to some embodiments of the invention, the thermal conductivity of the TPE material is between 148 and 177 mW/(m · K).
According to some embodiments of the invention, the thermal conductivity of the TPE material is between 148 and 166 mW/(m · K).
According to some preferred embodiments of the invention, the thermal conductivity of the TPE material is between 148 and 162 mW/(m-K).
According to some embodiments of the invention, the TPE material has a compression recovery of between 90% and 93.3%.
According to some preferred embodiments of the invention, the compression recovery of the TPE material is between 92.8 and 93.3%.
According to some embodiments of the invention, the compression recovery of the TPE material is between 92.4 and 93.3%.
According to some embodiments of the invention, the compression recovery of the TPE material is between 92.1 and 93.3%.
According to some embodiments of the invention, the TPE material has a density of 0.53-0.66 g/cm 3 In between.
According to some embodiments of the invention, the TPE material has a density of 0.53 to 0.61g/cm 3 In between.
According to some embodiments of the invention, the TPE material has a density of 0.53 to 0.59g/cm 3 In the meantime.
According to some preferred embodiments of the invention, the TPE material has a density of 0.53-0.55 g/cm 3 In the meantime.
According to some embodiments of the invention, the Shore A hardness of the TPE material at 25 ℃ is between 61 and 71.
According to some preferred embodiments of the invention, the Shore A hardness of the TPE material at 25 ℃ is 67-69. For example, may be about 68.
According to some embodiments of the invention, the TPE material has a Shore A hardness of 71-76 at-30 ℃.
According to some preferred embodiments of the present invention, the TPE material has a Shore A hardness of between 72 and 73 at-30 ℃.
According to some embodiments of the invention, the TPE material has a cellular structure.
The cell structure can effectively reduce the thermal conductivity of the obtained TPE material, and when the TPE material is applied to a refrigerator door seal strip, the thermal insulation performance of the door seal strip can be improved, so that the energy efficiency of the refrigerator is improved.
The cellular structure also helps to cushion the compression capacity and promote the compression recovery of the resulting TPE material.
According to some embodiments of the invention, the aspect ratio of the cell structure is between 3.3 and 4.8.
Slenderness ratio is in above-mentioned within range, and the orderliness in hole is showing and is promoting, has finally promoted the heat-proof quality of gained TPE material, when it is used for preparing freezing/cold storage equipment door strip of paper used for sealing, can show the refrigeration efficiency who promotes above-mentioned equipment.
According to some embodiments of the invention, the aspect ratio of the cellular structure is between 3.8 and 4.2.
According to some embodiments of the invention, the aspect ratio of the cellular structure is between 3.8 and 3.9.
According to the embodiment of the second aspect of the invention, the preparation method of the TPE material is provided, and specifically comprises the following steps:
mixing the preparation raw materials of the TPE material, granulating by using a double-screw machine, and carrying out extrusion foaming treatment on the granulated material by using a single-screw machine;
the single screw extruder extrusion foaming treatment adopts supercritical fluid matching to carry out pressurization extrusion foaming.
The mechanism of the preparation method is as follows:
when carrying out single screw rod machine extrusion moulding, a certain warm-up area of single screw rod machine channels into supercritical fluid, through the cavity pressure in the single screw rod machine behind the leading-in supercritical fluid of regulation and control, can effectively regulate and control gas in the TPE material and account for the ratio, form the micropore foaming, finally regulate and control the performance of gained TPE material.
The preparation method provided by the embodiment of the invention has at least the following beneficial effects:
when the TPE material is used for a door seal of refrigeration equipment, in order to improve the heat preservation and insulation effect, the TPE material can be subjected to foaming treatment in the process of preparing the TPE material. In the conventional technology, the foaming process is mainly to add a physical foaming agent or a chemical foaming agent to form a honeycomb or cellular structure. The basic steps of foam molding are the formation of a bubble nucleus, the growth or enlargement of the bubble nucleus, and the stabilization of the bubble nucleus. However, the method of adding a foaming agent to foam the material has the following problems: the foaming agent is not completely decomposed, has high residual quantity and large smell; the residual foaming agent is released to the environment along with the aging of the TPE material, so as to pollute the air or substances stored in the refrigeration equipment; has the disadvantages of environmental pollution and potential harm to human body; the TPE material has uneven foam pores, low smoothness of appearance, poor dimensional stability and low mechanical strength.
The invention adopts supercritical fluid to carry out foaming treatment (generally, the adopted gas is nitrogen), and can avoid the problems of incomplete decomposition and residual foaming agent release in the using process of the foaming agent; by controlling the cavity pressure of the single-screw extruder, the distribution uniformity of the obtained cells (cell structures) in the TPE material and the uniformity of the sizes of the cells can be obviously improved. Thereby improving the appearance, the dimensional stability and the mechanical strength of the TPE material and effectively reducing the density of the TPE material.
According to some embodiments of the present invention, the mixing method of the preparation raw materials comprises mixing the SEBS elastomer and the lubricating oil, and then mixing the mixture with other preparation raw materials.
Because the lubricating oil and the SEBS elastomer have high compatibility, but the SEBS elastomer and other components have poor compatibility, the mixing uniformity of the components of the preparation raw materials can be improved according to the material adding sequence.
It can be understood that the SEBS elastomer and the lubricating oil are mixed firstly, and the main function is wetting; therefore, whether stirring is carried out or not can be selected according to actual operation conditions.
According to some embodiments of the invention, the mixing of the mixture of SEBS elastomer and lubricating oil and other preparation raw materials is carried out in a high-speed mixer.
According to some embodiments of the invention, the feeding speed in the twin-screw machine is between 8 and 50 rpm.
According to some preferred embodiments of the invention, the feeding speed in the twin-screw machine is between 28 and 32 rpm.
According to some embodiments of the invention, the main machine in the twin screw machine rotates at a speed between 200-400 rpm.
According to some embodiments of the invention, the main machine in the twin screw machine rotates at a speed between 290-310 rpm. For example, about 300rpm may be specific.
According to some embodiments of the invention, the twin screw machine has ten temperature zones in total. And defining a temperature zone far away from the extrusion die head as a first temperature zone, and defining a temperature zone of the extrusion die head as a tenth temperature zone.
According to some embodiments of the invention, the temperature of the first temperature zone in the twin screw machine is between 130 ℃ and 150 ℃; for example, it may be specifically selected from about 140 ℃.
According to some embodiments of the invention, the temperature of the second temperature zone in the twin screw machine is between 150 ℃ and 170 ℃; for example, it may be specifically selected from about 160 ℃.
According to some embodiments of the invention, the temperature of the third temperature zone in the twin screw machine is between 170 ℃ and 190 ℃; for example, it may be specifically selected from about 180 ℃.
According to some embodiments of the invention, the temperature of the fourth temperature zone in the twin screw machine is between 170 ℃ and 190 ℃; for example, it may be specifically selected from about 180 ℃.
According to some embodiments of the invention, the temperature of the fifth temperature zone in the twin screw machine is 160-180 ℃; for example, it may be specifically selected from about 170 ℃.
According to some embodiments of the invention, the temperature of the sixth temperature zone in the twin screw machine is between 150 ℃ and 170 ℃; for example, it may be specifically selected from about 160 ℃.
According to some embodiments of the invention, the temperature of the seventh temperature zone in the twin screw machine is between 140 ℃ and 160 ℃; for example, may be selected from about 150 deg.c.
According to some embodiments of the invention, the temperature of the eighth temperature zone in the twin screw machine is 130 to 150 ℃; for example, may be selected from about 140 deg.c.
According to some embodiments of the invention, the temperature of the ninth temperature zone in the twin screw machine is 120 to 140 ℃; for example, may be selected from about 130 deg.c.
According to some embodiments of the invention, the tenth temperature zone in the twin-screw machine, i.e. the extrusion temperature of the pellets, is 100-120 ℃.
When the TPE material preparation raw materials pass through the double-screw machine, the temperature is increased and then decreased; namely, the initial temperature of feeding is low, so that smooth feeding is ensured, the high temperature of the intermediate temperature zone enables the preparation raw materials of the TPE material to be fully melted and uniformly mixed, and then the temperature is reduced, so that the smooth extrusion is ensured, the burst of the extruded granular material is also ensured, and the stability of the extrusion operation is improved.
Through the melting and plasticizing of the granulation process, the fluidity of the granules is improved, when the extrusion foaming treatment is carried out, the operation difficulty is reduced, and the uniformity of the foam holes of the obtained TPE material is improved.
According to some embodiments of the invention, the pelletizing further comprises water cooling the resulting material after the extruding and cutting with a high speed cutter to form the pellets;
according to some embodiments of the invention, the drying step is carried out before the extrusion foaming step. The drying may be carried out in an oven.
According to some embodiments of the invention, the temperature of the drying is between 50 and 70 ℃; for example, it may be 60 ℃.
According to some embodiments of the invention, the drying time is 7 to 9 hours, for example 8 hours.
According to some embodiments of the present invention, the single screw machine has seven temperature zones in total from the feeding section to the extrusion die section;
according to some embodiments of the invention, the temperature of the first temperature zone of the single screw machine is 120-140 ℃; for example, it may be specifically selected from about 130 ℃.
According to some embodiments of the invention, the temperature of the second temperature zone of the single screw machine is 130-150 ℃; for example, it may be specifically selected from about 140 ℃.
According to some embodiments of the invention, the temperatures of the third and fourth temperature zones of the single screw machine are in the range of 140-160 ℃, for example may be independently selected from about 150 ℃.
According to some embodiments of the invention, the temperature of the fifth to seventh temperature zones of the single screw machine is 110-140 ℃, for example, may be independently selected from about 130 ℃, 120 ℃ or 110 ℃.
Compared with the temperature of the temperature zone of the double-screw machine, the highest temperature of the temperature zone of the single-screw machine is lower, because the fluidity of materials in the single-screw machine is improved through the melting in the granulation process, the purposes of saving energy and improving the operability can be achieved on the basis that the performance of the obtained TPE material can be ensured by reducing the temperature.
According to some embodiments of the invention, the main machine speed of the single screw machine is between 150-200 rpm. The rotating speed of the host machine can influence the cell structure in the obtained TPE material, and within the range, the obtained TPE material is more combined with the requirements of freezing/refrigerating materials on door seals.
According to some preferred embodiments of the present invention, the main machine speed of the single screw machine is about 160rpm.
According to some embodiments of the invention, the injection pressure of the supercritical fluid is 7 to 9MPa.
According to some embodiments of the invention, the injection pressure of the supercritical fluid is about 8MPa.
According to some embodiments of the invention, the supercritical fluid is injected by a constant flow injection. Thereby, the saturated gas concentration in the blend (the mixture of material and gas in the single-screw machine) can be regulated and controlled, and the required micro-bubble pore structure can be obtained according to different foaming pressures.
According to some embodiments of the invention, the supercritical fluid comprises at least one of nitrogen and carbon dioxide. Because the fluid used is the main component in the air, even if the fluid is not used completely and escapes, the fluid does not affect the environment.
According to some embodiments of the invention, the injection location of the supercritical fluid is the third temperature zone of the single screw machine. In the temperature range of the third temperature zone, the melt has the best fluidity, so that the structural uniformity of cells in the obtained TPE material can be improved.
Therefore, the temperature range of the single screw machine is 140-160 ℃ at the injection position of the supercritical fluid.
According to some preferred embodiments of the present invention, the pressure of the single screw machine cavity is between 10-20MPa during the pressure extrusion foaming.
According to some preferred embodiments of the invention, the single screw machine has a cavity pressure of between 10-15 MPa.
According to some preferred embodiments of the invention, the single screw machine has a cavity pressure of between 12-13 MPa.
According to some embodiments of the invention, the outlet of the single screw machine has a diverging section and a converging section.
According to some embodiments of the invention, the diverging section has a cross-sectional area that is 1.5-3 times a cross-sectional area of the single screw machine cavity. In this stage, the material obtained is foamed under pressure.
According to some embodiments of the invention, the diverging section has a cross-sectional area that is about 2 times a cross-sectional area of the single screw machine cavity.
According to some embodiments of the invention, the cross-sectional area of the convergent section is 1/3 to 1/8 of the cross-sectional area of the cavity of the single screw machine.
At this stage, the cell structure in the resulting TPE material has a specific aspect ratio (equivalent to collapsing the cells). And simultaneously extruding the obtained material in a thin-wall anisotropic structure.
And adjusting the foaming rate, the orientation degree of a cellular structure and the specific form of the cellular structure in the obtained TPE material according to the sectional areas of the divergent section and the convergent section.
According to some embodiments of the invention, the cross-sectional area of the convergent section is 1/4 to 1/6 of the cross-sectional area of the cavity of the single screw machine.
According to some embodiments of the invention, the cross-sectional area of the convergent section is 1/5 to 1/6 of the cross-sectional area of the cavity of the single screw machine.
According to some embodiments of the present invention, when the TPE material is used for the door seal, the preparation method further comprises subjecting the TPE material obtained by the extrusion foaming process to drawing forming.
Specifically, the TPE material obtained from the extrusion foaming process may be drawn into a corresponding door seal mold to be cooled and shaped.
According to the embodiment of the third aspect of the invention, the door seal is provided, and the preparation raw material of the door seal comprises the TPE material.
Since the door seal adopts all technical solutions of the TPE material of the above embodiments, at least all the advantages brought by the technical solutions of the above embodiments are obtained.
According to the fourth aspect of the embodiment of the invention, the application of the door seal in the refrigeration equipment is provided.
Since the refrigeration equipment adopts all the technical solutions of the door seal of the above embodiments, at least all the beneficial effects brought by the technical solutions of the above embodiments are achieved.
Namely, when the refrigeration equipment comprises the door seal, the refrigeration efficiency can be effectively improved, and the energy consumption is reduced.
According to some embodiments of the invention, the refrigeration appliance comprises at least one of a refrigerator and a freezer.
Unless otherwise specified, "about" in the present invention means an error of ± 2%, for example, about 100 actually means 100 ± 2%.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic diagram of a manufacturing process of an embodiment of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and other embodiments obtained by those skilled in the art without inventive efforts are within the protection scope of the present invention based on the embodiments of the present invention.
In the description of the present invention, the meaning of a plurality is one or more, the meaning of a plurality is two or more, and the above, below, exceeding, etc. are understood as excluding the present numbers, and the above, below, within, etc. are understood as including the present numbers. If the first and second are described for the purpose of distinguishing technical features, they are not to be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
Unless otherwise specified, in the embodiments:
the SEBS elastomer is selected from the group consisting of the pelargonified SEBS YH-503T.
The POE elastomer is at least one selected from the group consisting of POE7447 and DF 610.
The reason why the triple well chemical DF610 was chosen is: the paint has excellent performances of aging resistance, ozone resistance, chemical medium resistance and the like.
After the American Dow POE7447 and the Mitsui chemical DF610 are combined, the heat resistance and the low temperature resistance of the obtained TPE material can be improved; improve the mechanical properties such as tensile strength, tearing strength and the like, and inhibit permanent deformation.
The polyolefin is selected from LDPE 8784ML in Exxon Mobil. Therefore, the polyolefin with lower density can further reduce the density of the TPE material on the basis of ensuring the forming performance of the TPE material.
The lubricating oil is selected from No. 10 white mineral oil (white mineral oil No. 10); the lubricating oil has high compatibility with the SEBS elastomer, the POE elastomer and the polyolefin, and the texture uniformity of the TPE material is finally improved.
The lubricant is selected from AC-6A available from Hall Winnie. The lubricant can reduce the friction force between the TPE material and a preparation instrument, can improve the compatibility among various preparation raw materials of the TPE material, and finally improves the appearance performance of the obtained TPE material; because the texture is uniform and the surface has no cracks, the mechanical property of the TPE material is finally improved.
The antioxidant is selected from a mixture of antioxidant 1010 and antioxidant 168. The antioxidant can optimize the aging resistance of the obtained TPE material, prolong the service life of the TPE material and improve the appearance performance of the extruded surface of the TPE material.
The dispersant is KY-220 (also called EBS 220) of Dongguan Xeno. The dispersant is a special dispersant for the EBS elastomer, and can effectively reduce the operation difficulty in the preparation process of the TPE material.
TABLE 1 compositions (unit: kg) of raw materials prepared in examples 1 to 5
Figure BDA0003872608900000121
Example 1
The TPE material is prepared in the embodiment, the specific formula is shown in Table 1, and the specific steps are as follows:
s1, mixing preparation raw materials:
mixing lubricating oil and SEBS elastomer, adding the lubricating oil and the rest raw materials into a high-speed mixer together after the lubricating oil is fully absorbed by the SEBS elastomer, and uniformly mixing;
s2, granulation:
adding the mixture obtained in the step S1 into a double-screw extruder for melt blending and granulation; wherein:
the temperatures of the first temperature zone to the tenth temperature zone of the double-screw extruder are respectively set to be 140 ℃, 160 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃, 140 ℃, 130 ℃ and 120 ℃;
the rotating speed of a main machine of the double-screw extruder is set to be 300rpm, and the feeding rotating speed is set to be 30rpm;
the smooth feeding can be ensured by setting the temperature of each temperature zone in the double-screw extruder;
the high temperature of the third temperature zone and the fourth temperature zone and the secondary high temperature of the nearby temperature zones can ensure that the mixture obtained in the step S1 is fully melted, and the uniformity degree of mixing is improved;
the tenth temperature, namely the temperature setting of the extrusion die head and the excessive temperature setting between the fourth temperature zone can avoid the mixture from cracking after melting and improve the extrusion stability;
cooling the extruded material with water, granulating by using a high-speed cutting machine to obtain thermoplastic elastomer (TPE) granules, and finally placing the granules in a 60 ℃ drying oven for 8h for drying treatment;
s3, extrusion foaming treatment:
the instrument of adoption is single screw machine, wherein:
the single screw machine has seven temperature zones, and the temperature settings are in turn: 130 ℃, 140 ℃, 150 ℃, 130 ℃, 120 ℃ and 110 ℃;
the reason why the temperature is set as such is: through the melting and plasticizing in the step S2, the fluidity of the TPE material is improved, so that the molding temperature of the extrusion process in the step is reduced compared with that in the previous step;
the main machine rotating speed of the single-screw machine is 160rpm;
the foaming method adopted by the extrusion foaming treatment is supercritical fluid microcellular foaming, wherein:
the supercritical fluid is nitrogen; therefore, the traditional foaming agent is replaced, and the influence of the foaming agent on the environment and the performance of the obtained TPE material is reduced;
the injection position of the supercritical fluid is a third temperature zone of the single-screw machine, the temperature of the temperature zone is the highest, the fluidity of materials in the single-screw machine is also the highest, the mixing degree of injected gas and molten materials is improved, and the uniformity of a foam structure in the obtained TPE material is improved;
the injection pressure of the supercritical fluid is set to be 8MPa, and the pressure in the cavity of the single-screw machine is 10MPa in the process of injecting the supercritical fluid;
the injection mode of the supercritical fluid is a constant-current mode, so that the concentration and the pressure of the gas in the single-screw machine cavity can be regulated and controlled more conveniently, and the density and the appearance of the cellular structure of the TPE material can be regulated more conveniently;
the extrusion foaming machine head of the single-screw machine comprises a divergent section and a convergent section which are sequentially connected, wherein the cross-sectional area of the divergent section is 2 times that of a cavity of the single-screw machine, and the cross-sectional area of the convergent section is 1/4 of that of the cavity of the single-screw machine.
Therefore, the mixture in the single-screw extruder is subjected to pressure relief foaming in a divergent section, and then the plastic porous TPE material is oriented in the flow direction under the action of a stretching flow field in a convergent section; through the treatment of the divergent section and the convergent section, the cell structure of the obtained TPE material is more uniform and ordered, and the mechanical strength of the TPE material is also improved to a certain extent.
S4, forming: and (5) drawing the material obtained in the step (S3) into a corresponding door seal mold for cooling and shaping, and cutting and storing according to the finally required door seal size.
The flow chart of this embodiment is shown in fig. 1.
Example 2
The embodiment prepares the TPE material, and the specific steps are as follows:
s1, mixing preparation raw materials:
the types and the proportions of the preparation raw materials are the same as those of the example 1;
mixing lubricating oil and SEBS elastomer, adding the lubricating oil and the rest raw materials into a high-speed mixer together after the lubricating oil is fully absorbed by the SEBS elastomer, and uniformly mixing;
s2, granulation:
adding the mixture obtained in the step S1 into a double-screw extruder for melt blending and granulation; wherein:
the temperatures of the first temperature zone to the tenth temperature zone of the double-screw extruder are respectively set as 140 ℃, 160 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃, 140 ℃, 130 ℃ and 120 ℃;
the rotating speed of a main machine of the double-screw extruder is set to be 300rpm, and the feeding rotating speed is set to be 30rpm;
the smooth feeding can be ensured by setting the temperature of each temperature zone in the double-screw extruder;
the high temperature of the third temperature zone and the fourth temperature zone and the secondary high temperature of the nearby temperature zone can ensure that the mixture obtained in the step S1 is fully melted, and the uniformity of the mixing is improved;
the tenth temperature, namely the temperature setting of the extrusion die head and the excessive temperature setting between the fourth temperature zone can avoid the mixture from cracking after melting and improve the extrusion stability;
cooling the extruded material with water, granulating by using a high-speed cutting machine to obtain thermoplastic elastomer (TPE) granules, and finally placing the granules in a 60 ℃ drying oven for 8h for drying treatment;
s3, extrusion foaming treatment:
the instrument of adoption is single screw rod machine, wherein:
the single screw machine has seven temperature zones, and the temperature settings are in turn: 130 ℃, 140 ℃, 150 ℃, 130 ℃, 120 ℃ and 110 ℃;
the reason why the temperature is set as such is: through the melting and plasticizing in the step S2, the fluidity of the TPE material is improved, so that the molding temperature of the extrusion process in the step is reduced compared with that in the previous step;
the main machine rotating speed of the single screw machine is 160rpm;
the foaming method adopted by the extrusion foaming treatment is supercritical fluid microcellular foaming, wherein:
the supercritical fluid is nitrogen; therefore, the traditional foaming agent is replaced, and the influence of the foaming agent on the environment and the performance of the obtained TPE material is reduced;
the injection position of the supercritical fluid is a third temperature zone of the single-screw machine, the temperature of the temperature zone is the highest, the fluidity of materials in the single-screw machine is also the highest, the mixing degree of injected gas and molten materials is improved, and the uniformity of a foam structure in the obtained TPE material is improved;
the injection pressure of the supercritical fluid is set to be 8MPa, and the pressure in the cavity of the single-screw machine is 13MPa in the process of injecting the supercritical fluid;
the injection mode of the supercritical fluid is a constant-current mode, so that the concentration and the pressure of the gas in the single-screw machine cavity can be regulated and controlled more conveniently, and the density and the appearance of the cell structure of the obtained TPE material can be regulated more conveniently;
the extrusion foaming machine head of the single-screw machine comprises a divergent section and a convergent section which are sequentially connected, wherein the cross-sectional area of the divergent section is 2 times that of a cavity of the single-screw machine, and the cross-sectional area of the convergent section is 1/4 of that of the cavity of the single-screw machine.
Therefore, the mixture in the single-screw machine is decompressed and foamed in a divergent section, and then the plastic porous TPE material is oriented along the flowing direction under the action of a stretching flow field of a convergent section; through the treatment of diverging section and convergent section, the cell structure of gained TPE material is more even, orderly, and the mechanical strength of TPE material also promotes to a certain extent.
S4, forming: and (4) dragging the material obtained in the step (S3) to a corresponding door seal mold for cooling and shaping, and cutting and storing according to the final required door seal size.
Example 3
This example prepared a TPE material, and the specific steps were:
s1, mixing preparation raw materials:
the types and the proportions of the preparation raw materials are shown in table 1;
mixing lubricating oil and SEBS elastomer, adding the lubricating oil and the rest raw materials into a high-speed mixer together after the lubricating oil is fully absorbed by the SEBS elastomer, and uniformly mixing;
s2, granulating:
adding the mixture obtained in the step S1 into a double-screw extruder for melt blending and granulation; wherein:
the temperatures of the first temperature zone to the tenth temperature zone of the double-screw extruder are respectively set to be 140 ℃, 160 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃, 140 ℃, 130 ℃ and 120 ℃;
the rotating speed of a main machine of the double-screw extruder is set to be 300rpm, and the feeding rotating speed is set to be 30rpm;
the temperature of each temperature zone in the double-screw extruder is set, so that smooth feeding can be ensured;
the high temperature of the third temperature zone and the fourth temperature zone and the secondary high temperature of the nearby temperature zones can ensure that the mixture obtained in the step S1 is fully melted, and the uniformity degree of mixing is improved;
the tenth temperature, namely the temperature setting of the extrusion die head and the excessive temperature setting between the fourth temperature zone can avoid the mixture from cracking after melting and improve the extrusion stability;
cooling the extruded material with water, granulating by using a high-speed cutting machine to obtain thermoplastic elastomer (TPE) granules, and finally placing the granules in a 60 ℃ drying oven for 8h for drying treatment;
s3, extrusion foaming treatment:
the instrument of adoption is single screw machine, wherein:
the single screw machine has seven temperature zones, and the temperature settings are in turn: 130 ℃, 140 ℃, 150 ℃, 130 ℃, 120 ℃ and 110 ℃;
the reason for setting the temperature as such is: through the melting and plasticizing in the step S2, the fluidity of the TPE material is improved, so that the molding temperature of the extrusion process in the step is reduced compared with that in the previous step;
the main machine rotating speed of the single-screw machine is 160rpm;
the foaming method adopted by the extrusion foaming treatment is supercritical fluid microcellular foaming, wherein:
the supercritical fluid is nitrogen; therefore, the traditional foaming agent is replaced, and the influence of the foaming agent on the environment and the performance of the obtained TPE material is reduced;
the injection position of the supercritical fluid is a third temperature zone of the single-screw machine, the temperature of the temperature zone is highest, the fluidity of materials in the single-screw machine is also highest, the mixing degree of injected gas and molten materials is improved, and the uniformity of a foam structure in the obtained TPE material is improved;
the injection pressure of the supercritical fluid is set to be 8MPa, and the pressure in the cavity of the single-screw machine is 10MPa in the process of injecting the supercritical fluid;
the injection mode of the supercritical fluid is a constant-current mode, so that the concentration and the pressure of the gas in the single-screw machine cavity can be regulated and controlled more conveniently, and the density and the appearance of the cellular structure of the TPE material can be regulated more conveniently;
the extrusion foaming machine head of the single-screw machine comprises a divergent section and a convergent section which are sequentially connected, wherein the cross-sectional area of the divergent section is 2 times that of a cavity of the single-screw machine, and the cross-sectional area of the convergent section is 1/5 of that of the cavity of the single-screw machine.
Therefore, the mixture in the single-screw extruder is subjected to pressure relief foaming in a divergent section, and then the plastic porous TPE material is oriented in the flow direction under the action of a stretching flow field in a convergent section; through the treatment of the divergent section and the convergent section, the cell structure of the obtained TPE material is more uniform and ordered, and the mechanical strength of the TPE material is also improved to a certain extent.
S4, forming: and (4) dragging the material obtained in the step (S3) to a corresponding door seal mold for cooling and shaping, and cutting and storing according to the final required door seal size.
Example 4
The embodiment prepares the TPE material, and the specific steps are as follows:
s1, mixing preparation raw materials:
the types and the proportions of the preparation raw materials are shown in table 1;
mixing lubricating oil and SEBS elastomer, adding the lubricating oil and the rest raw materials into a high-speed mixer together after the lubricating oil is fully absorbed by the SEBS elastomer, and uniformly mixing;
s2, granulating:
adding the mixture obtained in the step S1 into a double-screw extruder for melt blending and granulation; wherein:
the temperatures of the first temperature zone to the tenth temperature zone of the double-screw extruder are respectively set to be 140 ℃, 160 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃, 140 ℃, 130 ℃ and 120 ℃;
the rotating speed of a main machine of the double-screw extruder is set to be 300rpm, and the feeding rotating speed is set to be 30rpm;
the smooth feeding can be ensured by setting the temperature of each temperature zone in the double-screw extruder;
the high temperature of the third temperature zone and the fourth temperature zone and the secondary high temperature of the nearby temperature zone can ensure that the mixture obtained in the step S1 is fully melted, and the uniformity of the mixing is improved;
the tenth temperature, namely the temperature setting of the extrusion die head and the excessive temperature setting between the fourth temperature zone can avoid the mixture from cracking after melting and improve the extrusion stability;
cooling the extruded material with water, granulating by using a high-speed cutting machine to obtain thermoplastic elastomer (TPE) granules, and finally placing the granules in a drying oven at 60 ℃ for 8h for drying treatment;
s3, extrusion foaming treatment:
the instrument of adoption is single screw rod machine, wherein:
the single screw machine has seven temperature zones, and the temperature setting is as follows in sequence: 130 ℃, 140 ℃, 150 ℃, 130 ℃, 120 ℃ and 110 ℃;
the reason why the temperature is set as such is: through the melting and plasticizing in the step S2, the fluidity of the TPE material is improved, so that the molding temperature of the extrusion process in the step is reduced compared with that in the previous step;
the main machine rotating speed of the single screw machine is 160rpm;
the foaming method adopted by the extrusion foaming treatment is supercritical fluid microcellular foaming, wherein:
the supercritical fluid is nitrogen; therefore, the traditional foaming agent is replaced, and the influence of the foaming agent on the environment and the performance of the obtained TPE material is reduced;
the injection position of the supercritical fluid is a third temperature zone of the single-screw machine, the temperature of the temperature zone is highest, the fluidity of materials in the single-screw machine is also highest, the mixing degree of injected gas and molten materials is improved, and the uniformity of a foam structure in the obtained TPE material is improved;
the injection pressure of the supercritical fluid is set to be 8MPa, and the pressure in the cavity of the single-screw machine is 15MPa in the process of injecting the supercritical fluid;
the injection mode of the supercritical fluid is a constant-current mode, so that the concentration and the pressure of the gas in the single-screw machine cavity can be regulated and controlled more conveniently, and the density and the appearance of the cellular structure of the TPE material can be regulated more conveniently;
the extrusion foaming machine head of the single-screw machine comprises a divergent section and a convergent section which are sequentially connected, wherein the cross-sectional area of the divergent section is 1.5 times that of a cavity of the single-screw machine, and the cross-sectional area of the convergent section is 1/4 of that of the cavity of the single-screw machine.
Therefore, the mixture in the single-screw machine is decompressed and foamed in a divergent section, and then the plastic porous TPE material is oriented along the flowing direction under the action of a stretching flow field of a convergent section; through the treatment of the divergent section and the convergent section, the cell structure of the obtained TPE material is more uniform and ordered, and the mechanical strength of the TPE material is also improved to a certain extent.
S4, forming: and (4) dragging the material obtained in the step (S3) to a corresponding door seal mold for cooling and shaping, and cutting and storing according to the final required door seal size.
Example 5
This example prepared a TPE material, and the specific process was:
s1, mixing preparation raw materials:
the types and the proportions of the preparation raw materials are shown in table 1;
mixing lubricating oil and SEBS elastomer, adding the lubricating oil and the rest raw materials into a high-speed mixer together after the lubricating oil is fully absorbed by the SEBS elastomer, and uniformly mixing;
s2, granulating:
adding the mixture obtained in the step S1 into a double-screw extruder for melt blending and granulation; wherein:
the temperatures of the first temperature zone to the tenth temperature zone of the double-screw extruder are respectively set as 140 ℃, 160 ℃, 180 ℃, 170 ℃, 160 ℃, 150 ℃, 140 ℃, 130 ℃ and 120 ℃;
the rotating speed of a main machine of the double-screw extruder is set to be 300rpm, and the feeding rotating speed is set to be 30rpm;
the smooth feeding can be ensured by setting the temperature of each temperature zone in the double-screw extruder;
the high temperature of the third temperature zone and the fourth temperature zone and the secondary high temperature of the nearby temperature zone can ensure that the mixture obtained in the step S1 is fully melted, and the uniformity of the mixing is improved;
the tenth temperature, namely the temperature setting of the extrusion die head and the excessive temperature setting between the fourth temperature zone can avoid the mixture from cracking after melting and improve the extrusion stability;
cooling the extruded material with water, granulating by using a high-speed cutting machine to obtain thermoplastic elastomer (TPE) granules, and finally placing the granules in a drying oven at 60 ℃ for 8h for drying treatment;
s3, extrusion foaming treatment:
the instrument of adoption is single screw rod machine, wherein:
the single screw machine has seven temperature zones, and the temperature setting is as follows in sequence: 130 ℃, 140 ℃, 150 ℃, 130 ℃, 120 ℃ and 110 ℃;
the reason why the temperature is set as such is: through the melting plasticization in the step S2, the fluidity of the TPE material is improved, so that the molding temperature of the extrusion process in the step is reduced compared with that in the previous step;
the main machine rotating speed of the single screw machine is 160rpm;
the foaming method adopted by the extrusion foaming treatment is supercritical fluid microcellular foaming, wherein:
the supercritical fluid is nitrogen; therefore, the traditional foaming agent is replaced, and the influence of the foaming agent on the environment and the performance of the obtained TPE material is reduced;
the injection position of the supercritical fluid is a third temperature zone of the single-screw machine, the temperature of the temperature zone is highest, the fluidity of materials in the single-screw machine is also highest, the mixing degree of injected gas and molten materials is improved, and the uniformity of a foam structure in the obtained TPE material is improved;
the injection pressure of the supercritical fluid is set to be 8MPa, and the pressure in the cavity of the single-screw machine is 12MPa in the process of injecting the supercritical fluid;
the injection mode of the supercritical fluid is a constant-current mode, so that the concentration and the pressure of the gas in the single-screw machine cavity can be regulated and controlled more conveniently, and the density and the appearance of the cell structure of the obtained TPE material can be regulated more conveniently;
the extrusion foaming machine head of the single-screw machine comprises a divergent section and a convergent section which are sequentially connected, wherein the cross-sectional area of the divergent section is 1.5 times that of a cavity of the single-screw machine, and the cross-sectional area of the convergent section is 1/6 of that of the cavity of the single-screw machine.
Therefore, the mixture in the single-screw machine is decompressed and foamed in a divergent section, and then the plastic porous TPE material is oriented along the flowing direction under the action of a stretching flow field of a convergent section; through the treatment of the divergent section and the convergent section, the cell structure of the obtained TPE material is more uniform and ordered, and the mechanical strength of the TPE material is also improved to a certain extent.
S4, forming: and (4) dragging the material obtained in the step (S3) to a corresponding door seal mold for cooling and shaping, and cutting and storing according to the final required door seal size.
Comparative example 1
This comparative example prepared a TPE material, which specifically differs from example 1 in that:
(1) In the step S3, in the process of injecting the supercritical fluid, the pressure in the cavity of the single-screw machine is 0MPa.
(2) In step S3, the cross-sectional area of the divergent section is 1 time of the cross-sectional area of the cavity of the single-screw machine, and the cross-sectional area of the convergent section is 1 time of the cross-sectional area of the cavity of the single-screw machine. I.e. it is equivalent to not having a diverging section and a converging section.
Comparative example 2
This comparative example prepared a TPE material, which specifically differs from example 1 in that:
in the step S3, in the process of injecting the supercritical fluid, the pressure in the cavity of the single-screw machine is 0MPa.
Test example
The test example tests the performance of the TPE materials obtained in the examples 1-5 and the comparative examples 1-2, and specifically:
the thermal conductivity was measured as (22.5 ℃): the test was carried out as specified in the standard document numbered GB 3399-1982. Sampling rules are as follows: sampling at the position where a proper test sample block can be obtained, wherein the number of the samples is at least 2, and averaging the test results. And (3) testing conditions: an EKO flat plate mutual heating method is adopted, the average temperature is 22.5 ℃, the cold plate is set to be 10 ℃, and the hot plate is set to be 35 ℃; a standard sample block of 200mm multiplied by 25mm is tested in a constant temperature and humidity room (the temperature is 25 +/-2 ℃, and the humidity is 50 +/-10%);
the test method of the compression recovery rate comprises the following steps: the initial thickness d of the test specimen was measured by the method described in GB/T6342 0 Placing the sample between two flat plates, compressing to 80% of the sample thickness, maintaining the state for 22h, maintaining the ambient temperature at 70 deg.C, maintaining the ambient temperature at 25 deg.C, removing the two flat plates, recovering the sample for 30min, testing the final thickness d of the sample, and calculating the compression recovery rate d/d 0 ×100％。
The density is carried out by adopting a method disclosed in a national standard document with the number of GB/T1033.1-2008;
the shore hardness test is carried out according to the method disclosed in the national standard document with the number GB/T2411-2008;
the testing method of the length-diameter ratio of the foam hole is as follows: sample preparation was carried out by the method provided in reference number GB/T12811 and the length and diameter of not less than 100 cells were recorded and the average of the ratio of length to diameter was calculated.
The test results are shown in table 2.
TABLE 2 Performance results of TPE materials obtained in examples 1-5 and comparative examples 1-2
Figure BDA0003872608900000201
In table 2, "-" indicates that no test was performed, specifically because the parameters of the preparation method were adjusted in comparative examples 1 to 2, the obtained TPE material had no cell structure, or the cell structure was irregular and uneven, and thus a reasonable cell aspect ratio could not be counted.
From the results in table 2, it can be seen that the TPE material obtained by combining the preparation raw materials and the preparation method provided by the present invention has lower thermal conductivity, higher compression recovery, lower density, lower hardness and suitable cell aspect ratio. Therefore, when the TPE material is applied to the door seal of the refrigerator, the service life of the door seal is long due to high compression recovery rate; because the hardness is lower, the obtained door seal has higher fit degree with other parts of the refrigerator, and further reduces the energy consumption of the refrigerator; because the density is lower, the density of the foam holes is higher, and the thermal conductivity is lower, so that the cold insulation effect of the refrigerator can be improved, and the energy consumption of the refrigerator can be reduced; the proper cell orientation and length-diameter ratio equivalently improve the consistency of the obtained TPE material, and further improve the processability and the appearance performance of the obtained TPE material, so that the TPE material is suitable for manufacturing refrigerator door seals in various shapes.
Compared with the examples 1-2, if the pressure in the cavity of the single-screw machine is increased, the thermal conductivity, the density and the hardness of the obtained TPE material can be reduced; but the compression recovery rate is reduced to some extent. The reason is that the pressure in the cavity of the single-screw extruder is increased, which is equivalent to that in the preparation process of the TPE material, the proportion of gas in the mixture in the single-screw extruder is increased, so that the density of the cellular structure of the obtained TPE material is increased, and the length-diameter ratio of the cells is increased; meanwhile, the cell structure is increased, and the structural stability is reduced, so that the compression recovery rate is slightly reduced.
Comparing example 1 with example 3, it is understood that when the amounts of the SEBS elastomer and the POE elastomer are reduced, the compression recovery rate is reduced to some extent because the compression recovery rate is related to the amount of the elastomer used in the raw material for preparation; meanwhile, the composition of the use amounts of the preparation raw materials determines the mixing uniformity of the preparation raw materials in the granulation process and also determines the uniformity of the foam pores in the foaming process, and compared with example 1, the proportion of the preparation raw materials in example 3 can reduce the hardness and the heat conductivity of the obtained TPE material to a certain extent, and simultaneously reduce the compression recovery rate. Further, if the cross-sectional area of the convergent section is reduced, the orientation of the convergent section on the TPE material is improved, thereby increasing the aspect ratio of cells in the obtained TPE material.
It can be seen from comparing example 1 with example 4 that increasing the amounts of SEBS elastomer and POE elastomer in the raw materials for preparing TPE material resulted in substantially opposite trend to that of example 3, which further proves the effect of the proportioning of the raw materials for preparing TPE material mentioned in example 3. Meanwhile, the decrease of the density and the decrease of the thermal conductivity in the example 4 are also related to the increase of the pressure in the cavity of the single-screw extruder, that is, the density of the cell structure in the obtained TPE material is increased. Further, the aspect ratio of the bore is a result of the combined effects of the pressure in the chamber and the ratio of the cross-sectional areas of the converging and diverging sections. Thus, in example 4, although the ratio of the cross-sectional areas of the divergent section and the convergent section is reduced, the pressure in the cavity is greatly increased, and the aspect ratio of the cell structure in the final TPE material is still higher than that in example 1.
As can be seen from comparison between example 1 and example 5, if the ratio of the lubricant oil is increased, the lubricant oil also acts as a lubricant to some extent, and obtains a mechanical effect and an appearance effect equivalent to those of example 1. But after the proportion of the lubricating oil is greatly increased, the lubricating oil occupies a part of the cell structure, so that the thermal conductivity and the density of the obtained TPE material are increased to a certain extent. Meanwhile, the embodiment 5 simultaneously improves the cavity pressure and the sectional area ratio of the divergent section to the convergent section in the preparation process, so that the length-diameter ratio of the cell structure of the obtained TPE material is obviously improved.
As can be seen from comparison between example 1 and comparative examples 1 and 2, if the pressure in the cavity is 0MPa, it means that effective foaming is not achieved, and therefore the obtained TPE material has no cell structure, the corresponding density and thermal conductivity are significantly improved, and the compression recovery rate is significantly reduced.
Comparing comparative examples 1-2, it can be seen that the ratio of the cross-sectional areas of the converging section and the diverging section must be matched with the pressure in the chamber to function. In conclusion, the TPE material with low density, excellent mechanical property and good heat insulation performance is obtained by matching the preparation raw materials and the preparation method. Due to the excellent performance, the material is hopeful to be used for preparing door seals, and the refrigeration efficiency of refrigeration equipment is obviously improved.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims (22)

1. The TPE material is characterized by comprising the following raw materials in parts by weight:
Figure FDA0003872608890000011
2. the TPE material of claim 1, wherein the Shore A hardness of the SEBS elastomer is between 50 and 80.
3. The TPE material of claim 1, wherein the POE elastomer has a Shore A hardness of 60-64.
4. The TPE material of claim 1, wherein the POE elastomer is prepared from monomers comprising ethylene and octene.
5. The TPE material of claim 1, wherein the polyolefin has a melt index between 0.8 and 1.0g/10min at 190 ℃ under a 2.16kg test.
6. The TPE material of claim 1, wherein the polyolefin is selected from at least one of PP, LDPE, LLDPE and HDPE.
7. The TPE material of claim 1, wherein the raw materials from which the TPE material is prepared further comprise at least one of an inorganic filler, an antioxidant, a lubricant, and a dispersant.
8. The TPE material of any one of claims 1 to 7, wherein the thermal conductivity of the TPE material is between 148 and 181 mW/(m-K).
9. TPE material according to any of claims 1 to 7, wherein the compression recovery of the TPE material is between 90 and 93.3%.
10. The TPE material of any one of claims 1-7, wherein the TPE material has a cellular structure therein.
11. The TPE material of claim 10, wherein the aspect ratio of the cell structure is between 3.3 and 4.8.
12. The TPE material of any one of claims 1 to 7, wherein the TPE material has a density of 0.53 to 0.66g/cm 3 In the meantime.
13. A process for the preparation of a TPE material according to any of claims 1-12, wherein the process comprises the steps of:
mixing the preparation raw materials of the TPE material, granulating by using a double-screw machine, and carrying out extrusion foaming treatment on the granulated material by using a single-screw machine;
the single screw extruder extrusion foaming treatment adopts supercritical fluid matching to carry out pressurization extrusion foaming.
14. The method for preparing the polypropylene composition according to claim 13, wherein the pressure of the single screw machine cavity is between 10 and 20MPa when the pressure extrusion foaming is carried out.
15. The production method according to claim 13, wherein an injection pressure of the supercritical fluid is 7 to 9MPa.
16. The method according to claim 13, wherein the supercritical fluid is injected by a constant flow injection.
17. The method of claim 13, wherein the outlet of the single screw machine has a diverging section and a converging section.
18. The method of claim 17, wherein the diverging section has a cross-sectional area that is 1.5 to 3 times a cross-sectional area of the single screw machine cavity.
19. The method of claim 17, wherein the cross-sectional area of the convergent section is 1/3 to 1/8 of the cross-sectional area of the chamber of the single screw machine.
20. A door seal, characterized in that the door seal is made from a material comprising the TPE material according to any one of claims 1 to 12.
21. Use of a door seal according to claim 20 in a refrigeration appliance.
22. The use of claim 21, wherein the refrigeration appliance comprises at least one of a refrigerator and a freezer.
CN202211201637.8A 2022-09-29 2022-09-29 TPE material and preparation method and application thereof Pending CN115418070A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000313024A (en) * 1999-04-30 2000-11-14 Toyo Tire & Rubber Co Ltd Production of thermoplastic elastomer foam
CN101356215A (en) * 2005-12-05 2009-01-28 Jsr株式会社 Thermoplastic elastomer composition, foam product, and process for production of the composition or foam product
CN104151766A (en) * 2014-07-30 2014-11-19 广东金源科技股份有限公司 TPE (thermoplastic elastomer) material and preparation method thereof
CN104877245A (en) * 2015-05-26 2015-09-02 华南理工大学 Method for preparing rubber-toughened PS foam material through extrusion of supercritical fluid
CN106916468A (en) * 2017-03-21 2017-07-04 合肥华凌股份有限公司 Fretting map door seal pellet and preparation method thereof and gasket
CN114350051A (en) * 2022-02-09 2022-04-15 海信（山东）冰箱有限公司 Foaming material particle, preparation method and application thereof, refrigerator door seal and refrigerator

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000313024A (en) * 1999-04-30 2000-11-14 Toyo Tire & Rubber Co Ltd Production of thermoplastic elastomer foam
CN101356215A (en) * 2005-12-05 2009-01-28 Jsr株式会社 Thermoplastic elastomer composition, foam product, and process for production of the composition or foam product
CN104151766A (en) * 2014-07-30 2014-11-19 广东金源科技股份有限公司 TPE (thermoplastic elastomer) material and preparation method thereof
CN104877245A (en) * 2015-05-26 2015-09-02 华南理工大学 Method for preparing rubber-toughened PS foam material through extrusion of supercritical fluid
CN106916468A (en) * 2017-03-21 2017-07-04 合肥华凌股份有限公司 Fretting map door seal pellet and preparation method thereof and gasket
CN114350051A (en) * 2022-02-09 2022-04-15 海信（山东）冰箱有限公司 Foaming material particle, preparation method and application thereof, refrigerator door seal and refrigerator

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