TWI354679B - Fast heat-up thermoplastic polyester polymer compo - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to a thermoplastic polymer composition, and more particularly to a preform that can be heated up quickly before being blown, when applied to make a bottle. And the resulting bottle is a near-colorless thermoplastic polyester-based polymer composition, and a method for preparing the composition. [Prior Art] Thermoplastic polymers, especially polyethylene terephthalate (PET) or its copolyesters, are used in the manufacture of films, bottles or other containers for food or beverages. Very common. In general, the manufacturing process of the bottle is divided into two stages. The following is an example of the manufacture of a PET bottle. The first stage is to inject PET into the module to form a preform (b〇ttle piefoim), and the second stage is to compress The air is injected into the module and the preform is blown into a bottle. In the second stage, the temperature of the preform is heated to about 1 Torr to blow the bottle, so the rate of reheating becomes the second. The rate of the stage is determined by the steps. Generally, the heaters used in the commercial reheating step are quartz lamps which emit electromagnetic waves concentrated at a wavelength of 5 〇〇 nm to 2 〇〇〇 nm. However, PET has a low absorption rate of electromagnetic waves in the above wavelength range, and it is usually located because of impurities or additives contained in the inside, such as residual catalyst or other substances. Because electromagnetic waves are scattered by such substances or these substances Absorbing electromagnetic waves to allow the bottle embryo to absorb electromagnetic waves, so the re-cooking time of the PET composition has a great relationship with the transparency of the composition itself. When the PET composition contains impurities or more additives, the more Promotes the rate of reheating, but it also causes fogging of the preform. Furthermore, the deeper the color of the added substance, the shorter the electromagnetic wave capacity, the shorter the time for the embryo to heat, but the bottle cannot maintain a transparent and colorless state. (4) It cannot meet the current commercial red for colorless bottles or other types 1354679 A large demand for state containers, especially for the Asian market. The φ patent discloses the ability to absorb electromagnetic radiation by adding an additive to a thermoplastic polymer and reduce the time for reheating as follows

Pat·4408004 can also achieve this by using carbon black to achieve the reduction of reheating time. For example, the condition of 4 Na 81 can not reduce the reheating time; Us Pat.44G_4 and 5419936 use the reduction record Polymerization of the catalyst to increase the heating rate; Pat.4481314 & to some brewing (an hraqUin〇ne) type of dye can also achieve this purpose. U.S. Pat, 666 792 uses an iron compound that does not participate in the reaction, such as FeP FeSi or a combination thereof to reduce the reheating time; the 卩s p pair reveals the addition of activated carbon to increase the heating rate. All of the above additives are black or gray = light, will be full spectrum of light, so the color and haze of the test or other type of grain will have an unacceptable impact, the amount of impact and the amount of added In principle, the particle size of the additive can be used to some extent to reduce these effects, but not all. In addition, US Pat. 5,529,744 discloses a bottle made of a thermoplastic polymer containing metal particles (such as Sb, S" Ag, Au, Cu, As, Cd, Hg, Pt and/or Pd), which mainly utilizes a polymerization process. Adding a reducing agent and a compound of the foregoing metals and reducing the metal compounds to metal particles, particularly Sb, to increase the rate of reheating of the polyester, but the absolute yellowness of the bottle obtained by the patent disclosed herein is biased. Large, so can not get colorless bottles. Although these additives can reduce the heating time of the preform, but energy saving and improve the efficiency of the process, and can not produce a colorless bottle of commercial demand, therefore, there is a rapid increase in temperature And the bottle is made of a near-colorless thermoplastic polymer composition. 4 1354679 SUMMARY OF THE INVENTION The specific types of carbonaceous materials, metal compounds or metals disclosed in the preceding paragraphs that enhance the rate of reheating It cannot be rendered colorless after being added to the thermoplastic polymer, so it cannot meet the large demand for colorless bottles or other types of containers on the market. Applicant believes that the thermoplastic polymer composition should be able to rapidly heat up under the illumination of a quartz tube, except that by adding an amount of heat-conducting substance to the polymer by adding a substance capable of absorbing electromagnetic waves in the wavelength range as described above. The overall composition should be able to have better heat transfer properties, and thus increase the rate of temperature rise of the preform (such as preform) before processing, so the applicant attempts to select from the various metal powders to have good thermal conductivity and can The final bottle is colorless. However, as is known to those skilled in the art of polymer technology, the final color of the metal particles after doping with the polymer is controlled by an extremely complicated mechanism, so it is difficult to estimate from the individual colors of the particles. The final color that will be exhibited after being blended with the polymer. The applicant has studied it in many ways and finally found that aluminum, magnesium, zinc, tungsten and calcium are excellent choices for both heat conduction and colorlessness, as long as the specific types of metals are controlled. The powder is added to the thermoplastic polymer in a certain range, and is dispersed in the thermoplastic polymer to reach the preform. There is no particular limitation on the rapid temperature rise and the near-colorlessness of the bottle, and there is no particular limitation as to when or how to add the polymer preparation process. Therefore, the first object of the present invention is to provide a thermoplastic polyester which is rapidly heated. a polymer composition comprising a thermoplastic polyester polymer and a plurality of metal particles, wherein the thermoplastic polyester polymer has a number average molecular weight of between 1,000 and 60,000, and the metal particles are aluminum and magnesium. , zinc, tungsten, calcium particles, or a combination thereof. The thermoplastic polyester polymer composition of the present invention can be formed into a melt, a pellet, a sheet as needed. Or 5 containers (four) tai (four) suitable for making preforms and bottles. Well, 'is providing a method for preparing the thermoplastic, thermoplastic polymer composition, including step two in the thermoplastic One of the poly-based polymers is selected from the group consisting of two and four metal particles in the following group, a polymerization advancement stage, a liquid polymerization stage, a solid state polymerization stage, and an additive molding process. stage. The fast-heating thermoplastic polyester polymer of the present invention consists of 'heat-containing metal particles, so it can effectively increase the temperature rate of 1' and thus reduce the time for reheating before lifting (such as blowing): Reducing the cost of the process, the metal particles are selected and their final color development and transparency are dispersed in the polymer. Therefore, by appropriately controlling the amount of the metal particles added and the particle size and particle size, Finished products of thermoplastic polyester polymer compositions, such as bottles, are in a state of near-colorlessness, so they are in line with the market, especially in the Asian market, which is not possible with all of the previous cases. [Embodiment] Preferably, the metal particles in the composition of the present invention are aluminum particles. Preferably, in the thermoplastic polyester-based polymer composition of the present invention, the content of the metal particles is between 1 PPM and 200 PPM, more preferably based on the total weight of the thermoplastic polyester-based polymer. The ground is between 1 PPM and 100 PPM and, more preferably, between 20 PPM and 100 PPM, optimally between 25 PPM and 100 PPM. Preferably, the metal particles suitable for use in the present invention have a d5 〇 particle size of between 0.1 and 100 μηι, and more preferably have a d5 〇 particle size of between 0.1 1354679 and 50 μηι, further preferably The ground has a d5 〇 particle size of between 0.1 and 10 μm, and most preferably has a d50 particle size of between 0.1 and 5 μηι. Preferably, the thermoplastic polyester-based polymer suitable for use in the present invention is a polyester composed of at least one repeating unit A derived from a diacid component and at least one repeating unit B derived from a monodiol component. Preferably, the diol component comprises a C2~C16 aliphatic dicarboxylic acid, a C8~C16 aromatic dicarboxylic acid, or a combination thereof.

Optionally, the diacid component comprises at least one C8 to C16 aromatic dicarboxylic acid, and preferably, the C8 to C16 aromatic dicarboxylic acid is terephthalic acid. More preferably, the thermoplastic polyester polymer is a copolyester of polyethylene terephthalate, and preferably, based on the total number of moles of the diacid component, terephthalic acid is At least 60 mol% of the diacid component, and ethylene glycol is at least 60 mol% of the diol component based on the total moles of the diol component.

Optionally, the diacid component comprises two Cs to C16 aromatic dicarboxylic acids. In a specific embodiment of the present invention, the two c8 to C16 aromatic dicarboxylic acids are terephthalic acid and isophthalic acid, respectively. More preferably, the diacid component comprises 96 to 99 mol% of terephthalic acid and 4 to 1 mol% of metaphthalic acid. Optionally, the diol component comprises at least one C2 to C1 (and, more preferably, the diol component comprises at least one c2 to c5 diol. In one embodiment of the invention, The diol component contains ethylene glycol, and part of the ethylene glycol is dehydrated to form diethylene glycol (DEG) during the polymerization process, so that the copolyester of the polymerization product may be derived from diethylene glycol. Repeating unit B. Preferably, in the 7 t酉: based on the total number of moles of repeating unit B, the unit B derived from ethylene glycol is 95 to 99 mol%, and is derived from the second The repeating unit B of the diol is 5 to 1 mol%. Since the metal particles can be added at each j-stage of polymerization of the thermoplastic polyester-based polymer, the molecular weight of the thermoplastic polyester-based poly-object in the composition of the present invention is The thermoplastic polyester-based polymer covers a molecular weight range of liquid poly: (generally about 1 〇 100 100) and a solid state polymerization stage (generally about 1 〇〇 400), that is, having 1,0 〇〇1 a number average molecular weight between /000. Optionally, the thermoplastic poly, the polymer is 丨_ 45, _ _ number of average molecular, and further alternatively, the thermoplastic polyester polymer is a number average molecular weight between 1,000 and 35 '0 ,, while in the present invention The thermoplastic in the composition obtained in each stage of the I-incorporation, the polyglycol-based polymer has (3) Bu 19, surface and '0, number average molecular weight. The composition of Shi, Ming can be used for making Formed into a melt, ester granule, sheet or container, and is particularly suitable for making preforms and bottles. The invention also provides a thermoplastic polyglycol based on the present invention, and is formed into a product. a preform, and the preform preferably has a B*ghtness of between 75% and 100%, and a haze of between 2 and 8; more preferably, between 8 and 8%. Up to 1% of l* is between 2 and 3.5 halves. And preferably, the preform has a; 1 ΐί? a*', more preferably, between _2 and +2瓦生' 值 aH is about a value between 2 and G. Preferably, the b between you U: preferably has -in/too best, and the b* is in the range of about 〇 to 5 In each specific example, The prepared preform has a haze of between , and is between -1.36 and -1.42 and b* is between 4.73 and 4.98. The present invention also provides a thermoplastic poly-, and Preferably, the bottle has a haze of 槪:it and a haze of from 1 to 4. More preferably, h is a value of from about 〇·5 to Ο =. The bottle has - between _3 and +5 _ b*, preferably has a b* between _丨 and +4, and more preferably, the value of b*^ about 间3. In various embodiments of the present invention, the bottle of the bottle is between 2" and 4, a* is between -0.47 and b* is between 2.41 and 2% (nearly colorless). ). At the time of this writing, ...a* and bm are based on the color of the 976 CItL a*b* Macbethc〇1, and the spectrometer used in the measurement of the towel is 2 ϋ5. When the test sample is a preform, the sample thickness is set to 4 mm. When the test sample is a bottle, the sample thickness is set to 〇35 claws. 苴', the larger the L* value, the higher the brightness; a*>0 generation ', ^ color is greenish; b*&gt;0 means yellowish color, :: color is bluish. As for haze, it is measured by HAZE SUGA instrument and according to &amp; ASTM-D1003. The method for preparing the rapidly temperature-raising thermoplastic polymer composition comprises the steps of: adding the "genus particle", the polymerization stage, the liquid polymerization stage, in the stage of the group f from the thermoplastic; Solid state polymerization stage, segment. In the specific example of the present invention, the metal particle force "again" may be added in a time-addition or a stepwise addition manner, and the force of dispersing the metal particles in a liquid medium may be firstly performed according to the requirements of the process; At each stage of the above polymer polymerization or processing, the far-liquid medium is ethylene glycol. &quot;e Β ^ Ϊ 4 fruit. The metal particles such as Hai are in the phase 17 1 phase, such as injection: = = Preferably, it is first applied - dry: treated. Another: will: the pollution of the iSi / the eyebrows and make the particles more evenly dispersed, can be the first to the singer + sun Γ Γ. Mixing and first preparing the wire containing the metal particles, and then measuring the production line. [Examples] Hereinafter, the present invention will be further described by way of examples, and the comparative examples and efficiency tests are combined to demonstrate the advantages of the present invention, but the implementations The examples are for illustrative purposes only and are not intended to limit the invention. <Test method> Unless otherwise indicated, each test is carried out at normal temperature and pressure in the following manner: 1. Intrinsic viscosity test: a sample to be tested and dissolved in a solvent of 25 cc (volume ratio) 3: 2 phenol / tetrachloroethane solution) ', Charm and tested with Ubbelohde viscometer at 30C. 2. l*, a* and b* · is based on a use of 1976 CIE L* The significance of the parameters of the operation and the magnitude of the L*, a* and b* values measured by the Macbeth color eye 2145 spectrometer of the a*b* colorimetric method is as described in the previous embodiment. 3. Haze: Use The HAZE SUGA instrument was measured according to the ASTM-D1003 method. 1354679 &lt;Example 1&gt; Liquid polymerization stage

38 Kg of terephthalic acid (TPA), 0.9 Kg of benzoic acid (IPA), and 18.16 Kg of 1.125 g of aluminum powder (purchased from Xintao Applied Materials Co., Ltd., product name is aluminum powder and model number For AI-H03-P02, ethylene glycol (EG) having a particle size (d50) of 2±1 //m) is fed into a stirred tank and stirred into a paste, which is then poured into an esterification tank. The temperature is raised (the final temperature is 250 ° C) and the esterification is carried out for 6.5 hours at the same time. When the esterification rate is more than 95%, a polymerization product (esterified product, polymerization degree of about 7, and number average molecular weight of about 1350) can be obtained. The polymerization product was transferred to a polymerization tank, and 1260 g of a catalyst (antimony trioxide, Sb203) and 35 PPM of an antioxidant (phosphoric acid, H3P04) were added, and the mixture was heated to a vacuum to be polymerized to an inherent viscosity of about 0.6 dL/g. (Number average molecular weight: about 19,000), followed by pelletizing to obtain PET copolyester liquid polymerized ester particles doped with aluminum particles (in which the amount of aluminum powder added was 25 PPM based on the weight of PET).

In the solid state polymerization stage, the liquid polymerized ester granules are poured into a solidification reactor, and then heated and vacuumed, firstly heated to 85 ° C for drying for 2.5 hours, then heated to l 〇 5 ° C for 3 hours, and then heated to The pre-crystallization was carried out at 150 ° C for 2 hours, and then the temperature was further raised to 235 ° C to be polymerized until the intrinsic viscosity was about 0.85 dL/g (the number average molecular weight was 31,000), and then granulation was carried out to obtain aluminum-doped particles. PET copolyester solid polymerized ester granules. Regarding the repeating unit composition in the PET copolyester obtained after solid state polymerization, since EG is excessively added during polymerization, and some of the ethylene glycol is dehydrated during the polymerization to form diethylene glycol (DEG), the permeation meter 11 1354679 The amount of TPA and IPA raw materials added by the institute (completely reacted), and the amount of DEG in the copolymerization was determined by GC (Perkin Elmer auto system), and it was confirmed that in the PET copolyester, the structural unit A was The total Mohr number, the structural unit A derived from TPA 舆 IPA accounted for 97.7 mol% and 2.3 mol%, respectively, and the structural unit B derived from EG and DEG accounted for 97.6, respectively, based on the total Moiré of structural unit B. Mol% and 2.4 mol%. Embryo stage

The solid polymerized ester granules were dried at 160 ° C for 5 hours, poured into an injection machine (manufactured by Seiko Co., Ltd.), and the embryos were ejected at 275 ° C to 280 ° C. Blowing stage

The shot preform was placed in a cracking blow molding machine of Jiaming Machinery Co., Ltd., and heated at a temperature of 105 ° C for 50 seconds with a quartz lamp tube, and then the surface temperature of the preform was measured by an infrared thermometer (the measured results are shown in the table). 1)), then the softened preforms were placed in a blow mold cavity and blown into a bottle using a nitrogen pressure (18 to 32 Kg/cm3). The physical properties of the measured preforms and bottles are shown in Tables 1 and 2. &lt;Example 2&gt; The same PET as in Example 1 was obtained after solid state polymerization, except that the amount of aluminum powder mixed in the liquid polymerization stage was 50 PPM, and the same conditions as in &lt;Example 1&gt; The composition of the copolyester repeating unit, the measured physical properties of the preform and the bottle are shown in Tables 1 and 2. &lt;Example 3&gt; The preparation was carried out under the same conditions as in &lt;Example 1&gt; except that the amount of the aluminum powder mixed in the liquid polymerization stage was 100 PPM, and was obtained after solid-state polymerization of 12 1354679 *. The same PET copolyester repeating unit composition of Example 1 was measured, and the measured physical properties of the preform and the bottle are shown in Table 2 and Table 2. &lt;Comparative Example&gt; The same PET copolyester repeating unit as in Example 1 was obtained after solid state polymerization except that any powder was added in the liquid t-stage, and the same conditions as in <Example 1> were carried out. Composition, measured physical properties of preforms and bottles are shown in Tables 1 and 2. Table 1 Preform aluminum powder addition amount (PPM) Preform surface temperature °c L* a* b* Haze Comparative Example 0 113 82.43 -1.36 4.85 2.2 Example 1 25 118 81.5 -1.37 4.9 3.5 Example 2 50 122 79.94 -1.41 4.98 5.6 Example 3 100 129 78.31 -1.42 4.73 8.1 Table 2 Addition amount of preform aluminum powder (PPM) L* a氺b* Haze comparison example 0 89.81 -0.36 2.9 1 Example 1 25 90.94 -0.47 2.41 _ I _ 2.1 _ Example 2 50 90.5 -0.46 2.41 3.6 _ Example 3 100 89.71 -0.46 2.59 4

Collision_fruit and discussion: It can be seen from Tables 1 and 2 above that although the haze of 13 1354679 preforms obtained in Examples 2 and 3 was slightly higher, after blowing into bottles, Comparative Example 1 and Example 1 were 3 All have acceptable bottle brightness (L*~90) range and haze (Haze S 4) range acceptable to the industry. From the comparison of the surface temperature of the preform, it can be seen that the embodiment in which the aluminum powder is added can effectively shorten the preform heating time under the condition that the final product bottle is nearly colorless and transparent, so at the same heating time, the embodiment The preform can reach a higher surface temperature.

In summary, the present invention provides a thermoplastic polystyrene polymer composition by adding metal particles having high thermal conductivity properties at various stages of preparation of a thermoplastic polyester-based polymer, not only in the processing reheat stage. (especially the reheating of the preform) quickly heats up, while also obtaining a near-colorless and transparent final processed product (especially a bottle), which meets the market's demand for colorless containers, which is a black body or gray body absorption. These prior art techniques, which have particles to thermoplastic polyester polymers that have high reheating properties but lose color and clarity, are far from being.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All of them are still included in the scope of the patent application of the present invention. [Simple description of the diagram] [Explanation of main component symbols] 14

Claims (1)

1354679 Seven applications. The monthly polymer is more than one. a number average molecular weight between 00 and 6_〇; and, a multi-genus particle, the metal particles being aluminum, magnesium, rhodium, calcium particles to l〇1〇um, etc. and wherein the metal particles have a content of 0.1 The 魄 Β Β _ 粒径 粒径 , , , , , , , , 粒径 粒径 粒径 粒径 粒径 粒径 粒径 粒径 粒径 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于 基于The invention relates to the rapid temperature-raising thermoplastic polyester according to item 1. Two: and, in the matter, based on the total = 蚱 of the thermoplastic polyester polymer, the content of the special metal particles is between 1忡1^ to ι〇〇ρρΜ The rapidly temperature-raising thermoplastic polyester according to the third aspect of the invention, wherein the content of the metal particles based on the total concentration of the thermoplastic polymer is between 20 PPM and 100 PPM. The rapid-temperature-heating thermoplastic polyester compound according to the first aspect of the invention, wherein the metal particles have a particle size of between 0.1 and 1 μm (i50). 快速ίυΐί The rapid heating of the thermoplastic polyester vines described in item 6 of the above-mentioned items has a d50 particle size of between ο.1 and 10 μηη. The rapid temperature-increasing thermoplastic polyurethane composition according to Item 1, wherein the thermoplastic polyester-based polymer is composed of at least a repeating unit A of the adipic acid component and a unit of one or two B is composed of (4), wherein the diacid component "2 2, an aliphatic diCarb0xyiic acid, an aromatic dicarb xylic add of Q ~ μ, or a combination thereof The diol component comprises a diol of A to Cl oxime. 9. (4) 8 A quick-temperature thermoplastic polystyrene composition of the composition, wherein the diacid component comprises an aromatic diacid. The rapid-temperature-heating thermoplastic composition according to Item 9, wherein the c8-Ci6 aromatic dicarboxylic acid is Hashimoto-T acid. u· skillfully, the patent scope is i. The rapid rise "polymer composition" wherein the thermoplastic poly(tetra) polymerizes "poly = copolyester of ethylene methacrylate or polyethylene terephthalate. The rapidly temperature-raising thermoplastic poly 1354679 ester earth polymer composition according to claim 10, wherein the phthalic acid is at least the total amount of the diacid component, and the phthalic acid is at least 6 〇 m〇l%, and ethylene glycol is at least 60 mol% of the diol component based on the total moles of the diol component. 13. The rapidly heated thermoplastic polymer composition according to claim 8 wherein the diacid component comprises two C8 to C16 aromatic diacids. 14. The rapidly elevating thermoplastic polymer composition according to claim 13 of the patent application, wherein the di-Q~Ci6 aromatic dicarboxylic acid is a p-monocarboxylic acid and isophthalic acid, respectively. The rapidly temperature-raising thermoplastic polymer composition of claim 14, wherein the diacid component comprises 96 to 99 mol 〇 / 0 scoop of the diterpenic acid, and 4 to 1 mol % of isophthalic acid. The fast-heating thermoplastic poly-S composition of the 16 rtnf range of $8, wherein the diol component comprises an alcohol. 5-- The rapidly temperature-raising thermoplastic poly-ruthenium sulphide according to item 16, wherein the diol component comprises ethylene glycol. 18·= 申 专利 专利 专利 专利 专利 专利 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 And Ho Sheng--the repeating unit B of ethylene glycol is 1% of the 5η coffee. 17 1354679 19 The rapidly warming thermoplastic polyurethane polymer composition of claim 1 is used to form a melt, ester granule, material or container. ^ 20\ The rapidly warming thermoplastic polyester polymer composition according to claim 19 of the patent application is used to make a preform or bottle. 21 快速 The rapidly elevating thermoplastic polyester polymer composition according to claim 20 of the patent application is used to make a preform, and the preform has a ratio of 75°/〇 to 100°. /. The L* brightness, as well as a haze of 2 to 8 wei ^. • The rapid temperature-raising thermoplastic polyester polymer composition of claim 21, wherein the preform has an L* shell of between 80% and 1%, and A haze of between 2 and 3.5. 23. The rapidly warming bismuth plastic ester polymer composition according to claim 20 of the patent application is used to make a bottle and the bottle has an L between 88% and 1% 0%. * Brightness, and a g degree between /~4. 24. A fast literate polymer composition according to the scope of the patent application, wherein the thermoplastic polyester is water having a number average molecular weight of between 1 and 45,000. . Material, there is a 25. basis! The invention relates to a rapid temperature-raising thermoplastic polyester poly&amp; composition according to the invention of claim 4, wherein the thermoplastic polyester has a number average molecular weight of between 1,000 and 35,000, and has a 1354679 26. A method for preparing a rapidly temperature-raising thermoplastic polyester-based polymer composition according to any one of claims 1 to 25, comprising the steps of: selecting one of the thermoplastic polyester-based polymers from below The metal particles are added to the stages in the group: a polymerization feed stage, a liquid polymerization stage, a solid state polymerization stage, and a processing stage. The production method according to claim 26, wherein the metal particles are added at a liquid polymerization stage of the thermoplastic polyester-based polymer. i 19