TW318859B - - Google Patents

Description

Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^ 518559 v A7 ----- B7 V. Description of the invention () Background of the invention: The present invention is made of polyethylene terephthalate containing ω-hydroxycarboxylic acid The method of the component linear copolyester (COMET) is related to the copolyester itself and the application of the copolyester to manufacture hollow objects, especially bottles and containers. It is also used to manufacture COPET fabrics and filaments. When almost only homologous polyethylene terephthalate (PET) is used to make polyester fabrics and filaments, in fact, it is now exclusively used from 2 to 5 and occasionally up to 7 mol% The modified PET-based copolyester (COPET) type is used to make pET bottles for aerated sweeteners and similar liquids. Due to the lower melting point, the advantages at lower processing temperatures are the lower acetaldehyde content and the transparency of the glass due to the lower crystallization rate. The conventional auxiliary components include composite comonomers such as dicarboxylic acid (or methyl ester of dicarboxylic acid), diol and hydroxycarboxylic acid. Used in bottle-grade COPET to use isophthalic acid, naphthalene-2,6-dicarboxylic acid, 1,4-cyclohexanedimethanol, and diethylene glycol produced in a small amount during the in-situ homo-PET production It is better to wait (for example, see European Patent Publication No. Ep_〇〇41〇35). At the beginning of the production process, or in other words, under the action of esterification or transesterification, these auxiliary components are added to the two main components, namely: terephthalic acid or dimethyl terephthalate and ethylene glycol. At the end of the production of PET, the addition of the above-mentioned auxiliary components will lead to a sharp drop in viscosity, which will cause doubts about the processing. Therefore, in the prior art, PET particles for bottles and fabrics cannot be made simultaneously in the same esterification and polycondensation equipment, although the problem of how to remove the PET melt after the fabric use is now all It has been solved (see German patent DE_4033 987 C2). -2-This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) n · m---Γ-- ·----I--II (Please read the notes on the back before filling in this Page), 11 ◎ 18859 A7 ______B7_ V. Description of the invention (2) The prior art provides various starting points for the use of PET melts to make copolyesters. Nevertheless, the application of simple equipment quickly and without changing the intrinsic viscosity (IV ·) It can be made into a lower melt line type, that is, the purpose of non-branched long-chain statistical distribution or random distribution of copolyester is completely or only partially achieved. (The I.V. value is a traditional standard number used for the molecular weight of polyester in bottles). European Patent Publication No. EP-0 422 281 A1 describes a method in which the dianhydride of aromatic tetracarboxylic acid, preferably pyromellitic dianhydride, is metered into a PET melt and lacquered. Because the additional substances added in the polyaddition reaction connect the polymer bonds, the particles generated are even significantly lower at a lower temperature mainly due to the very rapid increase in the IV value in solid-phase polycondensation hand over. Theoretically, the result is a copolyester, and the amount of pyromellitic dianhydride, i.e. 0.6% by weight, is better due to the post-polycondensation, so as long as the isophthalic acid If it is additionally used as an auxiliary component, the maimerald at the melting point is only 2 ° C ° Finally, the dianhydride also has side effects, so that the second carboxyl group released to the anhydride group after the addition reaction, in the subsequent reaction At least sometimes cause branching. Therefore, although the so-called melt strength has increased in extrusion blow molding, the flow characteristics have also deteriorated. Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs ^^^ 1 1 ^ 1 In I Ln mtmm ^^^ 1 1-¾ T * (please read the precautions on the back before filling out this page) according to DE 41 31 362 A1 In the method disclosed in German Patent No. 1, the usual dicarboxylic acids and diols are used as auxiliary components, especially those with a low viscosity prepolymer containing a high proportion of comonomers. In this method, one or "one" is required to make a prepolymer. An additional reactor is needed, and one is used to mix the prepolymer with homopolymer-3.-This paper scale uses the Chinese national standard (CNS) A4 specification (210X297 gong mai) 3 3ϊ8〇59 V. Description of the invention (extruder. According to this method, no copolyester appears after the preferred melting and mixing time is ^ 5 ^ pounds, but instead It is just a mixture of granulation = physical poly 5 compounds, which still has substantially the same height as the homogenous PET. It is still calculated until the solid phase shrinkage is used. The copolyester is formed due to the same specific composition. The way to make the newspaper reported 1! The melting temperature of silk 61 is higher than 2 < > c Regarding the copolymerization method in this method; the description can be found in pages 44 to 51 of page 3 of the open literature;. = After only a sufficient time for melting and closing the wedge, only the block copolymerization: the upper Ϊ block copolymer cools after condensation During the reaction, the closer to the molecular chain t, if the distribution of auxiliary components is, the content of the mixed copolyester containing the comonomer is read as low. The shortcoming of this method is that it has a lower limit of #IV value, that is, it has The lower limit of the molecular weight of the comonomer-copolymerase. After all, the lower the lower limit of the IV value is dominated by the economy of the entire processing process due to the reduction of the working value of the polymerization mixture compared with the homogenous PET. The central standard of the Ministry of Economic Affairs Office staff consumer cooperation du printing n I nn I — n I-m too 1 ^ 1 1 ^ 1 n, 5J (please read the precautions on the back before filling this page) US Patent No. 1,68〇, 345 Describe a method that uses this method to dissolve aromatic polybromide in a reaction vessel, especially polybutene terephthalate and a relatively large amount of internal vinegar can be produced by continuous polyaddition Elastic polymerization. The set reaction conditions are temperature range from 21〇 to t , The reaction time is 30 minutes to 6 hours. The result is a block copolyester, which contains flexible segments that impart elasticity to polylactone and hard crystal segments of aromatic polyester. Disadvantages in addition to the long reaction time The difficulty of this method also lies in the fact that the non-reactive inner_steamed flying gas field is formed in the upper part of the reactor, and if no precautionary steps are taken (for example: positioning the reactor vertically or diagonally or incorporating it into the flue gas board) ;; Each problem appears and the quality becomes very bad. 1 This paper scale is applicable to China National Standard (CNS) A4 specification (210 X 297 Molu A7 B7) 5. Description of invention (4) It is also described in the following eight references The reaction between polyester and lactone:

Derwent Abstract No. AN-94-238850 cited Japanese Patent No. J 061 71507, describing an elastic copolyester with improved thermal stability obtained by the reaction of aromatic polyesters and lactone compounds, in which aromatic The diol component of the family polyester has a special formula. The cited patent information does not make any special statement about the manufacturing method, and such copolymer combinations are not suitable for making bottles. Printed by the Employee Consumer Cooperative of the Shenyang Standard Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling this page)

Derwent Abstract No. AN93-121484 cited Japanese Patent No. Γ05059192, which describes a continuous manufacturing method of elastic polyester film and sheet. Here, in a twin-screw extruder containing a lactone compound, aromatic crystalline polyester is continuously subjected to addition polymerization and undergoes a short holding time of up to 30 minutes at a temperature of up to 280 ° C, from which Directly made into plates. However, in order to obtain the advantages of high-quality plates, it is necessary to "pay the price", using very expensive machines, which are used as reactors and for devolatilizing unreacted lactones. Not only that, according to this method, there is no best way to add additional tin or phosphorus catalyst to the polyester, but it cannot be used in the field of food packaging. Also, under the conditions listed in the exemplary examples, only block copolyesters (aromatic polyester hard blocks and soft polylactone blocks) were produced without statistical copolyesters. The melting point of polyester relative to the amount of caprolactone decreases slightly, which becomes very obvious, which is related to the elastic characteristics.

Derwent Abstract No. AN90-159117 cited Japanese Patent No .: Γ0 2099555, describing a crystal with up to 5 wt% /?-Methyl d-valerolactone (MVL) as a comonomer and up to 50 wt% Accelerator -5-This paper scale uses the Chinese National Standard (CNS) A4 specification (210X297 mm). 316659 A7 _ B7_ is printed by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy. V. Invention Instructions (5) Copolymerization on PET substrate wine. Manufacturing is carried out by conventional methods by vinegaration and polycondensation (including ring-opening polymerization of lactone during polycondensation), while copolyester is used in opaque, highly crystalline injection molded parts.

Derwent Abstract No. AN90-159116 cited Japanese Patent No. J02099554, describing a copolyester similar to the kind disclosed in Patent No. J02099555. The only difference is that during polymerization, it replaces MVL and combines up to 2% by weight. £ -caprolactone.

Derwent Abstract No. AN85-078330 cited Japanese Patent No .: Γ60031525, describing a high-viscosity block copolyester, which is based on the homopolymerization of the solid phase (for example: pet) and inner cool (for example: ε-hexane Cool). Block copolyesters such as these still have a high melting point, which is similar to homopolyester, and therefore, such block copolyesters cannot be processed at lower processing temperatures, which is the temperature necessary to make bottles .

Derwent abstract No. ΑΝ8 4-259558 cited Japanese Patent No. J5915 7117, which describes a use of 2 to 5% by weight of lactones, such as: ε-caprolactone, at 180 to 260 ° C-an organic tin, A method of modifying a crystalline aromatic polyester (for example: PET or PEN = polyethylene naphthalate) by reacting an aluminum or titanium catalyst with an optional solvent. The resulting properties make polyester suitable for use in films, sheets and containers. Therefore, the object of the present invention is to provide a linear copolyester having the same viscosity (I.V.) with a lower melting degree, which is simple and rapid, without any disadvantages of the prior art. The purpose of the present invention is the method defined by the first feature of the patent application scope, the copolyester of the patent application scope item 1: L, and according to the patent application model-6-This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210X297mm) ------ „---- ^ 'Clothing -------, order ------ 1 (please read the precautions on the back before filling this page)

A7 B7 V. Description of invention (6) The use of items I2 and I3 is achieved. The subsidiary items of the patent application scope describe preferred embodiments of the method according to the invention. It has been proven that the use of comonomers in the form of compounds in lactones, especially ε-caprolactone, is best mixed with ρΕτ · melt in the form of simple monomers and allowed to -A closed system that prevents gas exchange reacts to achieve the purpose of the invention. After a few minutes and the amount of lactone, the mixing and reaction zone does not require a reactor or extruder to sink, it is surprising that a melting point reduction is linear and most of the statistical denaturation Polyester is formed in the melt. The fact that the anhydrous lactone is used but the intrinsic viscosity remains the same is also surprising. As disclosed in the literature, polylactone exceeds 200 at temperature. It is easy to decompose when it is above [see RD Lundbery et al., Journal 〇fp〇iymer science 7th Part Al, 1969, cross pages 2928-2929), but the temperature of pET melt is above 26〇eC The reason for this is also not expected by everyone. Although, in principle, the reaction between polyester and lactone and the resulting lactone-copolyester is known, it is surprising and unpredictable that statistical copolymerization can be obtained using the method of the invention Ester, this method uses a very simple device and does not require additional touch, and after the copolymerization brewing after the condensation polymerization reaction after slowing down, it can be suitable for manufacturing bottles containing beverages. To be specific, the method of the present invention includes the step of up to 10 mol% of a compound from the lactone family called the final ingredient and optionally further adding a dose into and mixing into the melt. The melt consists of a At least 90 mol% polyethylene is composed of polyester with an ester component. Immediately after passing through a one-one paper standard, the Chinese National Standard (CNS) A4 specification (210X297mm) is applied (read the precautions on the back before filling out this page) Γ Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs A 7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (7) The melting mold closing time is typically controlled by the device used and the time is less than 30 minutes, preferably up to 20 minutes, then , The molten material is further processed or unloaded to make it granular and then processed again. A preferred partial step in further processing operations is solid-phase polycondensation, which increases the molecular weight of the copolyester on the one hand and reduces the acetaldehyde content on the other. Crystallize and dry the granules before the local steps. As for the molding of the molded body, particularly the hollow object or the pre-forming of the body is preferred, the final step of the method of the present invention is formed. Another preferred way of further processing the copolyester melt of the present invention is to spin the copolyester into weaves and filaments. According to the method of the present invention, the reaction time for adding a lactone having a cyclic structure and preferably containing from 6 to 12 carbon atoms to the polyester chain is very short, therefore, it has substantial advantages over other modification methods . Also, the addition will not cause any split by-products and needs to be eliminated. Therefore, a gas exchange seal-type reaction device at a gas pressure higher than the vapor pressure of the lactone may be a simple tube through which a melt can flow and a cocurrent mixing device is provided. Here, a dynamic mixer can be used, preferably a static mixer. It is particularly particularly advantageous that the reaction time is short enough that it can be used after existing manufacturing processes such as conventional polyethylene terephthalate, for example, to complete the method according to the invention only in the partial melt stream without incidental disadvantages. The fact that the viscosity is not affected despite the lower melting point is of great significance for the mechanical properties of both the melt and the molded parts in which the copolyester according to the invention is developed for use. —8 — This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) n · ^^^^ 1 ^ 1. ^ 1 flu— km — ^ m mV I n nn f ^ i— nn i ^^ i— \ 一 穿 i (Please read the precautions on the back before filling out this page) A7 B7_ printed by the Employees ’Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Description of the invention (8) The lower melting point of the copolyester of the present invention depends on Depending on the amount added, the maximum amount used is 10 mol%, 0.5 to 8 mol% is advantageous and preferably 1 to 6 mol%, and 2 to 5 mol% is the most Falcon. This allows the copolyester to be processed at a lower temperature, which can effectively reduce the formation of acetaldehyde. For processing reasons, polyethylene terephthalate usually contains a small amount of diethylene glycol as a chain component, and this small amount of diethylene glycol can also be regarded as a comonomer. This method allows the use of polyesters containing up to 5 mol% diethylene glycol. This is essentially only because the total amount of comonomer does not exceed 10 mol%. The following examples illustrate the method according to the present invention in further detail. According to the method of the present invention, it is preferable to measure the amount of liquid lactone into a sealed device, for example: a pipe through which a melt can circulate and a static mixer therein can ensure that the inner vinegar is distributed in the PET melt. According to the method, the reactor and / or the extruder are not needed in the vinegar measuring, mixing and reaction zone. The melting mold closing time necessary for the lactone reaction, that is, from the moment the lactone is added to the PET melt until it is discharged is less than 30 minutes, preferably up to 20 minutes. Even after good mixing, the part of the stationary monomer that usually remains after the above mold closing time has reacted in the subsequent post-shrinkage. For this reason, in addition to the existing catalyst in PET, it is not necessary to additionally mix other catalysts. In this way, it can be used as a food package to prevent the problem of poisons, and therefore also represents an advantage of the method of the present invention. (Please read the precautions on the back before filling out this page) This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Invention Instructions PET melt, preferably using poly 6-associated terephthalate, which contains a constant diethylene glycol component for preparation purposes and a familiar catalyst and stabilizer. As other additives, the additives named in German Patent No. DE 27 15 932 C2 are used, for example: use-led additives. For the purpose of color adjustment, it is better to use the type in the prior art. The inherent viscosity is preferably in the range of 0.5 to 0.8 deciliters per gram (dl / g), and is usually equal to the viscosity of the fabric. Since the method of the present invention can be incorporated into the design of a flexible and economical plant, different parts of the same PET melt stream can be effectively used to produce woven or filaments after the subsequent matting treatment. The PET melt temperature is in the range from 265 to 310 ° C, preferably between 270 and 295 ° C. The gas pressure is higher than the vapor pressure of the lactone. As far as ε-caprolactone is concerned, the vapor pressure as a function of temperature can be approximately expressed by the following formula P = 4,6O87 * 1O5 * exp [-6581 / (0 + 273,15)] from P = vapor pressure, using bar ( bar) (absolute value) to represent and temperature, expressed by ° (:. The amorphous coarse copolyester particles obtained by the method of the present invention is best to use a method familiar in the bottle pellet industry to crystallize and polymerize in the solid phase The shrinkage device produces a higher inherent viscosity and a lower acetaldehyde content; so that the particles are made into processed (bottle-grade) bottle particles, and then processed in a bottle particle type to make, for example: preforms and bottles. The amount of lactone It is selected so that the reduced melting point required for the manufacture of bottles or preforms can be achieved. The above can be added by adding 2 to 5 mol% lactone-10-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) II ^ policy, words (read the precautions on the back and then fill out this page) A7 B7 printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs V. Description of invention (1 ()) This is done effectively, this is Because the effect on lowering the melting point is about The comonomers are the same, or in other words, about 2% per mole. 2C for special requirements, such as: clear and transparent without defects, even in very thick preforms, may be higher Concentration, up to the highest mole%. The following examples serve as the author of Kan Ming and strengthen the present invention. Example 1 The original material is a colorless amorphous PET particle containing the following material characteristics:-inherent viscosity (IV) 0.663 dl / g The intrinsic viscosity is determined by measuring the relative solvent viscosity R. V. In the solvent mixture consisting of equal mass ratio of phenol and 1,1 ·, 2,2 tetrachloroethane. The calculation is done using the Haggins equation Recalculation of the IV value, where KH = 0.35: \ / 1 λ / 1 1 + 4-Kh (RV-1) -1 (RV-Ί) -1 lV = -----. 一 = --- ( di / g) 2Kh-C 0,35-melting point (DSC, 20 ° C / min) 2 53.7 ° C Compared with the heating rate of 10 ° C / min, using the DSC-heating speed of -20 ° C / min The measured melting point is about 3 ° C lower-diethylene glycol content 2.0 mole%-di content (as Sb2〇8) 250 ppm Sb-scale content (as Η3Ρ04) 11 ppm P Crystallize the particles After drying, feed the pellets to a single screw for melt extrusion-L Γ n ^-mil m · fl ^ l > n ^ i «ϋ · ϋ ^^^^ 1 i ml mfl Ϊ ^ I " Please read the precautions on the back and then fill out this page) -11-This paper is printed using the Chinese National Standard (CNS) A4 (210X297). Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. Description (1: L) The machine is used to make a melt with a melt pressure of 100 bar. Afterwards, the melt travels through a heating tube in which a gear pump is installed and brought to a molding head with a pressure measurement of 50 bar and the two molten filaments can be squeezed to cool in water and granulate. The temperature is adjusted to 290 ° C. As the comonomer, the monomer ε-caprolactone manufactured by Interox Chemical Co., Ltd. was used. This compound turned into a liquid at room temperature, and the compound was fed into the pellet inlet adapter of the extruder by a metering pump, in which caprolactone was mixed with molten PET and started to react without revolatization. Therefore, the effort necessary to obtain the results of the first test approximates the most relevant prior art, for example: the one disclosed in Patent No. J05059192. Adjusting the amount of caprolactone to 5 mol% means that in the modified polyester, there are 5 lactone components for every 95 terephthalate components. Under the maximum capacity of the metering pump (2000 ml / h) and a total production of 71.2 kg / h, the resulting mold closing time is from the pellet charging inlet to the molding head (the effective melting mold closing time is estimated to be about 9 minutes ) To calculate for 10 minutes. The molten filament that stands out is clear, uniform and free of bubbles and steam. Surprisingly, the modified particles made in this way showed that on the one hand, the intrinsic viscosity remained almost unchanged (IV = 0.642) except that the original particles contained a small amount of residual moisture and caused a slight hydrolysis. dl / g), on the other hand, the melting point drops to 244.3 ° C, or in other words, decreases by 1.88 ° C / mol%. This in fact proves that caprolactone has been incorporated into the molecular chain and forms a statistical copolyester. Example 2 Using the same original particles as in Example 1, at the same time at room temperature -12-This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm)-^ policy (please read the back side first (Notes and fill in this page) A7 S18859 V. Description of the invention (12) '^ · I f policy (please read the notes on the back before filling in this page) Liquid y-butene brewing (from Fluka Chemical Co., Ltd.) The company obtained) into a similar experiment. The measured amount is again 5 mol%. However, the fuse strips coming out of the molding head have high volatility, and even if the method of prolonging the mold closing time (reducing the throughput) is used, the volatility cannot be substantially reduced. The melting point of the samples obtained after the mold closing time of about 20 minutes has passed is 251.7 ° C. A slight drop of 2 ° C in this melting point confirms the conclusion that when butyrolactone is not completely inert, it is obvious that only about 20% (approximately 1 grass ear%) of the reaction used reacts. The low anti-deer degree of y_butyrolactone is not very suitable for adoption. ~ Relatively comparison, from ε_caprolactone and above from the same series of lactones, namely: lactone_7 'lactone_8, lactone_9, lactone_1 (), lactone and laurolactone due to The lack of a stable ring is particularly suitable for the melt modification method according to the present invention (the number assigned to each lactone indicates the number of carbon atoms in the ring molecule). Example 3 ', an example of an aromatic lactone is phthalide, and its melting point is he. Although the degree of reaction is minimal, this phthalide is suitable for use as an example of lactones to be melted before they are measured in liquid form. The Dsc measurement showed that the heat of fusion content was H7 J / g. In a laboratory test, phthalide was kept in the liquid phase at 85 ° C for 3 hours under krypton gas, showing no change in color or melting point. Printed by the Consumer Cooperative of the Central Central Bureau of Economics of the Ministry of Economic Affairs. From the standpoint, it is possible to include a melting period in the process. Embodiment 4 In a real embodiment of the invention, the Sulzer company made of I3 SMX-type mixer elements and the inlet flange There is a liquid-13 _ 芈 (cns) A4 ^ (210X297mm) A7 B7 5. Description of the invention (13) The static mixer of the small tube for the injection of additives is embedded in the melt line between the melt extruder and the gear pump Using this device, the amount of £ -caprolactone of 4 mol% is added to the PET melt. According to this mixing ratio, using the above 13 SMX-type elements is theoretically achieved (according to the Sulzer mixing quality diagram). A mixing mass of 0.01 * / Ai (coefficient of variation). A coefficient of variation of 0.05 equivalent to about 10 mixing elements has been deemed to be practically homogeneous. The substance is a result of chemical reaction (transesterification). Transfer (physical d after istribution) With the effect of blending (mixing), the final homogeneity is actually better. The experiment is at a melting temperature of 290 ° C and a total throughput of 70 kg / h (ε-内 内Ester mass = 1567 ml / L)), at the beginning, using the same PET particles as in Example 1. The time from the charging of the static mixer to the melting of the molding head is 10 minutes. The melt pressure upstream of the molding head It is 50 bar. The intrinsic viscosity of the sample taken before the start of the caprolactone measurement is 0.653 dl / g and the intrinsic viscosity of the caprolactone copolyester is 0.655 dl / g, or in other words, the two viscosity values are actually the same. The melting point of COPET particles is 246.3 ° C, therefore, the molar effect on the melting point is 1.85 ° C / mol%, or in other words, almost the same as in Example 1, which further evidences that ε-caprolactone has Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). Analysis of the amorphous particles shows that about 95% of the used caprolactone is chemically combined Into the polyester chain, and about 5% is based on There are 0 physical bonding forms. Example 5 As a comparison of a novel fusion modification method, the Chinese National Standard (CNS) Α4 specification (210Χ297mm) ® ^ 8S59 A7 B7 V. Description of the invention (14 0.637 dl / g 247.7 ° C 1.3 mole% 130 ppm Sb 20 ppm P 20 ppm Co—made in a polyester batch (batch) system composed of esterification and polycondensation reactors Caprolactone COPET. At the beginning of the esterification, the addition of 4 mol% epsilon-caprolactone to the residual material from the same ingredients in the previous esterification reactor was completed. The results obtained from the selected technical method are the following amorphous COPET particles:-inherent viscosity (Iv)-melting point (DSC, 20 ° C / min)-diethylene glycol content-antimony content (as Sb2〇8) -Scale content (as h8p〇4) -Gu content (as C〇 (CH8C00) 2.4H20) Even if the conventional usage of caprolactone is used in the production of COPET, the influence on the melting point is roughly the same as in the method according to the invention . No free caprolactone was detected. Due to the addition of cobalt acetate, the color of the particles is slightly bluish. Example 6 The copet particles from Example 4 were crystallized at a product temperature of 210 in a banned dryer at i60 ° C. (: The solid phase is lifted and lowered in a vacuum drum dryer. Calculated with a product temperature of 22 ° C, it takes only 3.5 hours to reach an IV value of 0.82 dl / g 'This is due to the high amount of catalyst in the original pet. The acetaldehyde content can only be reduced to 2.8 ppm in this short time. On the other hand, no free caprolactone was found when the condensation proceeded afterwards The interest in the inside is the material performance in further processing: in a Demag DZ210-1200 / 1200 injection molding machine with an eight-cavity tool 15-This paper size is applicable to the Chinese national standard (CNS> A4 specification (210X297 Cli) ------ ^ --- ^-Γ. 策 ------ 1T (please read the notes on the back before filling out this page) Ministry of Economic Affairs, Central Bureau of Economics and Technology, Shellfish Consumer Cooperative Printing Printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Α7 Β7 V. Description of invention () 丄 3 A bottle with a weight of 48 grams is made from the shrinked and dried granules for use as an I · 5-liter bottle Pre-formed. Very surprisingly, it can still be injection-molded at a very low temperature of 265 ° C without defects and clear and transparent Preforms ○ In addition, bottle granules that have been recognized as setting an excellent standard on the market have been obtained, and injection molding requires a temperature of 5 ° C. The preforming according to the present invention is unique in that it uses polarized light No structure is visible in the preformed wall during observation, which makes this type of copolyester suitable even for thicker wall preforms for reusable (refillable) bottles, which can be reused In this case, the turbidity caused by the initial crystallization constitutes a problem when using normal bottle-grade copolymers. Example 7 In the same manner as in Example 6, the copET particles of Example 5 were continued Processing operations; effective post-condensation time is 10 hours, after this time, the inherent viscosity of the particles is 〇. M dl / g and the content of acetylene is 〇 $ ppm ° Despite the high viscosity, the particles can still be at normal standard temperature (The temperature of the melt distributor is 28 °.) It is injection molded into transparent preforms. A Sidel stretch blow molding machine is used to blow the above preforms / forms into bottles. These bottles are bright in appearance. Light purple blue. The content of acetaldehyde in the bottle complies with Coca-Cola standards, and in a swimming (moving) test made with water, it is almost impossible to find traces of physiologically indisputable ε-caprolene Ester, so, the use of this novel copolyester to make beverage bottles should have no restrictions. Brief description of the diagram: Figure 1 is a schematic diagram of comprehensive C0PET production. This paper size is applicable to China National Standard (CNS) A4 Specifications (210X297mm) ^ n 'ml (nn ^ — n ^^^ 1 I ^^^ 1 ml ^^^ 1 ^ J. (Please read the precautions on the back before filling this page) A7 ^ 28859 B7 5 Description of the invention (16) According to the description of the present invention and the possibilities provided by the method of the present invention, the following industrially most ideal and especially optimal structure of a large-scale polyester plant can be conceived: 1. Same-component PET melt The final reactor in continuous polycondensation 2. One side is the divergence point that leads to the use of textiles and the other side is the one that leads to the bottle-level use 3. Adding the powder of titanium dioxide 4. Measuring into the dioxide 2. Double Screw extruder (used in the synthesis of titanium dioxide) 6. Static mixer 7. Will The matted homogenous PET stream (fabric) is discharged for direct spinning of woven or filament 8. Addition of lactone 9. Liquid metering pump 10. Static mixer 11. COPET melt flow 12. Granulation 13 . Crystallization (as part of SSP system) 14 · Solid-phase polycondensation (SSP) 1 5. During the process of discharging COPET bottle-level particles into the lactone, other lactones can still be dissolved, for example: The coloring agent dissolved in the melt, especially a small amount of an inert additive amount of the blue colorant such as the blue color enhancer used for color adjustment, is more advantageous to be added to the PET melt. -17-This paper scale is applicable to China National Standard (CNS) Α4 specification (210X 297mm) (please read the precautions on the back and then fill out this page) Pack--1, 1T ----- Central Bureau of Standards, Ministry of Economic Affairs Printed by employee consumer cooperatives

Claims (1)

318659 A8 B8 D8 Date; Supplementary application scope of Mu U8 (revised version) Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 1. A method for manufacturing linear copolyesters containing ω-hydroxycarboxylic acid components It is made of polyester containing at least 90 mole% polyethylene terephthalate component and normal amount of diethylene glycol component and possible conventional catalysts and stabilizers, characterized by: At least one lactone-based compound containing 6 to 12 carbon atoms in a closed system and at a gas pressure higher than the vapor pressure of the lactone can be optionally combined with more additives but no additional catalyst. 10mol% proportion of the prepared polyester melt is added and thoroughly mixed with the melt, after the total mold closing time is less than 30 minutes and the temperature is in the range of 265 to 310 ° C, the resulting copolymer The ester is further processed or unloaded, granulated and then further processed. The copolyester and the original polyester have the same viscosity and the polymer chain contains randomly distributed ω-hydroxycarboxylic acid components, so the package is sealed. It is a certain amount of pressure and provided with a bore and comprising a mixer located downstream of the orifice of the dosing tube. 2. The method according to item 1 of the patent application scope is characterized in that further processing operations include the steps of crystallization, drying, solid-phase polycondensation, and making into a molded body. 3. The method according to item 1 of the patent application scope is characterized in that further processing operations include the steps of making weaves and filaments. 4. The method according to item 1 of the patent application is characterized in that the mixer is a static mixer. 5. The method according to item 1 of the patent application scope is characterized in that the lactone-based compound added in a metered manner is ε-caprolactone (ep silon-caprolactone 6. The method according to item 1 of the patent application scope is characterized in The lactone is added in a metering quantity ranging from 0.5 to 8 mol%. 1.18 — This paper scale is applicable to China ’s National Standard Rate (CNS) A4 specification (210X297 Gongmai) In n — ^ im .J ^ i ml ijn n (Please read the precautions on the back before filling in this page) Order-rns I1--· si8S59 A8 BS C8 _______P8 VI. Application for a patent garden ~ "1. 7 · According to the method of patent application item 6, its characteristics The lactone is added in a metering amount from 1 to 6 mol%. 8. The method according to item 6 of the patent application range is characterized in that the lactone is in a metering amount from 2 to 5 mol% It is added. The method according to item 1 of the patent application range is characterized in that the polyester contains up to 5 mol% of diethylene glycol, and the sum of the diethylene glycol component and the hydroxycarboxylic acid component does not exceed 10 mol% 10. According to item i of the scope of patent application The method is characterized by the maximum mold closing time of 20 minutes. 11. The method according to item 1 of the patent application range is characterized by the melting temperature ranging from 27 ° to 295. (: within the range. 12. The first patent application range Item method, characterized in that further additives are additives controlled by the use, and soluble inert additives. 13. Method according to item 12 of the patent application scope, characterized in that the soluble inert additives are color-adjusting additives. I4 · According to the patent application The method of any one of items 1, 2, or 4 to 13 in the range, after manufacturing by this method, the condensed linear copolyester contains a random distribution of hydroxycarboxylic acid components. Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Manufacturing ϋ I m m.tjl ϋ 1— mnn ϋ ϋ I n (please read the precautions on the back before filling this page) 15. According to the method of any one of items 1, 2 or 4 to 13, After being manufactured by this method, the condensed linear copolyester contains randomly distributed ω-hydroxycarboxylic acid components, and the post-condensed linear copolyester is used to manufacture hollow objects, especially bottles and containers. 16. According to the patent application The method according to any one of items 1 or 3 to 13, the linear copolyester produced by this method contains a random distribution of ω-hydroxycarboxylic acid components. -19 _ This paper size is applicable to China National Standard (CNS) A4 specification (210X297mm)