TWI233933B - Copolyester suitable for extrusion processing - Google Patents

Abstract

A copolyester mainly contains p-phthalic acid and ethylene glycol. The copolyester further contains 1 to 15 wt% of at least one special diol selected from the group consisting of 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, and 1-hydroxyl-2,2-methyl-propyl-hydroxytrimethylacetylester. Optionally, the copolyester is added to 0 to 1.0 mol% of trimellitic acid, trimellitic anhydride, or trimethylol propane. The copolyester, in its molten state, has an increased viscosity of 0.8 to 1.4 dl/g and can be processed into various plastic products through an extrusion process. The invented copolyester has good processing properties, and is free of dripping drawback during the working process. The products produced have smooth surface, good transparency, high impact resistance, heat resistance, hydrolysis resistance, and chemical resistance.

Description

1233933 发明 Description of the invention: [Background of the invention] Industrial system of the invention = | ==; ^ Fine purpose tree, tree shrew copolymerized vinegar, with characteristics of Newtonian fluid, it can show low pressure at high shear rate ίΙίίΓΓ knife speed It exhibits high viscosity characteristics, so it can be easily melted and extruded. It does not have the problem that the melt glue sags too fast. It is especially suitable for extruding clothes into various strange hollow containers. The hollow container made of this copolyester had a uniform thickness, and the stomach container wall had no seam line. σσ has the characteristics of slow crystallization rate, so when making it longer and deeper, it will not have the problem of crystal whitening. In particular, when manufacturing a nuclear plastic with a length exceeding, for example, centimeters, if the conventional conventional polyg is used to produce a molded product by melt extrusion, crystal whitening tends to occur. ’This copolyester is made of extrusion blow-molded containers with impact resistance, which is different from that of ordinary polyesters that are extruded and blow-molded. The molding surface of this copolyester produced by extrusion blow molding has a smooth surface, does not produce a shark_skin surface, and does not cause excessive gelation due to excessive cross-linking. fish eye) surface. β J See 豕, the melting point of this copolyester is lower than that of the traditional polyester, and it is allowed to be carried out at a lower processing temperature. The catalyst, stabilizer and colorant used in the manufacturing process of this copolyester They are all used by existing packaging polyester materials that have been mass-produced. They have no health and safety concerns about polyvinyl chloride (PVC products that may cause the release of toxic additives. This copolyester and others are suitable for extrusion processing. Compared with polyester, it does not particularly emphasize the need to add a cross-linking modifier to improve the sag of the melt and improve the rate of solid-phase polymerization. "The previous description of the technology of polyethylene terephthalate is made into hollow molding Behind the object is transparent 1233933 Ξ and has a high resistance to impingement, the domain has a good ㈣ gas barrier ΐ Yes === food production 1 content is not like the content of PVC 2, ΓΪΓ is widely used as food packaging materials There are two molding methods Species, a class (or extrusion) blow molding Π 弋, the left and right leaves of the mold _ in the molten state, so the two embryos |, Nen Niancai like this: Comparison of extrusion blow molding and injection blow molding The molding method has different processing characteristics, such as simple technology of plastic molding, cheap processing machinery and equipment, and mold cost: speed; easy and can be manufactured with complex shapes and long lengths; and mass production, simple shapes and added jade The technology is very high, so it is suitable for a large number of orders. From a practical point of view, two kinds of plastics are sufficient to meet the needs. Therefore, these two types of Jiawei machinery are still widely stored. Im (PET) is based on Injection blow molding is used to make each scraper: 2. The right side is obtained by melt extrusion when processed by 雠 blow molding method. ΑⅠΪΪ 胶 下 下 魏 转 成 成 财 易, this side bets on melting and drying Strain B * —general grade PETE “produces crystals” and has self-made chemical products. If it is processed for a long time, it will not be able to produce an acceptable product. Furthermore, because extrusion-blow molding is used to stretch the stretch rate of blow molding Very lower than injection blow molding, so the impact resistance is poor. It is easy to break. As shown by the above real calendar—the general grade ρετ processed silk final products can not be processed by the compaction method. As a result of the above, many patents have proposed polyester resins suitable for extrusion processing. 1233933 is summarized as follows: 1. US-A «5,182,359, EP-A-0532943, JP-A-5-125165 / 1993 published as diacids or their derived esters and diols containing 2 to 8 carbons Similar reactions, and the addition of the ethylene oxide adduct of bisphenol A to produce copolyesters suitable for extrusion processing. 2. US-A-4, 161, 579, 4,219,527, 4,234,708 published in terephthalic acid During the reaction with ethylene glycol, trimethylol propane (Pentaerythritol) or trimellitic acid (Trimelliticacid) is added as a cross-linking agent, and Benzoic acid or Stearic acid acts as a chain blocker. The polyester thus obtained is used for extrusion blow molding. 3: US-A_4,182,84 JP_A-55_92730 / 1980 proposed to synthesize terephthalic acid and ethylene glycol into a prepolymer, and then trimethylollprpane or pentaerythritol Or trime acid (Trime leg c acid) is added to make the ester and solid phase polymerization is performed to obtain a polymer suitable for extrusion processing. 4.US + j, 554,329 published with terephthalic acid and isophthalic acid (18 ° C) and ethylene glycol. Pentaerythritol is added as a branching agent, and m-Anisic acid is added. Manufacture of copolyesters suitable for extrusion blow molding. 5: US_A-3,558,557, 4,188,357, 4,196,275 published with terephthalic acid, ethylene glycol, bisphenol A diethylene glycol ether (Bisphen〇ia digly Co ether) and a small amount of polyfunctional branching agent Copolymer vinegar suitable for extrusion processing. % 6.EP 0774 477A2 published in terephthalic acid and ethylene glycol plus 4% bifunctional alicyclic or aliphatic (called al unit, such as cyclohexane dimethanol = monoformic acid) ' Or 0.5 to 7 mole% of aromatic diols (referred to as & units, such as η-mesobacteric acid) are anti-reproductive-species co-parents. Or, — Add α5 ~ 7 mole% of bifunctional substance (referred to as 1233933 [4 (2 light ethoxy) phenyl] propionate), and I〆 contains three functional groups (referred to as b2 mono ;, Formimole: 0% ~ 0.5mol% containing at least three official materials: Junacic acid), and one or more of the methyl esters. From this, a pre-5 compound is first produced, and this compound is prepared. After grinding into a powder, add 0.1 ~ 5.0 f 1 /. Extruder of the green dicarboxylic acid 'green abender brand extruder to knead end), cut into ester particles and then carry out solid-phase polymerization reaction, so that the molecular weight of 1 〇⑽ can be Extrusion blow molding. , 8 · Zhongyi First Republic of China Invention Patent No. 307780 # A copolymerized vinegar was added to terephthalic acid and ethylene di ^ and added with 2- [4_ (2_hydroxyethoxy) phenyl] _2_ [3 ' Ethyl) _4, _ (2_hydroxy ^ yl) phenyl] propane and / or 1,4-bis (2_ethoxy) _2_ (2_ethyl) benzene triol, its content Oiq mole% of the sum of diols and triols. This table tennis polyester can also be extruded and blow molded. 'However, in the above-mentioned first method, insufficient melt viscosity will be encountered, the molten embryo body will sag severely, cannot be stably processed, and there will be a rough surface on the surface during low temperature molding. In the above-mentioned second manufacturing method, although the use of a cross-linking agent and a chain blocker can improve the viscosity of the molten state, it also results in a faster crystallization rate than the unmodified polyester, and whitening of the crystals will occur when making longer finished products. phenomenon. And the finished product made from this copolyester also has the surface roughening phenomenon caused by item 1. In the aforementioned third method, there is also a phenomenon that the crystallization rate is faster as in the second item. In the third method, additional additions such as isophthalic acid or jj ^ Qpentyl glycol inhibit the 1233333 f crystallization rate, but it still cannot improve the phenomenon of rough surface caused by gels caused by excessive cross-linking. . —In the fourth method mentioned above, 'Pentaerythritol and meta-anisic acid can be added to obtain a higher melting degree and produce less gel, and the addition of meta-phthalic acid inhibits crystallization to be more than 3G cm in length. The product will still encounter the phenomenon of rough surface and crystal whitening. The mouth is in the fifth manufacturing method described above, because its double hope a structure modifier causes an amorphous phase, and the dazzling tree increases the molecular weight, which will cause the melt viscosity that cannot reach the high level =, which will cause melting during processing and molding. Embryo body drooping severely. If the phase 1 ^^ is added with a large amount of bis_A digan, this will make the polymer react in the melting tirr, leading to poor solution, and the polymerization will turn yellow and

Shao-Guan viscosity cannot be properly controlled. K In the aforementioned 6th and 8th manufacturing methods, the copolyester did obtain a good molded article during extrusion; however, its published patent =: fat; aromatic diols or aromatic bis_, etc. Are set to less than y / 疋 ^ 3, in order to avoid encountering the polymer cut i? Fi when performing solid phase polymerization? For non-adhesion, the solid-phase reaction temperature must be reduced to cause the reaction rate i to be slow, so that the impact resistance of the molded article is partially suppressed. Especially when the shape is complex and the hollow space is 11, there is still the risk of breaking. ^ The method used by the inventors is more unfavorable. "The raw shirt is better than the 7th makeup towel mentioned above. It will prevent the copolyesters from forming a gel-like fisheye phenomenon. However, the text of the present invention can only be used to form a severe drooping phenomenon of the molten embryo. The inspection cylinder will be made in this way. Based on the introduction of the above various technologies, the hair can have the following views: Copolyester, 1233933 1. Na gift width = general purpose polymer can be at a lower temperature than When the squeezing is performed, the molten embryo will have a large phenomenon; when it is too large, it will show a stable and even vertical flow phenomenon, and there will be no unevenness. Especially when the length of the guard is longer than 3〇 公 Γ ίί For 5 pieces, 'more money is better than silk red. The rate of crystallization is very slow, _Mitj_ (Die) goes to the finished product, so it will be transparent, so the entire molded object will appear transparent and It has good grades; polyacetate tt, when the molded object is more than 30 cm in length, 'the phenomenon will be more obvious ^, χκ§θ the surface of the molded object is smooth, there is no excessive cross-linking to cause the gel mold, In fact, the machine can make I 5 iff directly from the commercialized surface blowing machine. The appearance of this bottle is smooth and highly permeable. The thickness of the bottle is evenly distributed without gel or infusible particles. The position of the bottle cap is well formed, and the seams on the left and right leaves of the bottle are formed. Good line ^; and ^ accumulation bulge phenomenon, and the bottle made in this way can pass the U meter and drop test, there will be no cracking phenomenon. Σ 7 · Real = During the test, it was found that choosing a certain structure is special Diols can reduce the amount of cross-linking agent added, and even the best effect of the present invention is to select a bis-alcohol with a special structure without adding a cross-linking agent to achieve the properties of non-Newtonian fluids. The chain-linking agent causes excessive cross-linking to cause gelation. 8. The copolymerized vinegar of the present invention can be used under vacuum, reduced pressure or inert gas (such as nitrogen) at a temperature lower than the copolymerization point. _ 杂 血 灭 viscosity (referred to as IV). [Overview of the Invention] 1233933 To achieve the above purpose, this Mao Ming arranged a series of studies on diacid and ethylene glycol composed of diacid or its ester-forming derivative. Reaction ^ ^ less = branch For example, trimellitic acid or anhydride. It is possible to enter both sides of the iff special structure, but it is within the scope of the addition of flammable fiber for energy production and post-processability and cost considerations. There is no serious problem of sagging of the embryo when molding. Because of the mold molding ability and the thickness distribution of the embryo body is uniform. Up to now, some special structures are selected, even if the above is not added. The purpose of the branch material and tincture is to make the copolymerized vinegar achieve non-Newtonian fluid special acoustic yarn, ΓΪ2ίΙ5 low viscosity characteristics, and high viscosity at low shear rate to achieve the above effect. Here mentioned to avoid the embryo body sagging The phenomenon must be emphasized in the process of adding, the copolymerized vinegar of the present invention can be suitable for the production of embryos. There will be no serious impurities leading to uneven thickness. Although adding a branching agent can improve the melting of the embryos. Strength, but when added in an excessive amount, the gel phenomenon will appear as a fish-eye shape on the molded object. 0: Velvet: the technology is to reduce the occurrence of gel phenomenon. It is usually added with a single shellfish as a chain. Paved, but the present invention In the test county, monofunctional A: = ί: ρ system effect, but the polymerization rate will also be partially inhibited. When making ^ _ degrees, often the color will be yellow, so the present invention does not emphasize the addition of monofunctional groups substance. The purpose of adding bis-ols is to make the molded objects have superior mechanical properties and impact resistance; and the special structure of bis-ols can not only give good results, but also can inhibit the crystallization rate. The body will not be more likely to encounter embryo whitening when manufacturing objects longer than 3G cm. According to the present invention, the invention can be suitable for producing objects with embryo body length of 30 days, and no embryo whitening phenomenon will occur. In addition, this month's choice of double _ addition of silk into the g g 'will cause a decrease in impurities; in this way, the melt viscosity of 11 1233933 decreases, so the melt extrusion to take into account the solution resistance, crystallization rate inhibition silk, In order to avoid excessive reduction in melt viscosity and take into account manufacturing costs, the ^ _ alcohols and the appropriate addition amount of the co-exit additions produced, the invention of the co-hybrid system _-known hybrid production equipment and production clothing = pre-polymerization This type of production process includes a continuous process using terephthalic acid or dimethyl acetate as the starting reactant. _: Under production method: = solid phase polymerization of the compound to increase the inherent viscosity of the copolymer. ===, 0.8 ~ 1.4dl / g ·, the production method of solid phase polymerization used in this invention is based on tank 7) heating S granules in a rotary tank and carrying out under vacuum environment, the other is-9 ^ 'Type, after the vinegar particles undergo crystallization and drying', then pass inert gas into the polymerization tank) to increase polymer reduction. From the above description, the present invention proposes a kind of silk g |, which includes performing ester conversion or transesterification: (^) · a diphosphonic acid component consisting essentially of terephthalic acid or an ester-forming derivative thereof, (2) Diol units consisting essentially of ethylene glycol; additional additions: (3) At least one substance selected from the group: (a) 2-ethyl_2-butyl-1,3- Propylene glycol (Butyl-2_Ethyl_1, 3_PrOpanediol, hereinafter referred to as BEPG), its chemical formula is CH2CH3

HO-CH2-C-CHrOH CH2CH2CH2CH3 12 (1) 1233933 (b) 3-Methyl-l, 5-pentanediol (3-Methyl-l, 5_Pentanedio abbreviated as mpg), its chemical formula is as follows: CHs

I OH-CH2-CH2-CH-CH2-CH2-OH (2) (c) 2,4-Diethyl-1,5-pentanediol (2,4-Diethyl-1,5-Pentanediol, hereinafter referred to as DPG) , Its chemical formula is as follows: C2H5 C2H5

II OH-CH2-CH-CH2-CH-CH2-OH (3) (d) l-hydroxy-2,2-fluorenyl-propyl-hydroxytrimethylethylacetate (Hydroxypivalyl Hydroxypivalate, hereinafter referred to as HPHP), Its chemical formula is as follows: CHi CHs

I I 〇H-CHrC-CO-0_CH2-C_a ^ _〇H _ _

II CHs CHs Its weight is based on the weight of all copolyesters and is 15 to 15% by weight; when manufacturing this copolyester, or add another (4 translation less than one substance selected from the following group as cross-linking Agent: 13 1233933 Trimellitic acid

COOH

〇

COOH (b) Trimellitic anydride

〇

II 〇 〇 6 COOH μ (c) Trimethylol propane

HOH2C-CH2-CH.CH2-CH2OH

I

CH20H The weight is based on the weight of all copolyesters and is 0 to 10 mol%; when the weight is greater than 0.25 mol% based on the weight of all copolyesters, the molded articles of copolyesters will have a significant reduction Gummy phenomenon, the present invention moderately adds Benzoic acid, which ranges from 0 to 1.0 mole% based on the total copolyester. However, it must be emphasized that the optimal combination of ingredients of the copolyester of the present invention does not require the addition of a monofunctional substance to avoid slowing down the melt polymerization rate 14 1233933 and thus cause deterioration of color and other physical properties. The prepolymer is intended; this polymer is then subjected to melt polycondensation polymerization to form a polyester prepolymer for solid phase polymerization. [Detailed description of preferred specific examples] The preferred copolyesters of the present invention basically include the essence

=; =) Added to any of-(2) in formula (4)-or any two or more: the copolyester of the present invention must include at least one member selected from the group consisting of 3 =; 70% mixture of shellfish, the content of which is based on the weight of the copolymerized vinegar, which is @ 15 weight. The content of this unit is less than 1% by weight. . In addition, the melting point of the obtained copolyester will be too high, and it will increase during the extrusion 2 die. And the embryo body obtained by melt extrusion is extremely easy to produce.

Mind $ now ‘especially when manufacturing molded objects with a length of more than 2G cm. Furthermore, 'the molded article obtained therefrom has poor impact resistance, which is different from that of the air and space department', and it is dropped from a high place to the ground, causing a cracking phenomenon. If the content of lir70 is higher than 15% by weight, the melting point of the prepolymer of the copolyester will decrease by more than 11 to make the tetramer into an amorphous state. As a result, subsequent solid-phase polymerization will occur. As a result, the polymerization reaction cannot be stabilized, and it is difficult to improve the inherent viscosity of the prepolymer, which results in good molding during extrusion processing. Decathlon's copolyester includes substances selected from formula (1) to formula (4), the content of which is particularly higher than the weight of silk ester, which can make pre-hybridization _ polymerization will not easily adhere to each other, so as to ensure the solid phase High polymerization yields 15 1233933 viscosity products. And the _ point decreases moderately, which can promote the solid-phase polymerization rate of the prepolymer. The copolymer with high inherent viscosity obtained in ΤτΜ ^: Shiyi Range: " ΐίΓί ° ° ^ ϊϊ ϊϊίίίϋ The surface-shaped objects in this place have good mechanical properties, especially good county resistance. The hair _ Cong Yulin Silk ^ Sheng Bayou-body shaped handle fortune container ’from a height of more than 1 meter; the ground will not crack. Sugello to squeeze production machines from different brands seems to have higher requirements for the strength of the silk of the dissolved polymer. In addition, in the case of larger molded articles, some solvents need to be dissolved, and this material unit is also considered to be added. In the above special circumstances, the content of ίίΓΓ unit is based on the number of moles in the copolymer s, which is ⑽sii.o If the content of this unit is less than 0.05 mole%, the total amount of mold embryos extruded during molding will be The phenomenon of excessive sagging is especially encountered in the production of molded objects over 20 cm. "At the length of ^ m which is 0.25 mol%, the resulting copolyester will produce an excessively large two-t configuration image, so that both the preform and the surface formed during the molding process are extruded. Dilute particles can damage the appearance of the molded object. This ^ see ΐϊ 早 2 contains ΐ, but it is more obvious. In order to solve this phenomenon, the present invention also mentions a monofunctional substance with a small content, such as the addition of benzoic acid (Benzoicacid), Straight = monofunctional group with the same thing, and _ polymerization rate, = cause the physical properties and color reduction of the copolyester, etc .. The present invention is applicable to some cases where special requirements for melting strength, And not 16 1233933 Ξΐίΐ 交 f 'will take to add less than B mole% selected from formula (5) to formula ⑺-guan 4 base τ, and to emphasize again the use of Timton fluid in the present invention :; raw. Without adding a branching agent, a total of non-taurinyl monomers can also be achieved! If necessary, in addition to the above-mentioned terephthalic diphenyl unit, ethylene di: (the above formula (5) to cut) units, can also contain Based on the overall structure-methyl-HVT, h, other bifunctional compounds below 10 mole%; for example, m-phenylene-1 & 〇1 ^ 1111 (^ (^) Naphthalene dicarboxylic acid, glycol and cyclohexanedimethanol and the like.

佶 Intrinsic viscosity (1_ is also referred to as IV), which has different viscosity requirements depending on the type and type of molding equipment used. When extrusion blow molding is performed, it is 0.8 to L4dl / g. In terms of strength and appearance, the molded article is more preferably 0.9 to Udl / g. If the inherent viscosity of the copolyester is less than • g ', the melted embryo formed during compression molding is significantly sagging, which leads to further' if the intrinsic viscosity of the copolyester is greater than 1.4di / g, extrusion Compression blow molding of Sunichi Temple, the melt viscosity will be too large, the production and processing of the county will reduce the production efficiency of Guangya and cause obvious thermal crystallization, which will reduce the transparency. On the other hand, due to the excessively high inherent viscosity, the seam lines of the left and right two-leaf molds at the bottom of the blow-molded article will also be melted and affect the appearance of the article. Poorly formed and the resulting molded article has low mechanical strength.

The co-I ester of this Maoming 'has a glass transition temperature (Tias) of more than 70 ° C, so it can avoid the residual stress due to the residual stress after the molded article is removed from the mold during blow molding. Relaxation causes shrinkage and affects the appearance of the object. After the intrinsic viscosity of the copolyester of the present invention is increased by solid phase polymerization, the terminal carbonyl group (^ out (^ 1 Qiu (1§1 * 0111)) content is less than 30 microequivalents per gram (// is called 11 ^ 1 Coffee / magic, preferably less than 20 // equivaient / g, so as to avoid melting deterioration, yellowing of the color and the appearance of rough surface. The copolyester of the present invention, after solid phase polymerization to increase the inherent viscosity, Polyester 17 1233933 ^ The column crystal density analysis method is in the approximate range; if the crystallinity is lower than 2J, the skin is easy to stick to each other, which is not conducive to the solid-phase polymerization, and it will not be easy in the future. Drying. If the crystallinity is higher than 40/0, the ester particles are not easy to dissolve. During the pressing process, the extrusion machine has a problem of excessive load. In addition, some extrusion equipment will be found to have no effect. Appearance of the object. The crystallinity of the water on this day of the present invention is most preferably between 25 and μ%. 乂, copolymerization s purpose 'After solid phase polymerization to increase the inherent viscosity, scan with a slight difference; 225C to 240C, Its cold crystallization temperature is below 150 ° C, and even no peak of crystallization temperature appears.

The copolyester described in this article is based on the production stability, mold physical properties, mechanical strength, and productivity in extrusion blow molding, and its melting flow index is higher than the copolymerization turning point A / plate. (Melt £ 10 wrate, MFr for short) is 10 to 10 g / 10min ', more preferably 2.0 to 70 g / 10min. The manufacturing method of the copolyester of the present invention is as follows: (1) Put the following substances in the reactor and perform the esterification reaction; (a) terephthalic acid or its derivative (b) ethylene glycol (c ) At least one substance selected from the formulae ⑴ to ⑷, or (d) —a substance selected from the formulas (5) to (7),

Or (e) benzoic acid • where (ethylene glycol): (terephthalic acid) has an initial molar ratio of between 1.6 and 1.6; (c) the initial quantitative content of the substance is based on the copolyester Weight is between weight; (d) the initial metered content of the substance based on the copolyester is between 0 and 10 moles / 0 '(e) the initial metered content of the substance is based on the copolyester The molar number is between 0 and 200. The temperature of the esterification reaction is between 220 and 260 ° C, and the esterification pressure is between normal pressure and t0kg / Cm2. During the process, the water and alcohols produced must be distilled off. When the esterification reaction proceeds to a conversion rate of 95 to 98%, the esterification reaction is terminated and the pre-polymerization reaction is completed. 18 1233933 ΐ Section ^ f ends S purpose_add catalyst, the judgment of this copolymerization can use acetic acid As the catalyst, the two-chain, oxidized or a mixture of the above is used as the catalyst. It is also necessary to add ϋϊLtJ ‘Linosinic acid’ Trimethylphosphonic acid vinegar ’Triphenylphosphonic acid, triethyl clay, etc., and then add coloring agents, such as cobalt acetate. For 2 'to carry out the ageing reaction: the raw material combination reaction in Liuxian County is reversed, and the polycondensation reaction is performed in the degree of Tiguo to o ^ ol / vacuum I, f'. The inherent viscosity of the polymer is sliced (Chip). g Polymer is unloaded into cold, water and cut into circular kappa reaction: the polyester obtained through the riding reaction is cut to 24 = viscosity when broken, the viscosity is square, and it is dried, crystallized and polymerized. Good to use the roller ί man's soil τ. The solid phase copolymerization of the present invention is less blown and more conservative, == JL > The purpose of the copolymerization of the present invention can be produced in a short time and high yield by the aforementioned method. Injection can be performed by extrusion blow molding, sssss凾 Shape, different volume II: "Shot === Causes a variety of different good production of fine hybrid FFU The object obtained by this hybrid process can be good 19 1233933 Polyacetate low 2G to 3G ° C 'No melting will not occur. The purpose of the present invention is especially suitable for manufacturing hollow containers by melt extrusion blow molding. When processed in this way, the purpose of the copolymerization of the present invention is to exhibit stable and appropriate droop characteristics, so the droop time is maintained within a suitable range. And the preform has a uniform diameter. In addition, good dimensional accuracy, high transparency, and smooth surface are not produced in this place. 'Cereals or gels, good heat resistance and high impact resistance, especially when manufacturing long sound capacity 11 Shi 'will not encounter the phenomenon of crystal bleaching as in the same level. In particular, the present invention must emphasize that this copolyester USΐ has a volume of 2 liters with a length of more than 3G centimeters, and is directly processed by a blow-molded center line device. Inspection, no cracking will occur. When correcting == 's off secret melting machine, the test pressure performance and temperature are set to (fine miscellaneous duties) to (copolymers such as cocoa = what shape' there is no special miscellaneous system, for example or more ==== == layer fine (known as the coexistence of materials), vinegar can also be mixed with conventional additives such as dyes and vinegar as required, t 仃, the conventional resin of 4 and the copolymerization of the present invention [Example] was 6 卩Proof, but it must be stated that in the following example n and the comparative example, 1-poly rt C is indecently used to make this invention. The following examples show the physical and chemical properties of 2 homopoly vinegar) and 20 1233933 Ubelohde viscosity meter ( (Made in Taiwan) Measured at 25 ° C with a weight-to-weight ratio of 3: 2 in tetrachloroethane. (2) Melt flow rate (MFR) of polyester: measured by melt index (Toyo Seiki (Manufactured). The measurement method is based on the method of ASTM D1238. The polyester to be measured is first placed in a vacuum oven at i50 ° C for 4 hours. It is then melted at 270 C and extruded with a diameter of 2.1 under a load of 2160 grams. mm die mouth, measure its outflow rate (g / 10min). (3) Carboxyl end group content of polyester: Weigh 0.5 to 0.6 grams of polyester 50cc of solid benzene, heated to 180 ° C to dissolve, cooled to 80 ° C, added 20cc of isopropanol / water solution (weight ratio 9: 1), titrated with 0.01N KOH; calculated # eqUivaient / g of acid 9 (4) Glass transition temperature (Tg) and melting temperature (Tm) of polyester: Analysis is performed using Differential Scanning Calimetrics (model DSC-7 manufactured by Perkin-Elmer). The granules were first dried at 80 ° C for 2 hours under vacuum, then melted at 300 ° C and then cooled rapidly, and then analyzed for thermal properties at a heating rate of 20 ° C / min. (5) Cold crystallization temperature of polyester ( tcc): Same as the analysis equipment of item (4), after melting the ester granules at 28 ° C, the thermal properties are analyzed at a temperature drop rate of 10 ° C / min. Measurement of aa degree 1: Tetrachloride After carbon (ecu) and n-heptane are prepared into a solution, they are 'infused into a density gradient tube column, and the ester particles (final product) are placed in the column, and the density is converted from the position where the luster particles stay. Then calculate the crystallinity according to the following formula: X c (%) = {dc (d-da) / d (dc-da)} xl00 da represents the density of the completely amorphous polyester, and its value is 1 335; it also represents Fully crystallized Density, its value is 1.501 (7) Rheological analysis: Analysis by capillary rheometer (brand: Gottfert); polyester granules were first dried under vacuum at 150 C for 4 hours, and then rheometer It is melted at 27 °, and if it is a first-grade polyester, it is (melting point + 4 °). 〇 Melting, analyzing the dependence of melt viscosity on shear rate 21 1233933 (9) 2 Drop resistance analysis of empty molded objects: hollow containers made by extrusion blow molding, placed at ^ temperature for 24 hours, filled with water and The mouth of the bottle is sealed, and then vertically lowered from a height of 1.2 meters to the concrete floor, so that the bottom is in contact with the floor. The above test was repeated 5 times with the same bottle, and the results obtained were evaluated according to the criteria listed in Table 1 below. (10) Analysis of gel phenomenon on the surface of hollow molded objects: hollow volume state produced by extrusion blow molding, and the number of fish-eye particles in the gel was calculated from the area of 10cmx10cm of the bottle body. The results are shown in Table 2 below. Column Criteria Evaluation. 'Table 1 Evaluation criteria for impact resistance of the bottle ◎ (Excellent): No crack or crack after passing three or more tests 0 (Good): No crack or crack in the first and second tests, but found in the third test Crack or crack △ (minimum): No crack or crack in the first test, but crack or crack found in the second test X (bad): Crack or crack occurred in the first test

Table 2 Evaluation criteria of the gel phenomenon of the bottle ◎ (Excellent): 1 or less appears in the area of 10cmx10cm (Good): 3 or less appears in the area of 10cmx10cm △ (minimum): Within the area of 10cmx10cm Less than 5 X (bad): more than 5 within the area of 10cmx10cm 22 1233933 (π) Transparency evaluation of hollow molded objects: The evaluation of transparency is directly judged by the naked eye, as shown in Table 3 below as standard Table 3 ◎ (Excellent) ·· Directly to the naked eye, with a high degree of transparency and gloss level 0 (Common): Directly to the naked eye, with transparency but weak gloss △ (Table low limit): Directly to the naked eye, with transparency but poor gloss X (bad ): The bottle is opaque or partially crystallized. (12) Evaluation of the thickness distribution of the bottle body: Use the Thickness Analysis Effect Digital Thickness Gage manufactured by American company PANAMETRIC to analyze the thickness of the upper and lower positions of the bottle body. The thickness difference is used as the standard for evaluating the body thickness of the bottle, and the standards are listed in Table 4: Sub-Table 4 ◎ (Excellent): The difference between the upper and lower thickness is less than 0.1mm 〇 (Normal): The difference between the upper and lower thickness is 0.1 to 0.2mm △ (lowest Limit): 0.2 to 0.25mm difference in upper and lower thickness X (Bad): Thickness difference between upper and lower than greater than 0.25mm mm mm mm mm mm mam mm mm mm mm " " Coffee — turn to sleep — — — — — miscellaneous — — — — — — — — — — — — — Look at the sun_Painting the surface of the face and the meaning of the sun (Example 1) (1) Take 100 parts by weight of terephthalic acid and 57.48 parts by weight of ethylene glycol And 7.29 parts by weight of 2-ethyl-2-butyl-1,3-propanediol (BEPG, formula IX) to prepare a slurry. To the slurry, add 0.04 parts by weight of antimony acetate, 0.01 parts of acetic acid, and 0.01 23 1233933 parts of filling acid. The mash was heated to 26 ° C under an absolute pressure dish until the conversion rate of vinegar reached 95% or more; vacuum was then applied to make the reaction below hnmHg 'and the reaction temperature was 270. ^ The first stage of the polycondensation inverse library is then: the second stage of the polycondensation inverse u is performed under a higher vacuum and temperature, and the prepolymer is cut into a cylindrical shape. In order to fix the polymerization time and make the intrinsic viscosity of the pre-bins as low as possible within the range of 0.6 to 0 63 (! 1 / §. The pre-polymer chips obtained above are first lower than ⑽. Dry crystallization at a temperature of C for 6 hours, and then continue to polymerize at 215 ° C under a vacuum of ijmmHg for 40 hours to produce the final copolyester / · day, to j2) Polyester's analysis of the fine g rate 'Tg, Tm' TCC 'acid value and crystallinity. The design content of the bottle is dove milliliters, and the results can be evaluated by the methods described above, and each quality item can be evaluated (Example 2) to increase Γ%. The results are shown in Table 6. The previous analysis results of the obtained views are listed in Table 10. The various effects are mixed, and the various qualities (Examples 3 to 5) are high, and its melt strength: the obtained content of trimellitic anhydride is shown in Table 6 in terms of analysis results. Therefore, it is the analysis method in Example 1; the evaluation results of the various qualitative items are listed in Table 10. The effect was evaluated separately, and each product (Examples 6 and 7) was partially trimellitic anhydride with a different content of benzene and benzene, and the analysis method in Example 1 · Yuba Y 彳 gel phenomenon was added. The obtained copolyester was repeatedly tested. The results of the combined analysis are shown in Table 7. The obtained bottle was evaluated for its effect by the aforementioned 1233933 method, and the evaluation results of various quality items are listed in Table ι〇. (Examples 8 and 9) Example 1 was repeated except that a part of the content of trisylpropane was added, and Example 9 was further added with a content of phenylarsinic acid to suppress gelation. The obtained Qiu 1 analysis method in Example 1; each analysis result is shown in Table 7. All the results were evaluated by the method described below, and the evaluation results of each quality item were listed in (Examples 10 and 11). Example 1 was repeated, but substituted with 3-fluorenyl-L5-pentanediol. 2_methyl_2_butyl_13 diol; Example 11 additionally added a part of the content of trimellitic anhydride. The obtained analysis method was repeated in Example 1; the results of each analysis are listed in Tables 7 and 8 / the obtained bottles were evaluated for their effects by the aforementioned methods', and the evaluation results of each item f are shown in Tables 10 and 11. (Examples 12 and 13) Example 1 was repeated except that the aforementioned bis-alcohol modifier was replaced with 2,4-dimethyl'5-red alcohol; Example 13 also added a portion of trimellitic anhydride. The obtained copolyester was repeated for the analysis method in Example 1; the results of each analysis are shown in Table 8. The bottles were evaluated for their effects by the aforementioned methods, and the evaluation results of various quality items were listed in. (Example 14) Example 1 was repeated, except that the aforementioned bis-alcohol modifier was replaced by 1-woven-2,21-propyl-propyl trimethylacetate; the obtained copolyester was repeated as described in Example 1. The analysis methods in 丨 the various analyses and results are listed in Table 8. The obtained bottles were evaluated for their effects by the aforementioned method, and the evaluation results of various quality items are listed in Table 10.比较 (Comparative Example 1) The reaction of truthfulness 1 was carried out with 97 wt% of acryl monoacetic acid, 3 parts by weight of phthalic acid, and 57 48 parts by weight of ethylene glycol, but the conditions listed in _Polymer Silk 9 Attack. The results of each analysis are listed in Table 8. The obtained bottle was evaluated for its effect by the aforementioned method 'and the evaluation results of various quality items are listed in the table. (Comparative Example 2) A reaction of 100% by weight of p-phenylenedicarboxylic acid and 57.48 parts by weight of ethylene glycol was carried out as compared with 25 1233933 W, but a part of triphenylene was further added. The results of each analysis are listed in Table 8. The obtained # has the same melting strength as the United States, and each H item is filamentary in the table ω. Fortune Green evaluated its effects, (Comparative Examples 3 and 4) The effects were evaluated with 97 parts by weight of terephthalic acid and 3 parts by weight =

With 100 parts by weight of terephthalic acid and 57 48 of the reaction of Example 1, plus a partial content of acetic acid, such as the comparison of benzoic acid with # 微 减 Ϊ 目 # 4 The evaluation results of each H item are shown in Example 1 = L0l reset * parts, and the comparison of the didicarboxylic acid and 57.48 parts by weight of ethylene glycol as shown in the comparison column =? 1 plus an amount of M · cyclohexane dimethanol. Each analysis result The evaluation results are listed in the foregoing methods to evaluate its effect, and each quality item is shown in Table 5 on the compound codes used in the above-mentioned examples and comparative examples.

26 1233933 Table 5 BA BEPG 2-ethyl-2-butyl-1,3-propanediol 1,4-CHDM 1,4-cyclohexanedimethanol EG ethylene glycol HPHP 1 -hydroxy-2,2 -Fluorenyl-propyl-hydroxytrimethylethylacetate MPG 3-fluorenyl-1,5-pentanediol

PDG 2,4-Difluorenyl-1,5-pentanediol PTA Pure terephthalic acid TMA Trimellitic anhydride TMP Hydroxytrimethylpropane

27 1233933 Table 6 Example unit Example 1 Example 2 Example 3 Example 4 Example 5 Starting component dicarboxylic acid unit by weight PTA 100 PTA 100 PTA 100 PTA 100 PTA 100 Ethylene glycol by weight EG 57.48 EG 57.48 EG 57.48 EG 57.48 EG 57.48 is selected from formula (4) to (4) unit component weight parts (wt%) BEPG 7.29 (6%) BEPG 7.29 (6%) BEPG 7.29 (6%) BEPG 7.29 (6%) BEPG 7.29 ( 6%) selected from formula (5) to formula (7) unit component parts by weight (mole%) 0 0 TMA 0.0363 (0.03%) TMA 0.0729 (0.06%) TMA 0.145 (0.13%) monofunctional substance component parts by weight (Mole%) 0 0 0 0 0 Intrinsic viscosity of prepolymer dl / g 0.615 0.610 0.611 0.623 0.628 Vacuum of solid phase polymerization / temperature / time torr ° c / hr 1.5torr 215〇C / 40hr 1.5torr 215〇C / 50hr 1.5torr 215 ° C / 50hr 1.5 torr 215〇C / 50hr 1.5torr 215〇C / 50hr Polyester inherent viscosity dl / g 0.95 1.10 1.15 1.28 1.25 Polyester DEG content mol% 2.11 2.24 2.30 2.47 2.35 Polyester MFR g / 10min 8.8 5.5 5.3 7.1 3.17 polyester Tg ° C 75.6 76.0 74.5 74.8 74.1 polyester Tm ° C 230 230 230 230 230 polyester Tcc C No No No No No acid polyester valence β 15 11 13 9 11 Polyester crystallinity equ / g.% 25% 28% 29% 32% 29%

28 1233933

Table 7 --- --- Ί Example unit Example 6 Example 7 Example 8 Example 9 Example 10 Starting weight part of dicarboxylic acid unit PTA PTA PTA PTA PTA Starting 100 100 100 100 100 Ethylene glycol weight Parts EG EG EG EG EG Parts 57.48 57.48 57.48 57.48 57.48 selected from formula (1) to ingredients BEPG BEPG BEPG BEPG MPG formula (4) unit weight parts 7.29 7.29 7.29 7.29 7.29 (% by weight) (6%) (6%) (6%) ( 6%) (6%) (6%) selected from formula (5) to ingredients TMA TMA TMP TMP formula (7) parts by weight 0.289 0.289 0.180 0.180 0-(mole%) (0.25%) (0.25%) single Functional group composition BA BA BA Substance by weight 0.184 0.368 0 0.284 0 — (mole%) (0.25%) (0.50%) Intrinsic viscosity of prepolymer dl / g 0.635 0.590 0.610 0.612 0.595 Vacuum of solid phase polymerization / torr 1.5torr2 1.5torr2 1.5torr2 1.5torr2 1.5torr2 Temperature / ° G / 15 ° C 15 ° C 15 ° C 15 ° C 15 ° C Time hr / 50h / 50h / 50h / 50h / 50h Polyester inherent viscosity dl / g 1.38 1.07 1.00 0.98 1.05 Polyester DEG content mol% 2.51 2.40 2.37 2.41 2.35 Polyester MFR g / l0min 1.6 2.0 7.0 7.5 10.0 Polyester Tg ° C 73.8 73.6 73.9 74.0 72.0 Polyester Tm ° C '230 230 230 230 235 Polyester purpose Tcc ° C None None None None 150 Polyester acid value β equ / g 8 13 16 15 11 Polyester purpose crystallinity% 34 % 32% 31% 29% 43% 29 1233933 Table 8 Example unit Example 11 Example 12 Example 13 Example 14 Part by weight of diweilic acid unit PTA PTA PTA PTA 100 100 100 100 parts by weight of ethylene glycol EG EG EG EG parts 57.48 57.48 57.48 57.48 selected from formula (i) to ingredients MPG PDG PDG HPHP formula (4) unit by weight 7.29 7.29 7.29 7.29 (% by weight) (6%) (6%) (6%) (6%) Selected from formula (5) to component TMA TMA formula (7) unit weight part 0.0729 0 0.0729 0 (mol%) (0.06%) (0.06%) monofunctional component substance part by weight 0 0 0 0 (mol%) prepolymerization Intrinsic viscosity dl / g 0.605 0.601 0.612 0.592 Vacuum of solid phase polymerization / torr 1.5torr 1.5torr 1.5torr2 1.5torr2 Temperature / ° c / 215〇C 215〇C 15 ° C 15 ° C Time hr / 50hr / 50h / 50h / 50h Polyester inherent viscosity dl / g 1.10 1.09 1.12 1.06 Polyester DEG content mol% 2.40 2.43 2.45 2.21 Polyester MFR g / lOmin 4.8 10.5 5.8 9.5 Polyester Tg ° C 72.0 72.5 72.5 70.2 Polyester Tm ° C 235 233 233 225 Polyester Tcc ° C 150 145 145 Polyester-free acid number β equ / g 13 13 12 15 Poly Purpose Crystallinity% 41% 38% 35% 20% 1233933 Table 9 Example Unit Comparative Example Comparative Example Comparative Example Comparative Example Comparative Example 1 2 3 4 5 6 Dicarboxylic acid unit component PTA / DP PTA PTA / IPA PTA / IPA PTA PTA Initial weight part A 100 97/3 97/3 100 100 to 97/3 parts Ethylene glycol component EG EG EG EG EG EG 57.48 57.48 57.48 57.48 57.48 57.48 57.48 Special diol component CHDM modifier 0 0 0 0 0 4.34 (wt%) (3.75%) by weight TMA TMA TMA TMA TMA TMA 0 0.289 0.289 0.145 0.289 0 (mole%) (0.25%) (0.25%) (0.125%) ) (0.25%) Monofunctional component BA Substance by weight 0 0 0 0 0.184 0 (mole%) (0.25%) Prepolymer inherent viscosity dl / g 0.635 0.620 0.631 0.620 0.625 0.640 Solid-state polymerization vacuum / torr 1.5 torr 1.5torr 1.5 torr 1.5torr 1.5torr 1.5torr Temperature / ° c / 225 ° C / 225 ° C / 225 ° C / 225 ° C / 225 ° C / 215 ° C / Time hr 40hr 50hr 50h 50hr 50hr 50hr 50hr Polyester inherent viscosity dl / g 1.09 1.21 1.386 1.10 0.95 1.05 Polyester DEG content mol% 2.5 2.47 2.45 2.52 2.44 2.1 Polyester MFR g / lOmin 11 * 1.6 * 3.8 * 5.6 * 10.1 * 13.1 * Polyester Tg ° C 78.0 76.5 75.3 75.0 76.2 82 Polyvinyl Tm ° C 242 242 240 240 241 237 Polyester purpose Tcc ° c 170 172 178 175 170 Polyester-free acid value β equ / g 15 9 9 14 13 15 Polyester purpose crystallinity% 55% 55% 55% 55% 55% 40% Remarks: * : Melt test at 280 ° C

31 1233933 Table ίο Example / Comparative Example Results of Melt Extrusion Blow Molding Preform Bottle Drop Tendency Bottle Thickness Distribution Bottle Transparency Bottle Seam Case Bottle Gel Phenomenon Bottle Impact Impact Example 1 Juda ○ Good ◎ ◎ Implementation Example 2 Appropriate ◎ Good ◎ Example 3 Appropriate ◎ Good ◎ ◎ Example 4 Appropriate ◎ Good ◎ Example 5 Appropriate ◎ Good 〇 Example 6 is too small ◎ Seam slightly convex X △ Example 7 Too small ◎ Seam slightly convex Δ Δ Example 8 Appropriate ◎ Good X Δ Example 9 Appropriate ◎ Good X Δ Example 10 Great work ◎ Good ◎ ◎ Example 11 Appropriate ◎ ◎ Good 〇 Example 12 Slightly Large ◎ Excellent ◎ Example 13 is appropriate ◎ ◎ Good △ Example 14 is appropriate ○ Good ◎ ◎ Comparative Example 1 is too large XX is good ◎ X Comparative Example 2 is too small ◎ X seam slightly convex XX Comparative Example 3 is too small ◎ X joint Seam slightly convex XX Comparative Example 4 Appropriate ◎ X Good Δ X Comparative Example 5 Weighed Large XX Good XX Too Large X than Car Delivery Example 6 ◎ Good ◎ ◎

32 1233933 From the results in Tables 6 to 10, 2-ethyl-2-butyl-1,3-propanediol was added in Examples 1 to 9, and 3-methyl-1,5-pentane was added in Examples 10 and 11. Alcohol, Example 12 and 13 added 2, wood diethyl-1, 5-pentanediol, Example 14 added 1-hydroxy-2,2-dimethyl-propyl-hydroxytrimethylacetic acid, Its application is within the scope of the present invention, and it has a good molding effect; in particular, Examples 1 to 5, Examples 10 to 12, and Example 14 show superior processing effects and good properties of molded objects. . However, in Examples 6 and 7, an excessively high cross-linking effect caused excessive melt strength, resulting in a raised phenomenon in the finished seam line, and a gel phenomenon was noticeable. Examples 8 and 9 produced obvious gelation phenomenon, showing that the cross-linking effect was still too high. On the other hand, comparing 1 to 5, only one to 5 'was used to cover only ordinary PET with spotted ulcers. ^

33

Claims (2)

Scope of patent application: 1. A copolyester suitable for extrusion processing, which is composed of: (1) a bisphosphonic acid component composed of terephthalic acid or a derivative of the ester formed, or another addition Partial content of phthalic acid or naphthalenedicarboxylic acid; mixed with (2) diol units composed of ethylene glycol; characterized in that: (3) at least one selected from the following group is added as a cross The content of the crosslinking agent ranges from 1 to 15% by weight based on the weight of the copolymer. (A) 2-ethylbutyl-i, 3-propanediol (BEPG), the chemical formula (1) of which is as follows: CHr ~ C-CHrOH (〇I CH2CH2CH2CH3 (b) 3-Amidino ~ 1,5-pentanediol (MPG), whose chemical formula (2) is as follows: CHa CHrCHrCH-CHr ~ CHr ~ OH (2) (c) 2,4-diethyl— 丨, 5-pentanediol (dpg), whose chemical formula (3) is as follows: 34 1233933 C2H5 C2H5 II HO-CH2-CH-CH2-CH-CH2-OH (3) (1-hydroxy-2,2-difluorenyl) -Propyl-hydroxytrimethylacetamidate (position), its chemical formula (4) is as follows: CHs CHa II HO-CH2-C-CO-O-CH2-C-CH2-OH (4) II CHa CHs or (4) At least one selected from the following group is added as a cross-linking agent, and its content range is based on the molar number of the copolyester less than 1.0 mole%: 35 1233933 (a) trimellitic acid (chemical formula ( 5)) (b) Trimellitic anhydride (chemical formula (6)) 0 # (c) Tris (hydroxypropyl) propane (chemical formula (7)) HOH2C-CH2-CH-CH2-CH2OH (7) I CH2〇H 36 1233933 or additional fluorene content range based on the molar number of copolymerized vinegar is less than 10 mole% benzoic acid. 2. According to the application of the suitable extrusion processing in Zhunawei, where ⑶ & one or more mixtures of the group consisting of formula (1) to formula (4), the content range is 1 to 10% by weight based on the weight of the copolymerized vinegar. 3. Taxpayer: Declares that the copolymerized vinegar suitable for extrusion processing according to the patent No. ㈣, wherein the ⑷ is one or more of the cross-linking agents in the group consisting of chemical formula (5) to formula ，, and the content range Based on the copolyester mole number from 0 to 0.25 mole%. 4. For the copolyester suitable for extrusion processing according to the scope of the patent application (1), m-phenylene or naphthalene is added, which contains less than 10 mol% of Molar number recorded in the purpose of silk order. 5. If the application scope of the patent application item i is suitable for extrusion processing, the inherent viscosity of the copolymerized vinegar is 0.8 ~ 1.4. 6 ·-It is difficult to make molded objects, and Yu hate special item 1 is suitable for extrusion processing of copolymerized vinegar. 7 ·-A kind of hollow object for extrusion blow molding is manufactured by processing according to the oldest purpose of copolymerization in extrusion processing, which is applicable to extrusion processing. 37 Ming Patent Specification ———— (The format, order and bold text of this specification, please do not change it arbitrarily, ※ please do not fill in the mark part) ※ Application number: ※ Application date: Correction # 2 Classification: 1. Name of the invention: (Chinese / English) Co-polyester 适用 for applicants for extrusion processing. Applicant ... (One person) Name or name: (Chinese / English) NAN YA PLASTICS CORPORATION Representative: (Chinese / English) English) Wang Yongqing / Y_c. WANG Address of residence or business office: (Chinese / English) 201, 201 Dunhua North Road, 105, Taipei 201. Tung Hwa N. Rd Taipei Taiwan. Nationality: (Chinese / English) Republic of China ginseng, inventor ·· (One in total) Name: (Chinese / English) Jian Yuechun ZO-CHUNJEN. Address of Residence: (Chinese / English) No. 201, Dunhua North Road, 105 Taipei 201. Tung Hwa N. Rd Taipei Taiwan. Nationality: (Chinese / English) Republic of China 1