CN116554648A - Anti-aging and low-noise TPEE fiber material - Google Patents

Anti-aging and low-noise TPEE fiber material Download PDF

Info

Publication number
CN116554648A
CN116554648A CN202210110659.7A CN202210110659A CN116554648A CN 116554648 A CN116554648 A CN 116554648A CN 202210110659 A CN202210110659 A CN 202210110659A CN 116554648 A CN116554648 A CN 116554648A
Authority
CN
China
Prior art keywords
thermoplastic polyester
polyester elastomer
elastomer composition
composition according
total weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210110659.7A
Other languages
Chinese (zh)
Inventor
胡立峰
龚雪
赵锋
刘婷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yanfeng International Seating Systems Co Ltd
Original Assignee
Yanfeng International Seating Systems Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yanfeng International Seating Systems Co Ltd filed Critical Yanfeng International Seating Systems Co Ltd
Priority to CN202210110659.7A priority Critical patent/CN116554648A/en
Priority to PCT/CN2022/122351 priority patent/WO2023142505A1/en
Publication of CN116554648A publication Critical patent/CN116554648A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/12—Applications used for fibers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/04—Thermoplastic elastomer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present application relates to a thermoplastic polyester elastomer composition comprising, based on the total weight of the composition: a) 80-98% of thermoplastic polyester elastomer TPEE; b) 0.1-3% of diphenylamine antioxidant; c) 0.1-2.8% of fatty acid amide lubricant; and D) 0.1 to 2.5% of a tackifier which is an epoxy-functional polymer based on vinylaromatic compounds and (meth) acrylic compounds. Furthermore, the present application relates to a method for preparing such thermoplastic polyester elastomer fiber material. The fibrous material according to the invention can be used as a cushioning material in office chairs, sofas, mattresses, carpets, seating in vehicles.

Description

Anti-aging and low-noise TPEE fiber material
Technical Field
The present application relates to a TPEE fibrous material having in particular improved resistance to ageing and low noise and also improved resistance to degradation. The present application furthermore relates to a method for producing such a fibrous material.
Background
Thermoplastic polyester elastomers (TPEEs) are block copolymers that generally comprise a high melting point, high hardness crystalline polyester hard segment and a lower glass transition temperature amorphous polyether or polyester soft segment in their structure. The elastomer is in a two-phase association structure, wherein the hard chain segment can play a physical crosslinking role to endow the product with certain shape stability, and the soft chain segment can endow the material with high rebound resilience in an amorphous way. TPEE has both the softness and elasticity of rubber and the rigidity and workability of thermoplastics. Therefore, such materials are widely used in the fields of furniture, home appliances, office supplies, automobiles, trains, ships, or aerospace as cushioning materials, for example, cushioning materials in seating seats in office chairs, sofas, mattresses, carpets, vehicles.
In general, thermoplastic polyester elastomer raw materials are extrusion molded in a molten state into a continuously curved, randomly entangled, partially thermally bonded random fiber material, which is then cooled with a liquid by contacting each other to obtain a three-dimensional net-like structure.
CN103998668B discloses a three-dimensional network structure composed of thermoplastic polyester elastomer material. The thermoplastic polyester elastomer is a polyester block copolymer having a high-melting crystalline polymer segment (a) and a low-melting polymer segment (b). In this document, such a three-dimensional mesh structure can be used for seats and mattresses. According to this document, the three-dimensional network is made flexible in the direction of extrusion by alternately presenting loose regions of low bulk density and dense regions of high bulk density in a certain direction of extrusion during manufacture, thereby imparting reduced noise and aging resistance at temperatures of, for example, 80 ℃ or higher to the finished mattress.
However, the current market places higher demands on the aging resistance and noise reduction properties of TPEE fiber materials. In particular, when such a fiber material is required to be used for a seat cushion material for vehicles, it is desirable to be able to further improve the aging resistance of the TPEE fiber material, particularly at 140 ℃ or more, and also to enable the fiber to maintain its structure without losing its elasticity for a considerable period of time. In addition, it is also desired to further reduce frictional noise generated between filaments and improve the riding experience of passengers.
In addition, it has been found that TPEE fiber materials are susceptible to degradation during extrusion, and thus there is also a need to improve the degradation resistance of TPEE materials.
Disclosure of Invention
In view of the above technical problems, the inventors of the present application have found that the above technical problems can be effectively improved by screening and optimizing additives added to a TPEE matrix, i.e., TPEE fibrous materials having improved overall high temperature aging resistance, noise reduction and degradation resistance can be obtained.
Accordingly, a first aspect of the present invention relates to a thermoplastic polyester elastomer composition comprising, based on the total weight of the composition:
a) 80-98% of thermoplastic polyester elastomer TPEE;
b) 0.1-3% of diphenylamine antioxidant;
c) 0.1-2.8% of fatty acid amide lubricant;
d) 0.1-2.5% of a tackifier, which is an epoxy-functional polymer based on vinylaromatic compounds and (meth) acrylic compounds.
The second aspect of the invention relates to a process for the preparation of a thermoplastic polyester elastomer according to the invention.
Thermoplastic polyester elastomers TPEE suitable for use in the present invention are known per se and are not particularly limited as long as they contain both a crystalline polyester hard segment of high melting point and an amorphous polyether or polyester soft segment of lower glass transition temperature in the structure.
Accordingly, suitable thermoplastic polyester elastomers TPEE may include polyester-ether block copolymers having thermoplastic polyesters as hard segments and polyalkylene glycols as soft segments therein, or polyester-ester block copolymers having aliphatic polyesters as soft segments.
In an advantageous embodiment, the thermoplastic polyester elastomer TPEE may comprise a polyester-ester or polyester-ether block copolymer based on, for example, a polyester of an aromatic dicarboxylic acid with an aliphatic diol and an aliphatic polyester and/or polyether soft segment.
As the polyester-ether block copolymer, for example, at least one dicarboxylic acid selected from the group consisting of: aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid, naphthalene-2, 7-dicarboxylic acid, diphenyl-4, 4' -dicarboxylic acid, alicyclic dicarboxylic acids such as 1, 4-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid dimer acid, or ester-formable derivatives thereof, and the like; and at least one glycol component selected from the group consisting of: aliphatic diols such as 1, 4-butanediol, ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, etc., alicyclic diols such as 1, 1-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, etc., or ester-formable derivatives thereof; and at least one polyalkylene glycol selected from the group consisting of: such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol or ethylene oxide-propylene oxide copolymers having a number average molecular weight of about 300 to 5000.
As the polyester-ester block copolymer, for example, a ternary block copolymer composed of at least one of the above-mentioned dicarboxylic acid, diol, and polyester diol such as polylactone having a number average molecular weight of about 300 to 5000. In view of heat adhesiveness, hydrolysis resistance, stretchability, heat resistance, and the like, a ternary block copolymer formed of terephthalic acid or/and naphthalene 2, 6-dicarboxylic acid as a dicarboxylic acid, 1, 4-butanediol as a diol component, polytetramethylene glycol as a polyalkylene glycol, or a ternary block copolymer having polylactone as a polyester glycol is particularly preferable.
In some special cases, for example, those containing polysiloxane-based soft segments or polyolefin-based soft segments may also be used. These soft segments may be incorporated into the thermoplastic polyester elastomer by copolymerization or blending.
In an advantageous embodiment, the soft segment content of the thermoplastic polyester elastomer is preferably 15% by weight or more, more preferably 25% by weight or more, still more preferably 30% by weight or more, particularly preferably 40% by weight or more, and preferably 80% by weight or less, more preferably 70% by weight or less.
Such thermoplastic polyester elastomers are commercially available, for example, from Dissmann as Anitel or from DuPont et al.
The thermoplastic polyester elastomer composition according to the present invention should further comprise 0.1 to 3.0%, preferably 0.5 to 2.6%, more preferably 0.9 to 2.0% of a diphenylamine-based antioxidant, based on the total weight of the composition. The inventors of the present application have found that when a diphenylamine-based antioxidant (as compared to other conventional antioxidants such as hindered phenols or phosphites, etc.) is particularly selected and used in the thermoplastic polyester elastomer composition in the required amount of 0.1 to 3.0%, the aging resistance of the fiber material produced from the composition can be significantly improved after 7 days at 140 ℃, and the chalking phenomenon can be significantly improved. In particular, it has been found that when a diphenylamine antioxidant is used in combination with the additional components C) and D) as specified above, the material after this heat aging can have a compression set of < 11%, even < 10% and a rate of change in compressive strength of < 11%, for example < 10%, even < 8%.
Diphenylamine compounds suitable for use in the present application are a class of antioxidants that achieve antioxidant function by capturing free radicals in the polymer degradation chain reaction, eliminating peroxidized free radicals, and terminating the oxidation reaction. In general, diphenylamine-based antioxidants are based on derivatives of diphenylamine compounds, including both ketoamine and alkylated diphenylamines, for example they may have the following structural formula (I):
wherein R1 and R2 represent optionally one or more, preferably one, substituent(s) on the respective benzene ring selected from C1-C18, preferably C2-C12 or C3-C10 alkyl or aralkyl, provided that at least one R1 or R2 substituent is present in formula (I); and both R1 and R2 may also form a straight-chain or branched alkylene group having C1-C8, such as C3-C6, linking the two benzene rings.
Preferably, in formula (I) R1 and R2 are present and R1 and R2 represent one of said substituents on the respective benzene rings, or both R1 and R2 form said alkylene group linking the two benzene rings.
Here and in the context, the alkyl radicals mentioned are preferably straight-chain, branched or cyclic alkyl radicals having from 1 to 18, more preferably from 2 to 12 and from 3 to 10, C atoms, for example methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and the isomeric forms thereof. The alkylene group is a linear or branched alkylene group preferably having 1 to 8 or 3 to 6C atoms, such as ethylene, propylene, isopropylene and the like. The aralkyl group is preferably a phenylalkyl group such as benzyl, phenethyl, α -methylbenzyl, α -dimethylbenzyl, phenylisopropyl, etc.
Diphenylamine-based antioxidants are commercially available, for example, as Naugard 445, ble or DDA.
Particularly preferably, the diphenylamine-based antioxidant is selected from the following:
the inventors of the present application have found that when the amount of the diphenylamine-based antioxidant is less than 0.1%, the fiber material has low antioxidation efficiency, poor aging resistance, and pulverization is more likely to occur under heat aging conditions; and when the amount of the diphenylamine-based antioxidant is more than 3.0%, the aging performance cannot be further improved.
Furthermore, the inventors of the present application have found that if 0.1 to 2.8%, preferably 0.3 to 2.3%, more preferably 0.5 to 1.8% of a fatty acid amide-based lubricant based on the total weight of the composition is added to the composition, the noise reduction of the fibrous material made of the thermoplastic polyester elastomer can be further improved while also compromising the degradation resistance of the material. If the amount of the fatty amide-based lubricant to be added is too low, the desired noise reduction properties cannot be achieved. On the other hand, if the amount of the fatty amide-based lubricant is more than 2.8%, the extruded filaments are too smooth to cause bonding and entanglement between filaments, a three-dimensional network structure cannot be formed, and the product is sticky, has a slow rebound, and affects heat aging resistance and degradation resistance to some extent.
In this application, the so-called "lubricant" is sometimes also referred to as a "slip agent". Fatty acid amide-based lubricants suitable for incorporation into the thermoplastic polyester elastomer compositions of the present application to reduce noise in fibrous materials are compounds that contain an amide group as well as a saturated or unsaturated aliphatic group from a molecular structure perspective. The fatty acid amide lubricant may contain one or more, such as two, amide groups in the molecule. The aliphatic group is then preferably a linear, branched or cyclic saturated or unsaturated aliphatic group, which preferably has from 6 to 40, more preferably from 8 to 30, such as from 10 to 25, carbon atoms, and optionally may have one or more, such as two, carbon-carbon double bonds.
Particularly preferably, the fatty acid amide-based lubricant is selected from erucamide, oleamide, stearic acid amide such as vinyl distearate amide or amide wax, and the like.
Such fatty acid amide type lubricants are known in the art and are commercially available.
Furthermore, the inventors have found that the degradation resistance of the polyester elastomer can be further improved, in particular when the TPEE fiber material is extruded in an extruder, if a certain amount of tackifier, in particular 0.1 to 2.5%, preferably 0.5 to 2.2% by weight based on the total weight of the composition, of an epoxy functional tackifier based on a polymer of a vinyl aromatic compound monomer and a (meth) acrylic compound monomer is further added to the thermoplastic polyester elastomer composition.
The epoxy-functional vinyl aromatic monomer and (meth) acrylic monomer-based polymer is a polymer having a main chain composed mainly of vinyl aromatic monomer units and (meth) acrylic monomer units, and a plurality of epoxy-containing side chain groups grafted on the main chain. Advantageously, the epoxy-functional polymer based on vinylaromatic and (meth) acrylic monomers has 90%, preferably 95%, more preferably 98% or 99%, and even consists entirely of vinylaromatic and (meth) acrylic monomer units. The epoxy groups may be attached to the polymer backbone, for example, via a C1-C12, preferably C2-C8 (oxy) alkylene group.
The "(meth) acrylic compound" refers to a compound having a methacryloyl group or an acryl group, preferably a compound having a methacryloyloxy group or an acryloyloxy group, such as methacrylic acid, acrylic acid, a C1-C12 alkyl acrylate, a C1-C12 alkyl methacrylate, glycidyl acrylate, and the like.
The vinyl aromatic compounds include styrene monomers and derivatives thereof, particularly alkyl (e.g., C1-C8 alkyl) or halogen substituted styrene monomers such as styrene, alpha-methylstyrene, alpha-chlorostyrene, or p-methylstyrene, and the like, with styrene being preferred.
In a preferred embodiment, the tackifier is a copolymer of epoxy-functionalized styrene and glycidyl (meth) acrylate.
The epoxy functionalization of the polymer can be carried out in a conventional manner. For example, this can be achieved by adding the copolymerizable monomer having an epoxy group in an amount corresponding to the required epoxy equivalent weight in the preparation of the copolymer. The copolymerizable monomer having an epoxy group is, for example, a vinyl monomer having an epoxy group, particularly, glycidyl (meth) acrylate.
The preparation of such tackifiers is known per se and the products are commercially available. Advantageously, the epoxy-functional polymers based on vinylaromatic monomers and (meth) acrylic monomers have a weight average molecular weight of from 2 to 40 ten thousand, preferably from 5 to 20 ten thousand, and their epoxide equivalent can be, for example, between 100 and 800g/mol, preferably between 150 and 650 g/mol. The epoxy equivalent represents the mass of the resin containing 1mol of epoxy groups, expressed in g/mol.
The weight average molecular weight was measured by GPC using polystyrene as a standard.
Here, the epoxy equivalent may be measured according to ASTM D1652.
In addition to the above-mentioned components, other additives may be added to the thermoplastic polyester elastomer composition of the present invention as long as they do not affect its use properties and its molding process. Such other additives include, for example, other antioxidants such as hindered phenols and phosphites, ultraviolet absorbers such as benzophenones and benzotriazoles, other lubricants such as calcium stearate or silicone based lubricants, deodorants, antimicrobials, mildewcides, colorants, fragrances, flame retardants, and moisture absorbers, and the like.
The other additives, if used, are added in an amount ranging from 0.1% to 8%, for example from 0.5% to 5%, based on the total weight of the thermoplastic polyester elastomer composition.
Preferably, phosphite antioxidants, hindered phenol antioxidants and/or ultraviolet absorbers, each in the range of 0.5-1.5% by weight based on the total weight of the composition, are further used. It is also preferred to use 0.1 to 5% each, based on the total weight of the composition, of a calcium stearate and/or a silicone-based lubricant.
A second aspect of the present application relates to a process for preparing a thermoplastic polyester elastomer according to the invention comprising: i) Providing the individual components of the thermoplastic polyester elastomer as described above and mixing them, ii) melt extruding the resulting composition into fibrous strands at a temperature of from 10 to 120 ℃ above its melting point, and iii) randomly entangling and bending the resulting strands to form a three-dimensional network.
In the context of the present application, "fiber" is sometimes used interchangeably with "wire" and refers to a linear material having a length that is much greater than the cross-sectional diameter (e.g., 20 times or more than 50 times), typically obtainable by melt extrusion. The cross-sectional shape of the wire or fiber is not particularly limited, and may be, for example, a circular cross-section, an elliptical cross-section, a polygonal cross-section, a hollow cross-section, or other irregular cross-section, which can impart compression resistance, bulk, or the like.
The mixing process of step i) may be carried out in any mixing device known in the art. Preferably, the individual components of the thermoplastic polyester elastomer composition are thoroughly mixed under stirring. The order of addition of the components is not particularly limited. The mixture formed can be immediately fed to a subsequent processing step.
Steps ii) and iii) are generally carried out continuously in succession. In one exemplary embodiment, specifically, a general melt extruder may be used to heat the thermoplastic elastomer composition obtained by mixing to a temperature 10 to 120 ℃ higher than the melting point to be in a molten state. For example, the extruder temperature may be set to a temperature of 180 to 300℃and preferably 200 to 280℃in the present invention. And then is ejected downwards by a nozzle with a plurality of orifices to naturally descend so as to form a ring. At this time, the ring diameter and the fineness and the number of bonding points of the wire rod are determined according to the distance between the nozzle face and the take-up conveyor belt provided on the cooling medium for solidifying the resin, the melt viscosity of the resin, the aperture diameter and the ejection amount of the orifice, and the like. The rings are produced by sandwiching the molten discharged wire material between a pair of collecting conveyors provided on the cooling medium at adjustable intervals, and the rings are brought into contact with each other by setting the hole intervals of the orifice to be hole intervals at which the rings can be brought into contact, whereby the rings form a random three-dimensional shape and the contact portions are welded. Then, the continuous wire rods which form a random three-dimensional form and the contact portions are welded are continuously introduced into a cooling medium (preferably water at room temperature) and solidified to form a net-like structure.
Subsequently, water removal and drying may be performed as needed. As an exemplary method of the present invention, after temporary cooling, a pseudo crystallization treatment is performed. The pseudo-crystallization treatment temperature is at least 10 ℃ lower than the melting point (Tm). When pseudo-crystallization is performed by a simple heat treatment, heat resistance and sagging resistance are improved. In addition, after the temporary cooling, the pseudo crystallization treatment can be performed simultaneously by setting the drying temperature to the annealing temperature in the drying step. In addition, pseudo crystallization treatment may be performed separately.
Finally, the resulting web structure may be cut to a desired length or shape for cushioning material. When the mesh structure of the present invention is used as a cushioning material, the resin, fineness, ring diameter and bulk density to be used are required to be selected according to the purpose and site of use.
The material according to the invention has a wide range of applications, for example as a cushioning material in furniture, household appliances, office supplies, automobiles, trains, ships or in the field of aerospace, for example in office chairs, sofas, mattresses, carpets, seating in vehicles.
Examples
The invention is further illustrated by the following examples, but it is obvious that the invention should not be limited to these specific examples.
List of raw materials
In the examples the following raw materials were used
TABLE 1
Preparation of thermoplastic polyester elastomer composition
100kg of TPEE is added into a high-speed mixer, and a plurality of thermoplastic polyester elastomer composite materials are respectively obtained by adding diphenylamine antioxidant, hindered phenol antioxidant, erucamide, vinyl distearamide, organosilicon lubricant and tackifier according to the percentage shown in the following table 2 (in the table, "\" represents no addition) under the stirring condition.
The composite obtained in each example was placed in a melt extruder at a temperature of 210 to 260℃and a single-hole spinning amount of 10 to 60g/min was blown down from the spinning holes, and passed through a heat-retaining region directly under the spinning holes, and the molten linear body was bent to form a ring, and the contact portions were welded to form a three-dimensional network structure, which was solidified by drawing the three-dimensional network structure in a molten state by drawing a conveying plate chain. The cured three-dimensional network structure was subjected to subsequent performance testing.
Performance testing
Compression set by heat aging
Samples were taken to a size of 100mm x 100mm according to the method of ISO 2440, stored at 140 ℃ for 168 hours, and conditioned under standard conditions for 24 hours. After measuring the height of the aged sample, the sample was compressed to 50% of the thickness of the sample, kept at 70 ℃ for 22 hours, stored in a free state in a standard environment for 30 minutes, and then the height of the sample was measured again to obtain a compression set value.
Heat aging compression strength variation
According to the method of ISO 2440, the compressive strength of a sample in the state of being obtained was measured after measuring the length and width of a sample having a size of 100mm by 100 mm. The test specimen was stored at 140 ℃ for 168 hours, then conditioned for 24 hours under standard conditions, and then tested for compressive strength after heat aging according to the same procedure for testing compressive strength values in the as-prepared state, to obtain a change in compressive strength.
Compressive Strength
According to the method of ISO 3386-1, the compressive strength value of a sample in the prepared state is measured after the sample size is 100mm X100 mm and the length and width dimensions are measured.
Noise value
In a mute room (the decibel number is less than 35), placing a sample on a platform, placing 70kg weights at a constant speed, respectively evaluating by using a decibel meter and human ears, reading the maximum value in the pressing process of the weights by using the decibel meter, and qualitatively evaluating the sound generated by the sample from sense organs.
Melt index
The resulting material sample was placed in a fixed inner diameter metal sleeve and heated and loaded, and the mass of the material melt flowing out of the die of the specified diameter was measured within 10 minutes.
TABLE 2 composition and Performance test results for the various examples
(the embodiment with the horn is according to the invention)

Claims (10)

1. A thermoplastic polyester elastomer composition comprising, based on the total weight of the composition:
a) 80-98% of thermoplastic polyester elastomer TPEE;
b) 0.1-3% of diphenylamine antioxidant;
c) 0.1-2.8% of fatty acid amide lubricant; and
d) 0.1-2.5% of a tackifier, which is an epoxy-functional polymer based on vinylaromatic compounds and (meth) acrylic compounds.
2. Thermoplastic polyester elastomer composition according to claim 1, characterized in that it comprises 0.5 to 2.6%, preferably 0.9 to 2.0% of diphenylamine-based antioxidants and/or 0.3 to 2.3%, preferably 0.5 to 1.8% of fatty acid amide-based lubricants, based on the total weight of the composition.
3. Thermoplastic polyester elastomer composition according to claim 1 or 2, characterized in that the diphenylamine-based antioxidant has the following structural formula (I):
wherein R1 and R2 represent optionally one or more, preferably one, substituent(s) on the respective benzene ring selected from C1-C18, preferably C2-C12 or C3-C10 alkyl or aralkyl, provided that at least one R1 or R2 substituent is present in formula (I); and both R1 and R2 may also form a straight-chain or branched alkylene group having C1-C8, such as C3-C6, linking the two benzene rings.
4. Thermoplastic polyester elastomer composition according to any of the preceding claims, characterized in that the alkylene group is a linear or branched alkylene group having 1 to 8 or 3 to 6C atoms, such as ethylene, propylene, isopropylene, and/or the aralkyl group is a phenylalkyl group, such as benzyl, phenethyl, α -methylbenzyl, phenylisopropyl.
5. Thermoplastic polyester elastomer composition according to any one of the preceding claims, characterized in that the fatty acid amide-based lubricant comprises one or two amide groups and an aliphatic group selected from linear, branched or cyclic saturated or unsaturated aliphatic groups, preferably having 6 to 40, more preferably 8 to 30, such as 10 to 25 carbon atoms, and optionally may have one or more, such as two carbon-carbon double bonds.
6. Thermoplastic polyester elastomer composition according to any of the preceding claims, characterized in that the fatty acid amide-based lubricant is selected from erucamide, oleamide, stearamide such as vinyl distearamide or amide wax, etc.
7. Thermoplastic polyester elastomer composition according to any one of the preceding claims, characterized in that it further comprises in the range of 0.5 to 1.5% each of phosphite antioxidants, hindered phenol antioxidants and/or uv absorbers, based on the total weight of the composition, and/or in the range of 0.1 to 5% each of calcium stearate and/or silicone lubricants, based on the total weight of the composition.
8. Thermoplastic polyester elastomer composition according to any one of the preceding claims, characterized in that the tackifier is a copolymer of epoxy-functional styrene and glycidyl (meth) acrylate, preferably having an epoxy equivalent weight of between 100 and 800g/mol, preferably 150 and 650g/mol, for example.
9. A method of making a thermoplastic polyester elastomer fiber material comprising: i) Providing the individual components of the thermoplastic polyester elastomer composition according to any one of claims 1 to 8 and mixing them, ii) melt extruding the resulting mixture into fibrous strands at a temperature 10-120 ℃ above its melting point, and iii) randomly entangling and bending the resulting strands to form a three-dimensional network.
10. An article comprising the thermoplastic polyester elastomer composition according to any one of claims 1 to 8 or the thermoplastic polyester elastomer fiber material made by the method according to claim 9, preferably a cushioning material in a seat in an office chair, sofa, mattress, carpet, vehicle.
CN202210110659.7A 2022-01-29 2022-01-29 Anti-aging and low-noise TPEE fiber material Pending CN116554648A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN202210110659.7A CN116554648A (en) 2022-01-29 2022-01-29 Anti-aging and low-noise TPEE fiber material
PCT/CN2022/122351 WO2023142505A1 (en) 2022-01-29 2022-09-29 Aging-resistant and low-noise tpee fiber material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210110659.7A CN116554648A (en) 2022-01-29 2022-01-29 Anti-aging and low-noise TPEE fiber material

Publications (1)

Publication Number Publication Date
CN116554648A true CN116554648A (en) 2023-08-08

Family

ID=87470365

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210110659.7A Pending CN116554648A (en) 2022-01-29 2022-01-29 Anti-aging and low-noise TPEE fiber material

Country Status (2)

Country Link
CN (1) CN116554648A (en)
WO (1) WO2023142505A1 (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102492267A (en) * 2011-12-02 2012-06-13 金发科技股份有限公司 Amylum category complete biodegradable material and preparation method thereof
KR101484390B1 (en) * 2012-04-24 2015-01-19 주식회사 엘지화학 Thermoplastic polyester elastomer resin composition and molding articles comprising the same
US11104795B2 (en) * 2013-03-29 2021-08-31 Basf Se Composition of reinforced polyalkylene terephthalate, preparation and use thereof
CN112724391A (en) * 2020-12-14 2021-04-30 新疆蓝山屯河高端新材料工程技术研究中心(有限公司) Application of chain extender in improving viscosity of polyester compound, modified polyester compound and preparation method thereof
CN113861628A (en) * 2021-08-30 2021-12-31 会通新材料(上海)有限公司 High-elasticity high-breathability 3D air fiber material and preparation method thereof

Also Published As

Publication number Publication date
WO2023142505A1 (en) 2023-08-03

Similar Documents

Publication Publication Date Title
JP4212643B2 (en) Biodegradable polyester resin composition, and molded product, foam and molded container obtained therefrom
KR100358424B1 (en) Monofilament and process for producing the same
KR20160075531A (en) Quiet, lightweight elastic mesh structure
CN107619584A (en) Lactic acid composite material, tableware and preparation method thereof
KR20130142193A (en) A blend composition, flexible tubing material and method of making the blend
JP5300395B2 (en) Polyester resin composition, fiber obtained from the resin composition, and method for producing the fiber
JP2023014248A (en) network structure
CN114133708B (en) Thermoplastic polyester elastomer and preparation method and application thereof
JPH08199052A (en) Plasticized polylactic acid and its molded item
CN116554648A (en) Anti-aging and low-noise TPEE fiber material
JP2011116949A (en) Polylactic acid-based resin composition, method for producing the same, and foam obtained from the same
JP6284429B2 (en) Thermoplastic elastomer resin composition and composite molded body
JP3701539B2 (en) Monofilament and manufacturing method thereof
JP5978674B2 (en) Elastic network structure with high vibration absorption
JP2023129674A (en) Biodegradable three-dimensional network structure
JP7253291B1 (en) Damping pad with low compression set
EP2261410A1 (en) Polylactic acid filament nonwoven fabric and production method thereof
JP2013095853A (en) Thermoplastic elastomer composition
CN113463217B (en) Dimensionally stable layered elastomer
JP5966472B2 (en) Elastic network structure with high vibration absorption
JP2020029089A (en) Fused deposition modeling-based resin composition for three-dimensional molding, and filament molding containing the same, and molded body
CN103804857A (en) Thermoplastic polyester elastomer composition and application thereof
CN114085494A (en) Low-noise high-elasticity 3D air fiber material and preparation method thereof
JP6786774B2 (en) Reticulated structure with excellent moldability
TW202026476A (en) Net-shaped structure body

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication