Thermoplastic polyetherester elastomer composition and products containing same

Abstract

To provide a thermoplastic polyetherester elastomer composition that consumes less energy during production, can be easily cut from strand into pellets, and is suitable for mass production.SOLUTION: Provided is a thermoplastic polyetherester elastomer composition in which polybutylene terephthalate chain and (polytetramethylene glycol)terephthalate chain are bonded. The melting point of this thermoplastic polyetherester elastomeric composition is in the range of 80°C to 160°C and the melting enthalpy is greater than 6 J / g.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a resin composition and an article containing the same, and more particularly to a thermoplastic polyetherester elastomer composition and an article containing the same. [Background technology]

[0002] Thermoplastic elastomers are polymeric materials with properties between those of rubber and plastic. They have the flexibility of rubber and the processability of plastic, making them widely used in a variety of fields.

[0003] Thermoplastic elastomers are generally divided into thermoplastic polyolefin elastomers (TPO elastomers), thermoplastic polyetherester elastomers (TPEE), thermoplastic styrene elastomers (TPS elastomers), thermoplastic polyurethane elastomers (TPU elastomers), thermoplastic vulcanizate elastomers (TPV elastomers), and thermoplastic polyamide elastomers (TPA elastomers).

[0004] Thermoplastic elastomers have the advantage of being readily available and diverse. Thermoplastic elastomers are primarily divided into block copolymers, graft copolymers, and polymer blends. A common commercially available block copolymer, such as ethylene-vinyl acetate copolymer (EVA), is composed of ethylene and vinyl acetate. Due to its low melting point, EVA can be melted and blended at low temperatures, which can control or reduce energy consumption. However, EVA's poor durability has prompted researchers to actively explore thermoplastic elastomers such as TPEE.

[0005] TPEE is a block copolymer consisting of polyester hard segments and polyether soft segments. TPEE offers excellent cushioning, elasticity, heat resistance, and chemical resistance. Because TPEE can provide high resilience and durability even at low temperatures, it is a preferred choice for a variety of applications requiring strict manufacturing conditions.

[0006] High-melting-point TPEEs have excellent heat resistance, but require relatively high temperatures for crosslinking reactions. As a result, the production of TPEEs consumes more energy and is not beneficial for mass production. In light of this, the present applicant seeks a low-melting-point TPEE that can reduce energy consumption and production costs for TPEE production. However, several manufacturing problems have been discovered. For example, during the step of cutting strands into pellets, the cutting blade is easily wrapped or wrapped around by molten TPEE, making the process of cutting strands into pellets less smooth, resulting in unacceptable pellet quality and uneven pellet sizes. Furthermore, the pellets are likely to stick together during subsequent processes such as packaging, transportation, or storage. Therefore, conventional TPEEs with low melting points are still not beneficial for mass production. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-147058 Summary of the Invention [Problem to be solved by the invention]

[0008] In this regard, the object of the present invention is to modify the TPEE composition to reduce energy consumption and overcome the problems associated with cutting the strands into pellets and the subsequent manufacturing process, making the TPEE composition of the present invention advantageous for mass production.

[0009] To achieve the foregoing objectives, the present invention provides a thermoplastic polyetherester elastomer (TPEE) composition comprising a first chain and a second chain bonded to each other: [ka] [ka] where: The ratio of x to y (x / y) is 0.5 or more and 2.0 or less, and n is 6 or more and 15 or less, The melting point (Tm) of the TPEE composition is 80° C. or higher and 160° C. or lower, and the enthalpy of fusion (ΔHm) of the TPEE composition is greater than 6 J / g.

[0010] By controlling the melting point and enthalpy of fusion, the TPEE composition of the present invention can be produced at a low temperature, avoiding problems associated with cutting the strands into pellets and subsequent manufacturing processes. Therefore, the goal of mass-producing the TPEE composition can be achieved. In other words, the TPEE composition of the present invention can be mass-produced more easily than the prior art.

[0011] Preferably, the second chain (O(CH2)4) in the above formula (II) n The number average molecular weight (Mn) of the (O(CH2)4) in the second chain is 500 or more and 1200 or less. n The Mn of the second chain can be, but is not limited to, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, or 1200. n The Mn of the second chain may be a value falling within a range between any two of the above values. More preferably, the (O(CH2)4)n Mn is 500 or more and 1000 or less.

[0012] Preferably, the ratio of the average repeat units of the first chain to the average repeat units of the second chain of the TPEE composition in Formula (I) and Formula (II) above (the ratio of x to y, abbreviated as x / y) is 0.5 or greater and 2.0 or less. In one embodiment, without limitation, x / y can be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. x / y can also be a value within a range between any two of the above values.

[0013] Preferably, n in the above formula (II) is 6 or more and 15 or less. In one embodiment, n can be, but is not limited to, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15, or a value within a range between any two of these values. More preferably, n can be 7 or more and 13 or less.

[0014] Preferably, the content of the second chain in the TPEE composition is 55% by weight or more and 83% by weight or less. In one embodiment, the content of the second chain in the TPEE composition can be, but is not limited to, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, ..., 82%, or 83% by weight. The content of the second chain in the TPEE composition can also be within a range between any two of the above values. More preferably, the content of the second chain in the TPEE composition is 60% by weight or more and 82% by weight or less.

[0015] In one embodiment, the TPEE composition of the present invention can be synthesized from dimethyl terephthalate (DMT), 1,4-butanediol (BDO), and poly(tetramethylene ether) glycol (PTMEG) through a condensation reaction. In another embodiment, the TPEE composition of the present invention can be synthesized from p-terephthalic acid (PTA), BDO, and PTMEG through a condensation reaction.

[0016] In one embodiment, the melting point of the TPEE composition may be 80° C. or higher and 160° C. or lower, and the enthalpy of fusion of the TPEE composition may be greater than 6 J / g. As described above, the TPEE composition of the present invention can be produced at low temperatures, avoiding the problems associated with cutting strands into pellets and subsequent manufacturing processes. Therefore, the TPEE composition of the present invention is advantageous for mass production.

[0017] In another embodiment, the melting point of the TPEE composition may be 80°C or higher and 120°C or lower, and the melting enthalpy of the TPEE composition may be greater than 6 J / g. As described above, the TPEE composition of the present invention is not only suitable for mass production, but also can be produced using EVA processing equipment according to different needs, which has the advantage of saving production costs.

[0018] In another embodiment, the melting point of the TPEE composition can be controlled to be less than 140°C, and the enthalpy of fusion of the TPEE composition can be greater than 6 J / g. In other embodiments, a crosslinking agent and / or crosslinking coagent can be optionally added to the TPEE composition to increase heat resistance and weather resistance. In one embodiment, the crosslinking agent can be, but is not limited to, dicumyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, sulfur, or bis(tert-butylperoxy-isopropyl)benzene. The crosslinking coagent can be, but is not limited to, triallyl isocyanurate.

[0019] In other embodiments, the melting point of the TPEE composition may be, but is not limited to, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, or 160°C. The melting point of the TPEE composition may be within a range between any two of the above values. Meanwhile, the melting enthalpy of the TPEE composition may be, but is not limited to, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 J / g. The melting enthalpy of the TPEE composition may be within a range between any two of the above values.

[0020] The present invention further provides a TPEE product comprising the aforementioned TPEE composition.

[0021] The TPEE product of the present invention may be, but is not limited to, shoe material, wire material, sealing material, electronic device casing, 3D printing wire material, vehicle material, power cord insulation material, foam material, medical container, medical tubing, packaging material, soundproofing material, or thermal insulation material. [Brief explanation of the drawings]

[0022] [Figure 1] 1 is a proton nuclear magnetic resonance ( 1 H-NMR) spectrum of TPEE of Example 1. DETAILED DESCRIPTION OF THE INVENTION

[0023] Below, examples of the TPEE composition and its products of the present invention are shown, along with several comparative examples for comparison. Those skilled in the art will easily understand the advantages and effects of the present invention from the following examples and comparative examples. The descriptions proposed herein are merely preferred embodiments for illustrative purposes and are not intended to limit the scope of the present invention. Various modifications and variations can be made to implement or apply the present invention without departing from the spirit and scope of the present invention.

[0024] <<TPEE Composition>> <Example 1> The production of the TPEE composition of Example 1 is described below.

[0025] A mixture of dimethyl terephthalate (DMT, 259 g), 1,4-butanediol (BDO, 175 g), and poly(tetramethylene ether) glycol (PTMEG, 300 g) with a number average molecular weight (Mn) of 650 was placed in a 3-liter autoclave, and then titanium butoxide (TBT, 1.2 g) was added as a catalyst. The temperature of the autoclave was set at 210 - 230 °C for esterification.

[0026] During esterification, methanol (melting point: 64.7 °C) was produced as a by-product. Methanol in the autoclave was boiled at 220 - 225 °C. Then, methanol was condensed with a condenser tube connected to the autoclave and recovered in a recovery tank. The temperature at the top of the condenser tube was lowered below 40 °C, and this point was taken as the end of esterification, and condensation was carried out immediately.

[0027] In the condensation stage, the temperature of the autoclave was raised to 240 - 250 °C, and the pressure in the autoclave was reduced to less than 1 mbar by a vacuum pump. The aforementioned temperature and pressure were maintained for about 200 minutes. When the melt flow index (MI) of the molten copolymer in the autoclave reached 16 g / 10 min - 18 g / 10 min, this point was taken as the completion of condensation. Next, the valve of the autoclave was opened, strands were pulled out, and the strands were cut into pellets. Here, the MI of the aforementioned molten copolymer was expressed in g (grams) of the molten copolymer flowing through a standard die with a diameter of 2.095 mm for 10 minutes at 230 °C and a loading weight of 2.16 kg.

[0028] A water channel through which water at 15°C was flowing was attached to the outlet of the autoclave valve. The molten copolymer was cooled and crystallized in this water channel, and then drawn into strands. The strands were fed into an extruder (manufacturer: Chen Yu, model: CY-P100) and cut into pellets with a particle size of 2 mm and a length of 3 mm. By driving the gear of the extruder, the molten copolymer was continuously fed into the water channel and drawn into strands. When there was no longer enough residue to form strands, the process of cutting the strands into pellets while drawing them was terminated.

[0029] <Examples 2 to 7> The TPEE compositions of Examples 2 to 7 were produced in substantially the same manner as the TPEE composition of Example 1. The differences from Example 1 were the amounts of DMT, BDO, and PTMEG, and the Mn of the PTMEG used in the production, and these parameters are shown in Table 1 below.

[0030] Without being limited to the implementations exemplified by the above examples, those skilled in the art can make various modifications and variations to obtain the TPEE composition of the present invention without departing from the spirit and scope of the present invention. For example, the timing of adding the catalyst can be appropriately changed as needed. For example, an additional catalyst can be added in the condensation stage to promote the reaction. That is, the timing of adding the catalyst is not limited to the esterification stage.

[0031] <Comparative Examples 1 to 3> The TPEE compositions of Comparative Examples 1 to 3 were produced in a manner similar to that of Example 1. The differences from Example 1 were the amounts of DMT, BDO, and PTMEG, and the Mn of the PTMEG used in the production. These parameters are shown in Table 1 below.

[0032] <Comparative Example 4> The TPEE composition of Comparative Example 4 was a commercially available product (manufacturer: DSM Arnitel, model: EM460-08).

[0033] The amounts of DMT, BDO, and PTMEG used in preparing the TPEE compositions of Examples 1 to 7 (E1 to E7) and Comparative Examples 1 to 3 (C1 to C3), as well as the Mn of the PTMEG, are listed in Table 1 below.

[0034] [Table 1]

[0035] As shown in Table 1, the Mn of the PTMEG used in producing the TPEE compositions of Examples 1 to 7 was in the range of 650 to 1,000.

[0036] <Test Example 1: Melting Point and Melting Enthalpy> The TPEE compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were used as test samples and analyzed by a differential scanning calorimeter (abbreviated as DSC, manufacturer: TA Instrument, model: Q-2000).

[0037] An aluminum tray containing 10 mg of the test sample and a blank aluminum tray were placed in a differential scanning calorimeter. The temperature of the differential scanning calorimeter was increased from room temperature at a rate of 10°C / min until a melting peak appeared, and the melting point was recorded. The temperature of the differential scanning calorimeter was then cooled to room temperature at a rate of 10°C / min. The enthalpy of fusion was calculated from the area between two lines: the line between the beginning and end of the melting peak and the curve of the melting peak. The results are shown in Table 3.

[0038] <Test Example 2: Content of second chain in TPEE composition> The TPEE compositions of Examples 1 to 7 and Comparative Examples 1 to 4 were used as test samples and analyzed by nuclear magnetic resonance spectroscopy (abbreviated as NMR, model: Bruker Avance-500).

[0039] In this test example, 40 mg of test sample was dissolved in d-chloroform in a sample tube, and the 1 H-NMR spectrum of each test sample was obtained.

[0040] The chemical shifts and integrals on the 1H-NMR spectrum corresponding to each functional group of the TPEE composition were analyzed as follows: The functional groups corresponding to each signal were shown as Formula (II) and Formula (II-I) below. The integral of the singlet at chemical shift 8.06 ppm (corresponding to the aryl group at the "a" position in formula (II) and formula (II-I) below) is set to 1.000, and the integral B of the singlet at chemical shifts 4.400 ppm and 4.410 ppm (corresponding to the butoxy group at the "b" position in formula (II) below), the integral B' of the triplet at chemical shifts 4.320 ppm and 4.355 ppm (corresponding to the butoxy group at the "b'" position in formula (II-I) below), and the integral C of the singlet at chemical shifts 3.378 ppm and 3.388 ppm (corresponding to the butoxy group at the "c" position in formula (II-I) below) are listed in Table 2.

[0041] [ka]

[0042] The content of the second chain in the TPEE composition is given by (72 × n + 148) / (72 × n + 148 + 220 × x). Here, y in formula (II-I) is 1, x is the ratio of the average repeating units of the first chain to the second chain, and x is given by (integral B) / (integral B'). n is the average repeating unit of (O(CH2)4) in one unit of the second chain, and n is given by [(integral C) / (integral B')] + 1. The content of the second chain in the TPEE composition is abbreviated as "content of the second chain." The results are shown in Tables 2 and 3.

[0043] [Table 2]

[0044] As shown in Table 2, the ratio of the average repeating units (x / y) of the first chain to the second chain of the TPEE compositions of Examples 1 to 7 was 0.7 or more and 2.0 or less, and the average repeating units (n) of (O(CH2)4) in one unit of the second chain of the TPEE compositions of Examples 1 to 7 was 7 or more and 13 or less.

[0045] As shown in Table 2, the content of the second chain in the TPEE compositions of Examples 1 to 7 was 60% by weight or more and 82% by weight or less, which was different from the content of the second chain in the TPEE compositions of Comparative Examples 1 to 4.

[0046] <Test Example 3: Possibility of mass production> The mass-productivity (ease of mass production) of the TPEE compositions of Examples 1 to 7 and Comparative Examples 1 to 4 was evaluated from two perspectives: one was the energy required to heat the TPEE compositions, and the other was whether the molten copolymer fed to the extruder could be properly cut into uniform pellets with a particle size of 2 mm and a length of 3 mm in the production of the TPEE compositions.

[0047] A melting point of a TPEE composition above 160°C means that more energy is required to heat the TPEE composition, which is not beneficial for mass production. Furthermore, if the cutting blade is wrapped or wrapped around the molten copolymer during cutting into pellets, the operator must stop the process of cutting the strand into pellets and manually remove the molten copolymer surrounding the cutting blade, which is not beneficial for mass production. On the other hand, if the pellet quality is unacceptable or the pellet size is not uniform (e.g., the molten copolymer is not completely cut, resulting in the appearance of the aforementioned pellets having indentations left by the cutting blade or pellets measuring up to 10 mm in length), this means that the production yield of cutting the strand into pellets is not good, which is not beneficial for mass production. Furthermore, if pellets stick together, even visible to the naked eye, during the subsequent packaging, transportation, and storage processes, this is not beneficial for mass production.

[0048] In the above evaluation, if a TPEE composition had any of the following problems: (1) excessive energy consumption for heating; (2) the molten copolymer tended to wrap around or wrap around the cutting blade when cutting the strand into pellets; (3) the pellets cut from the strand were of poor quality or had inconsistent sizes; or (4) the pellets tended to stick together during packaging, transportation, or storage, the TPEE composition was determined to be unsuitable for mass production, and its feasibility for mass production was rated "X." Conversely, if none of the above problems (1) to (4) were observed, the TPEE composition was determined to be suitable for mass production, and its feasibility for mass production was rated "Good." The results of this evaluation are shown in Table 3.

[0049] [Table 3]

[0050] As shown in Table 3, the melting points of the TPEE compositions of Examples 1-7 were less than 160°C, and the enthalpies of fusion of the TPEE compositions of Examples 1-7 were greater than 6 J / g. Therefore, the production of the TPEE compositions of Examples 1-7 was characterized in that (1) excessive energy was not consumed when heating the TPEE compositions, (2) the cutting blade was not easily enveloped and / or wrapped around by the molten copolymer during the step of cutting the strands into pellets, (3) the pellets were obtained with good quality and uniform size, and (4) the pellets did not adhere to each other during subsequent processes such as packaging, transportation, or storage.

[0051] In contrast, the TPEE compositions of Comparative Examples 1 to 4 had any of the problems (1) to (4) above. Therefore, the TPEE compositions of Comparative Examples 1 to 4 are not useful for mass production, and the drawbacks of the prior art could not be solved by the TPEE compositions of Comparative Examples 1 to 4.

[0052] In addition, the melting points of the TPEE compositions of Examples 4 and 5 were between 80°C and 120°C, which was advantageous for mass production. Because the melting points of the TPEE compositions of Examples 4 and 5 were close to that of EVA, the TPEE compositions of Examples 4 and 5 could be produced using EVA processing equipment as needed, which had the advantage of reducing TPEE production costs.

[0053] In summary, the TPEE composition of the present invention, which has a melting point of 80°C or higher and 160°C or lower, and a melting enthalpy of more than 6 J / g, can reduce the energy consumption for producing the TPEE composition and solve the problems associated with cutting strands into pellets and the subsequent manufacturing process, which is beneficial for mass production, thus improving the industrial value of both the TPEE composition and TPEE products.

Claims

1. 1. A thermoplastic polyetherester elastomer (TPEE) composition comprising a first chain represented by formula (I) and a second chain represented by formula (II) bonded to each other, wherein: 【Chemical 1】 【Chemistry 2】 where x is the number of repeating units in the first chain and y is the number of repeating units in the second chain, the ratio of x to y (x / y) is 0.5 or more and 2.0 or less, and n in formula (II) is 6 or more and 15 or less, A thermoplastic polyether ester elastomer composition having a melting point (Tm) of 80°C or higher and 160°C or lower, and a melting enthalpy (ΔHm) of more than 6 J / g and 17.54 J / g or lower.

2. The thermoplastic polyetherester elastomer composition according to claim 1, wherein the content of the second chains in the thermoplastic polyetherester elastomer composition is 60% by weight or more and 82% by weight or less.

3. The thermoplastic polyetherester elastomer composition according to claim 1 or 2, wherein the thermoplastic polyetherester elastomer composition has a melting enthalpy of 7 J / g or more and 17.54 J / g or less.

4. (O(CH ２ ) ４ ) ｎ The thermoplastic polyether ester elastomer composition according to any one of claims 1 to 3, wherein the number average molecular weight of the polyether ester elastomer composition is 500 or more and 1,000 or less.

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