TW200827382A - Amorphous copolyester and use thereof - Google Patents

Abstract

A amorphous copolyester is provided and synthesized by utilizing a diacid monomer and diol monomers. The amorphous copolyester includes a structure of the formula (1): The diacid monomer includes terephthalic acid and the diol monomers include ethylene glycol. Moreover, the diol monomers further include 1,3/1,4-CHDM (1,3/1,4-cyclohexane-dimethanol), and thus the amorphous copolyester is obtained when the adding amount of 1,3/1,4-CHDM between 20 and 100 mole% (equivalent percent of the diol monomers).

Description

。 。 。 。 。 。 。 。 Amorphous copolyesters in a wide amorphous region and their applications. [Prior Art] Polyethylene terephthalate (PET) (a thermoplastic polyester engineering plastic polymerized by the acidification of diacid and diol. This material has mechanical properties. It has a wide range of electrical characteristics, strong gas barrier, good light transmission, hardness, easy processing, and low cost, so it is widely used in many industries. However, due to its regular molecular structure, it is easy to accumulate and form a crystalline structure. In addition, it affects its light transmittance, impact resistance, dyeability, etc. Therefore, in many high-value industries, the application research of amorphous germanium copolymerization S can be seen everywhere. Currently, most amorphous copolyesters are mainly American Eastman Company. (Eastman Kodak company) synthesized 1,4 cyclohexane dimethanol (l,4-cyclohexanedimethano b abbreviated as m-CHDM) monomer-polymerized copolyester polymer (also known as PETG), or The isophthalic acid (IPA) polymerized amorphous copolyester is introduced; while the former has a relatively narrow amorphous region, and the amount of the 1,4_CHDM monomer is only 20 to 40%. Import IPA The reason is fragile and thus affects its mechanical and processing properties. [Invention] 5 200827382 P27950051TW 22115twf.doc/006 The present invention provides an amorphous copolyester to obtain a material which is simple in synthesis and has a wide amorphous region. The invention further provides an amorphous copolyester having a wide amorphous region to facilitate various molding processing applications. The invention further provides a material using an amorphous copolyester for use in containers, sheets and films. The present invention provides an amorphous copolyester which is synthesized from a diacid monomer and a diol monomer. The above amorphous copolyester comprises the structure represented by the formula (1):

Wherein 'the diacid monomer includes terephthalic acid (abbreviated as TPA)' and the diol monomer includes ethylene glycol (abbreviated as EG) and 1,3/1,4-cyclohexene Dihydric alcohol (i, 3/i, 4-cyclohexanedimethanol\_ written as 1,3/1,4-CHDM), wherein 1,3/1,4-cyclohexanedimethanol is added in the amount of diol 20~1〇〇mole%. In one embodiment of the invention, the synthesis reaction of the above diacid monomer with the diol monomer further comprises the addition of a polycondensation catalyst. Further, the polycondensation catalyst is 25 to 500 Ppm, which is a metal catalyst selected from one or more selected from the group consisting of lanthanide, titanium, lanthanide, tin, gallium, lanthanide, and combinations thereof. In one embodiment of the invention, the amorphous copolyester has an intrinsic viscosity greater than 0.5 dL/g. The present invention further provides an amorphous copolyester synthesized from a diacid monomer and a double 200827382 P27950051TW 22115twf.doc/006 alcohol monomer, the amorphous copolyester comprising the structure represented by the formula (2): --0CH2CH20—( 0 〇

(2) wherein the diacid monomer comprises terephthalic acid (TPA) and 5-tertiary-tert-butyl isophthalic acid (5tBIA); the diol monomer comprises ethylene glycol oxime) 3/1,4-cyclohexanedimethanol (1,3/1,4-(:11〇]\4), wherein the amount of 5tBIA added as a diacid and 1 in terms of dihydric alcohol equivalent The addition amount of 3/1, 4_cyclohexyl dimethanol is 2〇~1〇〇m〇le〇/〇. In another embodiment of the present invention, the above diacid monomer and diol monomer The synthesis reaction further includes adding a polycondensation catalyst. Moreover, the polycondensation catalyst is Μ~500 ppm, which is selected from the group consisting of lanthanide, titanium, lanthanide, tin, gallium, aluminum, and combinations thereof. One or more metal catalysts. In another embodiment of the present invention, the amorphous copolyester has an intrinsic I viscosity of more than 0.5 dL/g. The invention further provides a container comprising the above two The amorphous copolymer is one of them - as a material. Moreover, the above container may be a food container, a cosmetic bar or a pharmaceutical container. The seeded sheet 'includes the above two kinds of crystal system= Further, the above-mentioned sheet may be a sheet material or a sheet material. It is also proposed to provide a film comprising the above two kinds of amorphous copolymer materials, and the film may be a packaging material or a shrink film. 200827382 P27950051TW 22115twf .doc/〇〇6 The present invention is based on the use of 1,3/1, 4-cyclohexanthene-field^ as a monomer for synthesizing amorphous copolyesters (1'3/1'4___ wide amorphous, (4) The domain of the 妓 麟 麟 has a fairly wide and dazzling two m, but also can be on, the ring thus has two: = in a variety of industries 1, especially silk 81 can be widely used, Zhou kouyi for the valley, film With flakes.

The above-mentioned features and gravitational energy of the present invention are understood. The following is a detailed description of the following example: [Embodiment] The first embodiment: The crystal copolyester is synthesized from a diacid monomer and two diol monomers, and its structural formula is as shown in the following formula (丨)··

Wherein 'the diacid monomer includes terephthalic acid (abbreviated as TPA), and the diol monomer includes ethylene glycol (ethylene glycob abbreviated as EG) and 1,3/1,4_ Dimethanol (i, 3/i, 4-cyclohexanedimethanol, abbreviated as 1,3/1,4-CHDM), wherein 1,3/1,4-cyclohexanedimethanol is added in an amount of 20% of the diol equivalent 1〇〇mole%. In addition, the above-mentioned diacid monomer and diol monomer are generally synthesized by two-stage esterification and polycondensation, and a polycondensation catalyst is added in the reaction process 8 200827382 P27950051TW 22115twf.doc/0〇6, and the content thereof is about 25~5〇〇ppm. The polycondensation catalyst to be used is, for example, one or more selected from the group consisting of lanthanide, titanium, and tin, gallium, aluminum, and combinations thereof, and a catalyst; preferably yttrium acetate. Catalyst with titanium bismuth alloy. As for the formula (丨), the metal C is determined according to the addition amount of the diacid monomer and the diol monomer. Further, the above 1,3/1,4-cyclohexane-sintered methanol can be purchased from UNOXOLTM 34 Diol supplied by the Dow Chemical Company, and its composition is as follows:

(cis, trans)-1,4-cyclohexanedioxanol (cis, trans)-1,3_cyclohexanedodecanol UNOXOLTM 34 Diol Ingredient table · isomer (isomer) composition % content% Trans_l,3-CHDM 56.8 24 cis-l93-CHDM 32.8 trans-l, 4-CHDM 43.2 30.2 cis_l, 4_CHDM 13.0 Regarding the amorphous copolymerized vinegar represented by the formula (1) in the first embodiment, the synthesis route is as follows: 200827382 P27950051TW 22115twf.doc/006

TPA 1,3/1,4-CHDM EG ψ esterification polycondensation

Table 1 below shows the intrinsic viscosity and thermal properties of amorphous copolyesters synthesized at different monomer composition ratios, where T represents terephthalic acid (TPA) and E represents ethylene glycol. (EG), C represents 1,3/1,4-cyclohexanedimethanol (1,3/1,4-CHDM). Further, "PETGy/M" represents an amorphous copolyester synthesized using terephthalic acid, ethylene glycol and 1,3/1,4-cyclohexanedimethanol. 200827382 P27950051TW 22115twf.doc/006 Table 1 Copolyester TEC Intrinsic viscosity Tm 0 nole%) iJdL/g) (°C) PET 100 100 0 0.74 254^ PETGl53/i, 4l〇100 90 10 0.67 221 PETGi,3/i , 45 100 85 15 0.69 207 PETGu/1,42〇1 100 80 20 0.65 196 PETGu/i,430 100 70 30 0.77 PETGu/1,450 100 50 50 0.73 PETGu/1,470 100 30 70 0.73 Face __ PETGu/ 1,490 100 10 90 0.75 — The intrinsic viscosity in Table 1 is a solution of tetracylfluorene (tetrachl〇r〇ethane) and phenol weight ratio of 40:60, with a Ubbelum viscosity at 25 ° C The value obtained by the test (Ubbelohde viscometer). As can be seen from Table 1, the intrinsic viscosity of the amorphous copolyester of the first embodiment at different compositions was greater than 〇.5 dL/g. Temperature measurements were performed using a differential calorimeter to analyze the thermal properties at a rate of 20 C per minute, such as the melting temperature (Tm) in Table 1. As can be seen from Table 1, when 1110% (indicated by c) of 1,3/1,4-cyclohexanedimethanol is 20, the Tm is 196 ° C, and then increases by 1,3/1,4- The melting temperature of cyclohexane dimethanol cannot be measured; that is, the amount of 1,3/ι, 4_cyclohexane dimethanol added is 20 mole% or more of the dihydric alcohol equivalent to synthesize the present invention. A non-crystalline copolyester of one embodiment. Further, by plotting the relationship between the amount of 1,3/1,4-cyclohexanedimethanol qwm-CHDM) of Table 1 and the melting temperature (Tm), the amorphous system of the present invention can be more clearly seen. The polyester has a broad amorphous region (Figure 1). 11 200827382 P27950051TW 22115twf.doc/〇〇6 Second Embodiment: The amorphous copolyester of the second embodiment is synthesized from two bis-acid monomers and two diol monomers, and has the following structural formula ( 2) shown:

σ σ (2) wherein the diacid monomer includes terephthalic acid (ΤρΑ) and 5_3 butyl phthalic acid (5tBIA), and the diol monomer includes ethylene glycol (EG) and 丨 meaning^ - cyclohexanedimethanol (1,3/1,4-CHDM) in which the amount of 5ffiIA added in terms of dibasic acid equivalents and the addition of 153/1,4-cyclohexanedimethanol in terms of diol equivalents The total amount is 20 to 100 mole%, and when the above diacid monomer and the diol monomer are synthesized by two-stage esterification and polycondensation, a polycondensation catalyst is added during the reaction, and the content thereof is about 25 ~500 ppm range. The polycondensation catalyst used herein is, for example, a metal catalyst selected from the group consisting of lanthanide, titanium, lanthanide, tin, gallium, j aluminum, and combinations thereof; preferably acetic acid Tantalum and titanium-bismuth alloy catalyst. Further, A, B, c and d in the formula (2) are determined depending on the amount of addition of the diacid monomer and the diol monomer. The above cyclohexane dimethanol is also purchased from Dow Chemical International Co., Ltd. 1

Un〇x〇ltm 34 Diob supplied by Chemical Company) The synthesis route of the amorphous copolyester represented by the formula (2) in the second embodiment is as follows: 12 200827382 P27950051TW 22115twf.doc/006

HgC—C—CH3 ch3 Table 2 below shows the intrinsic viscosity and thermal properties of amorphous copolyesters synthesized at different monomer composition ratios, where T represents terephthalic acid (TPA) and tBI represents 5 - Tertiary butyl isophthalic acid (5tBIA), E for ethylene glycol oxime), 0: for 1,3/1,4-cyclohexanedidecyl alcohol (1,3/1,4-(:11 〇]^). Also, "PETGu/mB" represents an amorphous copolyester synthesized using the above four monomers. The intrinsic viscosity and melting temperature (Tm) in Table 2 are the same as in the first embodiment. Table 2 Copolyester T tBI EC Intrinsic viscosity (dL/g) Tg (°C) Tm (°C) (mole%) PET 100 0 100 0 0.74 78 254 PETGi3/i, 45B5 95 5 95 5 0.68 77 222 PETGu/m5B10 90 10 95 5 0.72 80 207 PETGi,3/i,41〇B10 90 10 90 10 0.65 79 — PETGH415B10 90 10 85 15 0.67 80 PETGj^/i^OBlO 90 10 80 20 0.64 80 — 13 200827382 P27950051TW 22115twf.doc/〇〇6 It can be seen from Table 2 that the intrinsic viscosity is greater than 0.5dL/g, and when m, ee% of 1,3/1,4-cyclohexanyl dimethanol (represented by c) ) is m〇le% of 1〇,5-three-stage di-m-benzenedi-f-acid (in tBI At this time, Tm cannot be measured; that is, the amorphous copolyester of the second embodiment of the present invention can be synthesized when the sum of c and tBI is 20 m〇le% or more. The glass transition temperature (Tg) can also be obtained by using a differential calorimeter at a rate of 20 ° C per minute. From Table 2, when the sum of c and the work is greater than or equal to 20 m〇le%, the amorphous system The glass transition temperature of the polyester does not decrease. Since the amorphous copolymerized vinegar of the above-mentioned first and second embodiments can be processed by a conventional molding method, it can be widely used in the market of materials, film materials, etc. In the case of a container in the form of a moon, the amorphous copolymerization of the present invention is particularly suitable for the production of a large-capacity thick layer; the mouth is transparent, not easily broken, and easy to be surface-processed, etc. 1,3/1,4 - The cyclohexyl sterol content is more resistant to chemicals, and the same advantages can be made in food, medicine, or ray, etc., to be added to various fields of the amorphous styrene vinegar of the present invention. .. Formulation: Dyes, etc. 'According to the requirements of different application fields; = mode In the case of a sheet, since the present invention has a better suitability, a high transparency, and no gastric breakage: the copolymerized vinegar is used in the production of a sheet or a sheet. Anvil, so it can also be used as a film. 'Because the amorphous system of the present invention has a high plasticity 14 200827382 P27950051TW 22115twf.doc/〇〇6 force 2 transparency, high gloss, low haze, easy to print, It is not easy to fall off and has a good natural shrinkage rate, so it can be widely used in the production of sheets such as scoop materials or shrink films. In summary, the present invention has a relatively broad amorphous system because it is used as a monomer for synthesizing an amorphous copolyester by using a ruthenium ring (1'3/1'4-CHDM). Copolymerization of the region. At the same time, : into: three-stage butyl isophthalic acid (5tBiA) monomer to make "two bismuth, water § day, so you can get effective to prevent the glass transition temperature from falling, and the amorphous copolymerization of the present invention is turned into Having a == sheet in the material itself can be used to make a variety of containers or as a packaging material or as received - although the invention has been disclosed in the preferred embodiments as above, which is not intended to limit the invention, and is generally Those skilled in the art can make some changes and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention is subject to the patent application attached. ^ [Simple description of the figure] According to the first embodiment of the present invention, the relationship between the amount of addition and the dissolution temperature of the amorphous copolymerized vinegar heart '4 5 hexamidine-methanol (6) VIII'.

Af 〇 15

Claims (1)

200827382 P27950051TW 22115twf.doc/006 X. Application for Patent Park: 1· An amorphous copolyester synthesized from a diacid monomer and a diol monomer, the amorphous copolyester comprising the formula (1) structure: (1) wherein 'the bis-acid monomer comprises terephthalic acid (abbreviated as TPA); the diol monomer comprises ethylene glycol (ethylenegly C〇l, abbreviated as EG) and 1,3/1, 4. Cyclohexanol (l, 3/l, 4-cyclohexanedimethanol, abbreviated as 1,3/1,4-CHDM), wherein the amount of 1,3/1,4-cyclohexanedimethanol added It is 20~1〇〇mole of dihydric alcohol equivalent. /. . 2. The amorphous copolyester according to claim 1, wherein the polycondensation catalyst is further included in the synthesis reaction of the bisacid monomer and the diol monomer. 3. The amorphous copolyester according to claim 2, wherein the polycondensation catalyst is 25 to 500 ppm. 4. The amorphous copolyester according to claim 2, wherein the polycondensation catalyst is selected from the group consisting of lanthanide, titanium, lanthanide, tin, gallium, aluminum, and combinations thereof. One or more of the metal catalysts. 5. The amorphous copolyester according to claim 1, wherein the organic viscosity is greater than 0.5 dL/g. 6. A kind of amorphous copolyester, which is synthesized from a diacid monomer and a diol monomer. 200827382 P27950051TW 22115twf.doc/006 The '5H amorphous conjugated vinegar comprises the structure shown by the formula (2): π (2) wherein 'the bis-acid monomer comprises terephthalic acid (TPA) and 5-tert-butylisophthalic acid (abbreviated as 5tBIA); the diol Monomers include ethylene glycol (EG) and 1,3/1,4_; 己 烧 Τ · (1,3/1,4-ο>^1ο1ιεχ&ηε(ϋιηε1;1ι&ηο1, 1 , 3/1,4-CHDM), wherein the amount of 5tBIA added in terms of dibasic acid equivalents and the amount of 1,3/1,4-cyclohexanedimethanol in terms of diol equivalents are 2〇~1 in total非晶m〇ie〇/0. 7. The amorphous copolyester according to claim 6, wherein the synthesis reaction of the bis-acid monomer and the diol monomer further comprises adding a polymerization 8. The condensed catalyst. 8. The amorphous copolyester according to claim 7, wherein the turmeric water-repellent catalyst is 25 to 500 ppm. 9. As described in claim 7 A crystal copolyester, wherein the polycondensation catalyst is selected from the group consisting of a metal catalyst including one or more of a lanthanide, a titanium system, a lanthanide, a tin system, a gallium system, an aluminum system, and a combination thereof. Patent application scope The amorphous copolyester according to item 6 has an intrinsic viscosity of more than 0.5 dL/g. 17 200827382 P27950051TW 22115twf.doc/006 11. A container comprising an amorphous copolyester as a material, wherein: The crystal copolyester is synthesized from a bis-acid monomer and a diol monomer, and the amorphous fluorene copolymer S is intended to include a structure not represented by the formula (1). Wherein the bis-acid monomer comprises terephthalic acid; the diol monomer comprises ethylene glycol and 1,3/1,4-cyclohexanedimethanol, wherein 1,3/1,4-cyclohexane The amount of methanol added is 20 to 100 mole% of the equivalent of the diol. 容器12. The container according to claim 11 is a food container. 13. The container of claim 11 is a cosmetic container. 14. The container of claim 11 is a pharmaceutical container. 15. A container comprising: an amorphous copolyester, wherein: the amorphous copolyester is synthesized from a bis-acid monomer and a diol monomer, the amorphous copolyester comprising the formula (2) ) the structure shown: H3C—C—ch3 18 200827382 P27950051TW 22115twf.doc/006 _ (2) wherein 'the bis-acid monomer comprises terephthalic acid and 5-tris-butyl isophthalic acid (5tBIA); the diol monomer includes B a diol and a cyclohexane-sintered dimethanol, wherein the amount of 5t BIA added in terms of dibasic acid equivalents and the amount of 1,3/1,4-cyclohexanol in terms of diol equivalents are 2 〇 1 〇〇mole% 〇16. The container of claim 15 is a food container. 17. The container according to claim 15 of the patent application, which is a cosmetic container. The container according to claim 15 is a pharmaceutical container. 19. A film comprising an amorphous copolyester, wherein: the amorphous copolyester is synthesized from a bis-acid monomer and a diol monomer, the amorphous copolyester comprising the formula (1) The structure shown: One one one V (1) wherein the bis-acid monomer comprises p-dicarboxylic acid; the diol monomer comprises ethylene glycol and 1,3/1,4-cyclohexanedime, wherein 1,3/1, ' The cyclohexane dimethanol is added in an amount of 2 (^4 〇〇 mole% 〇 2 〇 of the diol equivalent equivalent of the film described in claim 19, which is a packaging material. 200827382 rz /y^uuilTW 22115twf.doc /006 21. The film according to claim 19, which is a shrink film. 22. A film comprising *^ amorphous 糸 vinegar as a material ^ wherein · the amorphous copolyester is made of a diacid When the monomer is synthesized with a diol monomer, the amorphous yttrium copolymer S is intended to include the structure of the formula (2). HaC—c—ch3 ch3 (2) wherein the bis-acid monomer comprises terephthalic acid and 5-tri-tert-butyl dicarboxylic acid (5tBIA); the diol monomer comprises ethylene glycol and 1, 3/1 , 4-cyclohexanedimethanol, wherein the amount of 5tBIA added in terms of dibasic acid equivalents and the amount of 1,3/1,4-cyclohexanedimediol in terms of diol equivalents are 20 to 100 moles in total. % 〇 23. The film as described in claim 22, which is a packaging material. 24. The film of claim 22, which is a shrink film. 25. A sheet comprising a material of an amorphous copolyester, wherein: 'the amorphous copolyester is synthesized from a bis-acid monomer and a diol monomer, and the amorphous germanium copolymer is intended to include Structure of the formula (1) · 20 200827382 ϊά/^Κ)ό5 1TW 22115twf.doc/006 Wherein the bis-acid monomer comprises terephthalic acid; the diol monomer comprises ethylene glycol and 1,3/1,4-cyclohexanedime, wherein 1,3/1,4-cyclohexane The alkanohydrin is added in an amount of from 20 to 100 mole% of the bisphenol equivalent. 片26. The sheet according to claim 25, which is a sheet. 27. The sheet of claim 25, which is a sheet material. 28. A sheet comprising a non-crystalline copolyester, wherein: the amorphous copolyester is synthesized from a bis-acid monomer and a diol monomer, and the amorphous germanium copolymer is intended to comprise (2) The structure of the whole (7) wherein the bis-acid monomer comprises terephthalic acid and 5-tris-butyl phthalic acid (5tBIA); the diol monomer comprises ethylene glycol and 1,3/1,4-cyclohexane Dimethanol, of which 21 200827382 P27950051TW 22115twf.doc/006 The amount of 5tBIA added in terms of double acid equivalent and the amount of 1,3/1,4-cyclohexanedimediol in terms of diol equivalents are 20~ 100 mole% 〇29. A sheet as described in claim 28, which is a sheet. 30. The sheet of claim 28, which is a sheet material. twenty two