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WO2024128811A1 - Résine de polyester et son procédé de préparation - Google Patents

Résine de polyester et son procédé de préparation Download PDF

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Publication number
WO2024128811A1
WO2024128811A1 PCT/KR2023/020575 KR2023020575W WO2024128811A1 WO 2024128811 A1 WO2024128811 A1 WO 2024128811A1 KR 2023020575 W KR2023020575 W KR 2023020575W WO 2024128811 A1 WO2024128811 A1 WO 2024128811A1
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WIPO (PCT)
Prior art keywords
formula
polyester resin
paragraph
ppm
group
Prior art date
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PCT/KR2023/020575
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English (en)
Korean (ko)
Inventor
노경규
박노우
김호섭
홍충희
신미
박기현
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Kolon Industries Inc
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Kolon Industries Inc
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Publication date
Priority claimed from KR1020230085833A external-priority patent/KR20240092539A/ko
Application filed by Kolon Industries Inc filed Critical Kolon Industries Inc
Priority to CN202380059894.9A priority Critical patent/CN119731236A/zh
Publication of WO2024128811A1 publication Critical patent/WO2024128811A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters

Definitions

  • the present disclosure relates to polyester resins and methods of making them.
  • PET polyethylene terephthalate
  • TPA terephthalic acid
  • EG ethylene glycol
  • terephthalic acid the main raw material of terephthalic acid is paraxylene, which is manufactured by refining crude oil. Accordingly, the production and use of terephthalic acid causes depletion of crude oil resources. In addition, when terephthalic acid is decomposed, carbon dioxide emissions increase, causing environmental pollution and climate change such as warming.
  • furan dicarboxylic acid is a material derived from biomass, which prevents depletion of crude oil resources and can minimize environmental pollution and climate change due to its biodegradability.
  • furan dicarboxylic acid is a compound with low thermal stability, and causes thermal discoloration such as yellowing and browning during the esterification reaction with the diol component.
  • a polyester resin with reduced terminal acid value, suppressed heat discoloration, and improved mechanical properties is provided.
  • a method for producing a polyester resin that can improve physical properties by reducing the terminal acid value, suppress thermal discoloration of the polymer, and improve mechanical properties.
  • the polyester resin according to one embodiment includes a copolymer containing a repeating unit represented by the following formula (1), is crosslinked by an ether-based crosslinking agent represented by the following formula (2), and has a terminal acid value of 5 meq/kg to 5 meq/kg. It is 20meq/kg.
  • a 11 is a straight-chain or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms
  • R 11 is a halogen group, a hydroxy group, an alkoxy group, or an alkyl group
  • n 11 is a repeating unit. is the number of repetitions
  • n 12 is an integer from 0 to 2
  • a 21 and A 22 are each independently a straight-chain or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxy group.
  • Formula 2 may include Formula 2A, Formula 2B, Formula 2C, Formula 2D, or a combination thereof.
  • the polyester resin may have a terminal acid value of 6 meq/kg to 11 meq/kg.
  • the polyester resin may have ⁇ IV, which is the difference between intrinsic viscosity values measured at 35°C and 25°C, of 0.2 dl/g to 1.6 dl/g.
  • the polyester resin may have an L* value of 94 or more and a b* value of 5.0 or less according to the CIE1976 L*a*b* colorimeter.
  • the polyester resin has a glass transition temperature (Tg) of 85°C to 100°C and a melting temperature (Tm) of It may be 200°C to 240°C.
  • the elongation rate of the polyester resin may be 130% or more.
  • a method for producing a polyester resin according to another embodiment is to form an oligomer by reacting an aromatic dicarboxylic acid-based compound including a furan dicarboxylic acid-based compound, an aliphatic diol-based compound, and an ether-based crosslinking agent represented by the following formula (2). esterification reaction step to prepare, and
  • It includes a polymerization step of polymerizing the oligomer to produce a polyester resin, wherein the polyester resin has a terminal acid value of 5 meq/kg to 20 meq/kg.
  • a 21 and A 22 are each independently a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxy group.
  • the ether-based crosslinking agent may be added in an amount of 10 ppm to 5000 ppm based on 1 kg of the polyester resin.
  • Formula 2 may include Formula 2A, Formula 2B, Formula 2C, Formula 2D, or a combination thereof.
  • the aromatic dicarboxylic acid compound is isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, 4,4'-stilbendicarboxylic acid, 2,5-thiophenedicarboxylic acid, or these It may further include a mixture of
  • the furan dicarboxylic acid-based compound may be a compound represented by the following formula (3).
  • R 31 is a halogen group, a hydroxy group, an alkoxy group, or an alkyl group
  • R 32 and R 33 are each independently a hydroxy group or an alkoxy group
  • n 32 is an integer of 0 to 2.
  • the aliphatic diol-based compound may be a compound represented by the following formula (4).
  • a 11 is a linear or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms.
  • the molar ratio of the aromatic dicarboxylic acid-based compound and the aliphatic diol-based compound may be 1:1.5 to 1:5.0.
  • the polymerization step may include a pre-polymerization step of pre-polymerizing the oligomer, and a polycondensation step of subjecting the pre-polymerized polymer to a polycondensation reaction.
  • the polyester resin according to one embodiment has a reduced terminal acid value, suppressed heat discoloration, and improved mechanical properties.
  • a method for producing a polyester resin according to another embodiment can improve physical properties by reducing the terminal acid value, suppress thermal discoloration of the polymer, and improve mechanical properties.
  • alkyl refers to a saturated, monovalent aliphatic hydrocarbon radical, including straight and branched chains, having the specified number of carbon atoms.
  • the alkyl group typically has from 1 to 20 carbon atoms (“C 1 -C 20 alkyl”), preferably from 1 to 12 carbon atoms (“C 1 -C 12 alkyl”), more preferably from 1 to 12 carbon atoms (“C 1 -C 12 alkyl”). 8 carbon atoms (“C 1 -C 8 alkyl”), or 1 to 6 carbon atoms (“C 1 -C 6 alkyl”), or 1 to 4 carbon atoms (“C 1 -C 4 alkyl”) ) contains.
  • alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, etc. Includes.
  • Alkyl groups may be substituted or unsubstituted. In particular, unless otherwise specified, an alkyl group may be substituted with one or more halogens, up to the total number of hydrogen atoms present on the alkyl moiety.
  • C 1 -C 4 alkyl is a halogenated alkyl group, for example a fluorinated alkyl group having 1 to 4 carbon atoms, such as trifluoromethyl (-CF 3 ) or difluoroethyl (-CH 2 Contains CHF 2 ).
  • Alkyl groups described herein as optionally substituted may be substituted with one or more substituents, and the substituents are independently selected unless otherwise stated.
  • the total number of substituents is equal to the total number of hydrogen atoms on the alkyl moiety to the extent that such substitution satisfies chemical sense.
  • Optionally substituted alkyl groups typically have 1 to 6 optional substituents, often 1 to 5 optional substituents, preferably 1 to 4 optional substituents, more preferably 1 to 3 optional substituents. It may contain a substituent.
  • Suitable optional substituents for alkyl groups include, but are not limited to, C 1 -C 8 alkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, 3-12 membered heterocyclyl.
  • C 3 -C 8 cycloalkyl 3- to 12-membered heterocyclyl, C 6 -C 12 aryl or C 5 -C 12 heteroaryl, each C 1 -C 8 alkyl, C 2 -C 8 alkenyl. , C 2 -C 8 alkynyl, C 3 -C 8 cycloalkyl, 3-12 membered heterocyclyl, C 6 -C 12 aryl and 5-12 membered heteroaryl are optional as further defined herein. It can be replaced with .
  • divalent aliphatic hydrocarbon i.e., alkylene
  • alkylene refers to a divalent hydrocarbyl group having a specified number of carbon atoms, capable of linking two other groups together.
  • Alkylene often refers to -(CH 2 ) n -, where n is 1 to 8, preferably n is 1 to 4.
  • alkylene may also be substituted with other groups and may contain at least one degree of substitution (i.e., an alkenylene or alkynylene moiety) or ring. The open valency of an alkylene need not be at the opposite end of the chain.
  • Alkylene groups are unsubstituted or substituted by the same groups described herein as suitable for alkyl.
  • halo or halogen refers to fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), unless otherwise specified.
  • hydroxy refers to the group -OH, unless otherwise specified.
  • alkoxy refers to a monovalent -O-alkyl group in which the alkyl portion has the specified number of carbon atoms.
  • the alkoxy group typically has 1 to 8 carbon atoms (“C 1 -C 8 alkoxy”), or 1 to 6 carbon atoms (“C 1 -C 6 alkoxy”), or 1 to 4 carbon atoms ( “C 1 -C 4 alkoxy”).
  • C 1 -C 4 alkoxy is methoxy (-OCH 3 ), ethoxy (-OCH 2 CH 3 ), isopropoxy (-OCH(CH 3 ) 2 ), tert-butyloxy (-OC( Includes CH 3 ) 3 ) and the like.
  • the alkoxy group is unsubstituted or substituted on the alkyl portion by the same groups described herein as suitable for alkyl.
  • the alkoxy group may be optionally substituted with one or more halo atoms, especially one or more fluoro atoms, up to the total number of hydrogen atoms present on the alkyl part.
  • haloalkoxy groups having a certain number of carbon atoms and substituted with one or more halo substituents, for example, when fluorinated, "fluoroalkoxy" groups, typically such groups have from 1 to 6 carbon atoms.
  • the fluorinated alkyl group is typically a fluoroalkoxy group substituted with 1, 2 or 3 fluoro atoms, such as C 1 -C 6 , C 1 -C 4 or C 1 -C 2 fluoroalkoxy. It may be specifically referred to as a group.
  • C 1 -C 4 fluoroalkoxy is trifluoromethyloxy (-OCF 3 ), difluoromethyloxy (-OCF 2 H), fluoromethyloxy (-OCFH 2 ), difluoroethyloxy ( -OCH 2 CF 2 H) and the like.
  • the terms “optionally substituted” and “substituted or unsubstituted” mean that the particular group described may have no non-hydrogen substituents (i.e., unsubstituted) or that the group may have one or more non-hydrogen substituents. It is used interchangeably to indicate that it may have a substituent (i.e., substituted). Unless otherwise specified, the total number of substituents that may be present is equal to the number of H atoms present on the unsubstituted form of the group being described.
  • substituents are independently selected from the list of substitutes, the groups selected are the same or different. It will be understood throughout this specification that the number and nature of optional substituents will be limited to the extent that such substitutions satisfy chemical sense.
  • the CIE1976 L*a*b* color space is defined by the CIE (International Commission on Illumination) and corresponds to the color space currently standardized globally.
  • the L* value represents brightness in color coordinates and ranges from 0 to 100, with a value of 0 meaning complete black and 100 meaning complete white.
  • a* indicates whether the color is biased towards red or green. If this value is positive, or "+”, it is red, and if it is negative, or "-", it is green.
  • b* indicates whether the color is biased towards yellow or blue. If this value is a positive value of "+”, it is yellow, and if it is a negative value of "-”, it is blue.
  • a method for producing a polyester resin according to an embodiment is to form an oligomer by reacting an aromatic dicarboxylic acid-based compound including a furan dicarboxylic acid-based compound, an aliphatic diol-based compound, and an ether-based crosslinking agent represented by the following formula (2). It includes an esterification reaction step, and a polymerization step of polymerizing the oligomer to prepare a polyester resin, wherein the polyester resin has a terminal acid value of 5 meq/kg to 20 meq/kg.
  • a 21 and A 22 are each independently a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxy group.
  • the terminal acid value of the polyester resin can be reduced and thermal discoloration can be suppressed by adding an ether-based crosslinking agent.
  • an oligomer is prepared by reacting an aromatic dicarboxylic acid-based compound including a furan dicarboxylic acid-based compound, an aliphatic diol-based compound, and an ether-based crosslinking agent represented by the following formula (2).
  • the furan dicarboxylic acid-based compound may be a bio-derived material.
  • the furan dicarboxylic acid-based compound may be a compound represented by the following formula (3).
  • R 31 is a halogen group, a hydroxy group, an alkoxy group, or an alkyl group
  • R 32 and R 33 are each independently a hydroxy group or an alkoxy group
  • n 32 is an integer of 0 to 2.
  • the furan dicarboxylic acid-based compound may be 2,5-furandicarboxylic acid or an ester thereof, in which case, in Formula 3, R 32 and R 33 are hydroxy groups. Or it is an alkoxy group, and n 32 may be 0.
  • the aromatic dicarboxylic acid-based compound may further include additional aromatic dicarboxylic acid components in addition to the furan dicarboxylic acid-based compound.
  • the aromatic dicarboxylic acid may be an aromatic dicarboxylic acid having 8 to 20 carbon atoms, for example, an aromatic dicarboxylic acid having 8 to 14 carbon atoms, or a mixture thereof, and may include naphthalene dicarboxylic acids such as isophthalic acid, terephthalic acid, and 2,6-naphthalene dicarboxylic acid. It may be a boxylic acid, diphenyl dicarboxylic acid, 4,4'-stilbendicarboxylic acid, or 2,5-thiophenedicarboxylic acid.
  • Terephthalic acid is a dicarboxylic acid such as terephthalic acid, its alkyl ester (lower alkyl ester with 1 to 4 carbon atoms such as monomethyl, monoethyl, dimethyl, diethyl or dibutyl ester), and/or their acid anhydride. It may react with the diol component to form dicarboxylic acid moiety such as terephthaloyl moiety.
  • Aliphatic diol-based compounds can provide excellent compatibility and elongation to polyester resins.
  • the aliphatic diol-based compound may be a compound represented by the following formula (4).
  • a 11 is a linear or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms.
  • the aliphatic diol-based compound may include an aliphatic diol-based compound having 2 to 20 carbon atoms, for example, 2 to 12 carbon atoms.
  • examples of such aliphatic diol compounds include ethylene glycol, diethylene glycol, triethylene glycol, propanediol (1,2-propanediol, 1,3-propanediol, etc.), 1,4-butanediol, pentanediol, and hexanediol.
  • the aliphatic diol-based compound may be ethylene glycol or 1,4-butanediol.
  • a 11 may be C 2 alkylene (ie, ethylene) or C 4 alkylene (ie, butylene).
  • an aromatic dicarboxylic acid-based compound is reacted with an aliphatic diol-based compound to produce an aromatic oligomer with a low degree of polymerization.
  • the molar ratio of the aromatic dicarboxylic acid-based compound and the aliphatic diol-based compound may be 1:1.5 to 1:5.0. If the molar content of the aliphatic diol-based compound is too high compared to the molar content of the aromatic dicarboxylic acid-based compound, the reaction speed may be slowed or the productivity of the resin may be reduced, and if the molar content of the aliphatic diol-based compound is too small, unreacted aromatic dicarboxylic acid may occur. Residual boxylic acid components may cause foreign matter to occur and the transparency of the resin may decrease.
  • An ether-based crosslinking agent may be added during the esterification reaction. Additionally, a cross-linking agent may be added during the polymerization step.
  • the ether-based crosslinking agent is a crosslinking agent containing an ether group (R-O-R). It reacts with the terminal of the oligomer generated during the esterification reaction or polymerization step, and can obtain an ending capper effect while improving the reaction rate, thereby changing the color. Excellent polyester resin can be produced.
  • the ether-based crosslinking agent is represented by the following formula (2).
  • a 21 and A 22 are each independently a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxy group.
  • a 21 and A 22 may be the same or different, and may each independently be a straight-chain or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms substituted with a hydroxy group.
  • Formula 2 may include Formula 2A, Formula 2B, Formula 2C, Formula 2D, or a combination thereof.
  • the cross-linking agent contains 40% by weight or more of oligomers, for example, 50% by weight or more, 80% by weight, or 90% by weight or more, based on 100% by weight of the total oligomer content formed in the esterification reaction step.
  • the polyester may be added at the time of manufacture, or in an amount of 30% by weight or less, for example, 20% by weight or less, or 10% by weight or less, based on 100% by weight of the total polyester content produced in the polymerization step. there is.
  • the amount of crosslinking agent may be 10 ppm to 5000 ppm based on 1 kg of polyester resin, which is the final polymer, for example, 10 ppm to 3000 ppm, 100 ppm to 3000 ppm, or 300 ppm to 3000 ppm, for example For example, it may be 100 ppm to 5000 ppm, 100 ppm to 3000 ppm, 500 ppm to 3000 ppm, 1000 ppm to 3000 ppm, or 1000 ppm to 2000 ppm.
  • the amount of the crosslinking agent may be 100 ppm to 2000 ppm based on 1 kg of polyester resin, which is the final polymer. If the amount of the cross-linking agent is less than 100 ppm, the terminal acid value is high, so brittleness may decrease when commercialized (manufacturing films, bottles, etc.), and if it exceeds 2000 ppm, the elongation is low and may be brittle. There is. If the amount of crosslinking agent added is less than 300 ppm based on 1 kg of polyester resin, which is the final polymer, the terminal acid value may be high, which may reduce brittleness when commercialized (manufacturing films, bottles, etc.), and if it exceeds 3000 ppm. It has low elongation and can easily break.
  • a heat stabilizer may be added during the esterification reaction.
  • the heat stabilizer contains 10% to 90% by weight of oligomer, for example, 15% to 80% by weight, or 20% to 70% by weight, based on 100% by weight of the total oligomer content formed in the esterification reaction step. It can be put in at the point of creation. By adding the heat stabilizer at the above-mentioned time, a stable reaction can be achieved and the acid value of the finally manufactured polyester resin may appear low.
  • Heat stabilizers may include, for example, phosphoric acid, trimethylphosphate, triethylphosphate, triphenylphosphate, trimethyl phosphono acetate, triethyl phosphono acetate, or mixtures thereof.
  • the input amount of the heat stabilizer may be 5 ppm to 250 ppm, for example, 10 ppm to 220 ppm, 15 ppm to 200 ppm, or 20 ppm to 180 ppm, based on phosphorus (P) element.
  • the amount of heat stabilizer added is 0.01 to 1.00 parts by weight, for example, 0.02 to 0.90 parts by weight, 0.03 to 0.70 parts by weight, or 0.05 to 0.50 parts by weight, based on 100 parts by weight of aromatic dicarboxylic acid. It could be wealth.
  • the catalyst activity will decrease, which will lengthen the reaction time and reduce the reaction conversion rate. Additionally, the acid value of the final manufactured polymer may increase, and if the content of the heat stabilizer is too small, the chip color and heat resistance may decrease. This may deteriorate.
  • the esterification reaction can be carried out by simultaneously adding an aliphatic diol-based compound and an aromatic dicarboxylic acid-based compound.
  • the esterification reaction may proceed as a primary esterification reaction and a secondary esterification reaction.
  • the secondary esterification reaction may proceed at a higher temperature than the primary esterification reaction.
  • a heat stabilizer or cross-linking agent may be added in the secondary esterification reaction step.
  • the esterification reaction step may be performed in a nitrogen (N 2 ) atmosphere at a temperature ranging from 160° C. to 260° C. for 1 hour to 8 hours.
  • the esterification reaction step can be appropriately adjusted depending on the raw material mixing ratio, specific characteristics of the desired polyester resin, etc.
  • the esterification reaction step may be performed at a temperature range of 180°C or higher, 160°C or higher, 170°C or higher, or 180°C or higher and 260°C or lower, 240°C or lower, or 220°C or lower.
  • the esterification reaction step may be performed for at least 1 hour, at least 1.5 hours, or at least 2 hours, but at most 8 hours, at most 7 hours, or at most 6 hours.
  • the reaction yield may be low or sufficient reaction may not occur, and the physical properties of the final polyester resin may be reduced. If the temperature, pressure, reaction time, etc. of the esterification reaction exceed the respective ranges, the appearance of the produced polyester resin is likely to turn yellow, or the depolymerization reaction may proceed, preventing the polyester resin from being synthesized in the production method. It may not be possible.
  • the esterification reaction step can be performed batchwise or continuously.
  • esterification reaction step may be performed in the presence of an esterification reaction catalyst.
  • an esterification reaction catalyst can be added to the esterification reaction step to improve the reaction rate from the beginning of the reaction and shorten the time the polyester resin is exposed to heat.
  • the esterification reaction catalyst may be a titanium-based compound, a germanium-based compound, an aluminum-based compound, a tin-based compound, or a mixture thereof.
  • Titanium-based compounds include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate, Triethanolamine titanate, acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide/silicon dioxide copolymer, titanium dioxide/zirconium dioxide copolymer, etc.
  • Tin-based compounds include tributyltin, tin diacetate, tin dioctoate, tin dilaurate, or dibutyltin dilaurate. etc. can be mentioned.
  • a compound represented by the following formula (5) can be used as an esterification reaction catalyst.
  • a is an integer from 1 to 15
  • b is an integer from 2 to 25
  • c is an integer from 1 to 5
  • d is an integer from 0 to 5
  • e is an integer from 1 to 5
  • M is Ti, Co, Zn, Mn, Sn, Sb, or a combination thereof.
  • the esterification reaction catalyst may be used in an amount of 10 ppm to 1000 ppm based on the central metal atom in the polyester resin being synthesized. If the content of the esterification reaction catalyst is too small, it may be difficult to significantly improve the efficiency of the esterification reaction, and the amount of reactants not participating in the reaction may greatly increase. Additionally, if the content of the esterification reaction catalyst is too high, the external physical properties of the produced polyester resin may deteriorate. In addition, if the content of the esterification reaction catalyst is too high, yellowing of the produced polyester resin may occur and the external physical properties may deteriorate.
  • the oligomer is polymerized.
  • the polymerization step may include a pre-polymerization step of pre-polymerizing an oligomer, and a polycondensation step of subjecting the pre-polymerized polymer to a polycondensation reaction.
  • the oligomer is prepolymerized to prepare a polymer with a higher degree of polymerization than the esterification reaction product.
  • the polymerization step including a prepolymerization step, a polycondensation step, or both, may occur in the presence of a catalyst.
  • the polymerization reaction catalyst may be a compound represented by the following formula (6).
  • a is an integer from 15 to 150
  • b is an integer from 20 to 300
  • c is an integer from 5 to 40
  • d is an integer from 0 to 5
  • e is an integer from 1 to 5. At this time, c/e may be 4.
  • a is an integer from 44 to 100
  • b is an integer from 98 to 194
  • c is an integer from 8 to 18
  • d is an integer from 2 to 4, and 5 ⁇ c/e ⁇ It could be 18.
  • the polymerization reaction catalyst may be a catalyst containing a -Ti-O-P- bond, a catalyst containing a -Ti-P-O- bond, or - while satisfying the above-mentioned conditions a, b, c, d, e, c/e.
  • a catalyst containing a Ti-O- bond the trade-off relationship between thermal discoloration and molecular weight can be resolved.
  • the compound represented by Formula 6 may include compounds represented by Formulas 61 to 63 below.
  • the polymerization reaction catalyst may be used in an amount of 2 ppm to 100 ppm based on the central metal atom of the polyester resin being synthesized. If the content of the polymerization reaction catalyst is too small, the amount of reactants that do not participate in the reaction may greatly increase, and if the content of the polymerization reaction catalyst is too large, it may remain as inert particles and deteriorate the physical properties of the polymer.
  • the weight ratio of the polymerization reaction catalyst to the esterification reaction catalyst may be 0.015 to 0.3, for example, 0.015 to 0.2. If the weight part of the polymerization reaction catalyst is less than 0.015 parts by weight of the esterification reaction catalyst, the reaction time may be delayed due to a decrease in the polymerization reaction rate, and if the weight part of the polymerization reaction catalyst exceeds 0.3, the reactants may be discolored due to side reactions. there is.
  • a heat stabilizer can also be used in the prepolymerization process, and its use can minimize thermal discoloration not only during the prepolymerization process but also during the subsequent polycondensation reaction.
  • the heat stabilizer is trimethyl phosphonoacetate, triethyl phosphonoacetate, phosphoric acid, phosphorous acid, polyphosphric acid, and trimethyl phosphate. It may be a phosphorus-based heat stabilizer including phosphate (TMP), triethyl phosphate, trimethyl phosphine, triphenyl phosphine, or a mixture thereof.
  • TMP phosphate
  • triethyl phosphate trimethyl phosphine
  • triphenyl phosphine triphenyl phosphine
  • Pre-polymerization can be performed under temperature controlled conditions (thermal pre-condensation).
  • the prepolymerization may be performed including raising the temperature until it reaches a temperature range of 220°C to 260°C, maintaining the reached temperature, and prepolymerizing the second esterification reaction product.
  • the pressure when the temperature is increased, the pressure can be reduced until it reaches 0 atm to 0.3 atm, and then the achieved pressure can be maintained when the achieved temperature is maintained.
  • the pre-polymerization step is a step of changing from normal pressure to vacuum before proceeding to the polycondensation reaction (vacuum), which will be described later, and may be a step of gradually changing from normal pressure (1 atm) to vacuum (0 atm). If the pre-polymerization step is omitted, the esterification reaction product may volatilize during the rapid transition to a vacuum state, causing a bump phenomenon, reducing the yield of the final polyester resin, and adversely affecting its physical properties.
  • the prepolymerized polymer is subjected to a polycondensation reaction.
  • the poly-condensation step may be performed for 1 hour to 7 hours in a vacuum atmosphere, at a temperature range of 220° C. to 300° C., and under a pressure of 0.8 torr to 0.4 torr or less.
  • the polycondensation reaction step may be carried out at a vacuum level higher than 0 atm.
  • the degree of vacuum is measured with a vacuum gauge, and polymerization is usually performed in the range of 0.8 torr to 0.4 torr.
  • a polycondensation reaction catalyst can be used.
  • the polycondensation catalyst may be added to the product of the esterification reaction before the start of the polycondensation reaction, may be added to the mixture containing the diol component and the dicarboxylic acid component before the esterification reaction, and may be added during the esterification reaction step. It may be possible.
  • a compound represented by the above-mentioned formula (6) can be used, or a titanium-based compound, a germanium-based compound, an antimony-based compound, an aluminum-based compound, a tin-based compound, or a mixture thereof can be used.
  • Titanium-based compounds include tetraethyl titanate, acetyltripropyl titanate, tetrapropyl titanate, tetrabutyl titanate, polybutyl titanate, 2-ethylhexyl titanate, octylene glycol titanate, lactate titanate, Triethanolamine titanate, acetylacetonate titanate, ethyl acetoacetic ester titanate, isostearyl titanate, titanium dioxide, titanium dioxide/silicon dioxide copolymer, titanium dioxide/zirconium dioxide copolymer, etc.
  • Germanium-based compounds include germanium dioxide (GeO2), germanium tetrachloride (GeCl 4 ), germanium ethyleneglycoxide, germanium acetate, copolymers using these, and mixtures thereof. etc. can be mentioned.
  • the method for producing a polyester resin may further include the step of preparing a chain-extended polyester resin by adding a chain extender after the polymerization step.
  • a polyester resin with desired physical properties can be manufactured by increasing the molecular weight through a chain extension reaction.
  • polyisocyanate compounds As the chain extender, polyisocyanate compounds, aromatic amine compounds, etc. can be used.
  • Polyvalent isocyanate compounds include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, hexamethylene diisocyanate, and triphenylmethane. It may include triisocyanate or a mixture thereof, and the aromatic amine compounds include, in particular, 3,5-diethyl-2,4-diaminotoluene and 3,5-diethyl-2,6-diaminotoluene. Lonza's DETDA80 product mixed at a weight ratio of 20:80 can be used.
  • a polyester resin according to another example includes a copolymer containing a repeating unit represented by the following formula (1), is crosslinked by an ether-based crosslinking agent represented by the following formula (2), and has a terminal acid value of 5 meq/kg. to 20 meq/kg.
  • a 11 is a straight-chain or branched divalent aliphatic hydrocarbon group having 1 to 15 carbon atoms
  • R 11 is a halogen group, a hydroxy group, an alkoxy group, or an alkyl group
  • n 11 is a repeating unit. is the molar ratio
  • n 12 is an integer of 0 to 2.
  • a 21 and A 22 are each independently a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxy group.
  • a 21 and A 22 may be the same or different, and may each independently be a straight-chain or branched aliphatic hydrocarbon group having 1 to 5 carbon atoms substituted with a hydroxy group.
  • Formula 2 may include Formula 2A, Formula 2B, Formula 2C, Formula 2D, or a combination thereof.
  • the amount of the ether-based crosslinking agent may be 10 ppm to 5000 ppm based on 1 kg of copolymer, for example, 10 ppm to 3000 ppm, 100 ppm to 3000 ppm, or 300 ppm to 3000 ppm, For example, it may be 100 ppm to 5000 ppm, 100 ppm to 3000 ppm, 500 ppm to 3000 ppm, 1000 ppm to 3000 ppm, or 1000 ppm to 2000 ppm.
  • the amount of the crosslinking agent may be 100 ppm to 2000 ppm based on 1 kg of polyester resin, which is the final polymer. If the amount of the cross-linking agent is less than 100 ppm, the terminal acid value is high, so brittleness may decrease when commercialized (manufacturing films, bottles, etc.), and if it exceeds 2000 ppm, the elongation is low and may be brittle. There is.
  • the polyester resin has a number average molecular weight (Mn) of 20,000 g/mol to 50,000 g/mol, for example, 23,000 g/mol to 35,000 g/mol, 23,000 g/mol to 30,000 g/mol, 23,000 g/mol. mol to 27,000 g/mol, or 23,000 g/mol to 25,000 g/mol.
  • the number average molecular weight of the polyester resin is less than 20,000 g/mol, not only is it difficult to process it into a film for use as a packaging material, but the desired modulus may not be achieved. On the other hand, if it exceeds 50,000 g/mol, the viscosity may increase and productivity and yield may be lowered.
  • the polyester resin may have an L* value of 94 or more, an a* value of -0.5 to 0, and a b* value of 5.0 or less according to the CIE1976 L*a*b* color system.
  • the L* value may be 96.4 or more, the a* value may be -0.5 to 0, and the b* value may be 4.1 or less.
  • the measurement method of the polyester resin colorimeter is as follows. Dissolve 2 g of polyester resin sample in 20 ml of Hexafluoroisopropanol (HFIP) (0.1 g/ml in HFIP). Konica Minolta's CM-3700A product measures the colorimeter of the sample solution in a Tuartz cell dedicated to solution colorimeter measurement.
  • HFIP Hexafluoroisopropanol
  • the L* value of the polyester resin may be 94 or higher, or 96.4 or higher, and 100 or lower, 99 or lower, or 97.5 or lower. If the L* value is less than 94, there may be a problem of low transmittance or haze when turning into a film.
  • the a* value of the polyester resin may be 0 or less, -0.03 or less, -0.06 or less, or -0.1 or less, and may be -0.5 or more, -0.52 or more, -0.54 or more, or -0.56 or more. If the a* value exceeds 0, the film may appear red.
  • the b* value of the polyester resin may be 5.0 or less, or 4.1 or less, and 0 or more, 1 or more, or 2.2 or more. If the b* value exceeds 5.0, there may be a problem with the color of the film.
  • the color characteristics of a polyester resin can be adjusted by the monomer reaction sequence during the manufacturing process, the amount of monomer used, etc.
  • the polyester resin may have ⁇ IV, which is the difference between intrinsic viscosity values measured at 35°C and 25°C, of 0.2 dl/g to 1.6 dl/g, for example, 0.65 dl/g to 0.67 dl/g.
  • ⁇ IV is the difference between intrinsic viscosity values measured at 35°C and 25°C, of 0.2 dl/g to 1.6 dl/g, for example, 0.65 dl/g to 0.67 dl/g.
  • the polyester resin may have a terminal acid value of 5 meq/kg to 20 meq/kg, for example, a terminal acid number of 8 meq/kg to 20 meq/kg, 8 meq/kg to 15 meq/kg, or 8 meq/kg. kg to 10 meq/kg.
  • the terminal acid value refers to the content of COOH at the polymer terminal, and the terminal acid value of polyester can be measured by a titrimetric method according to modified ASTM D7409. Specifically, 1 g of sample is accurately weighed and placed in a vial. Add 20 ml of O-cresol reagent using a pipette. Dissolve by stirring in a 100°C dissolution bath for 1 hour.
  • the polyester resin may have a glass transition temperature (Tg) of 85°C to 100°C, for example, 87°C to 94°C .
  • the polyester resin may have a melting temperature (Tm) of 200°C to 240°C, for example, 205°C to 220°C.
  • the elongation (%) of the polyester resin may be 130% or more, for example, 150% or more, or 180% or more.
  • the polyester resin may further include a heat stabilizer at 0.1 ppm to 100 ppm based on phosphorus (P) element, for example, 0.1 ppm to 50 ppm, 0.1 ppm to 20 ppm. , or it may be further included at 1 ppm to 20 ppm. If the content of the heat stabilizer is less than 0.1 ppm, the polymer may be discolored, and if it exceeds 100 ppm, the activity of the polymerization catalyst may decrease, slowing the reaction rate, and reducing the viscosity of the polymer.
  • P phosphorus
  • TBT Tributyltin
  • DPE Dipentaerythritol
  • PA phosphoric acid
  • the temperature inside the reactor is raised for 1 hour to proceed with the temperature raising process to 260°C, and at the same time, the pressure is gradually lowered over 1 hour using a vacuum pump so that the pressure inside the reactor reaches 0 atm from 1 atm. Proceed with preliminary polymerization.
  • a polyester resin was obtained in the same manner as in Example 1-1, except that the cross-linking agent content was added at 2000 ppm based on 1 kg of final polymer.
  • polyester was prepared in the same manner as in Example 1-1, except that DPG (Dipropylene glycol) represented by the following formula 2A, formula 2B, or a mixture thereof was added as a crosslinking agent. Obtain resin.
  • DPG Dipropylene glycol
  • a polyester resin was obtained in the same manner as in Example 2-1, except that the cross-linking agent content was added at 2000 ppm based on 1 kg of final polymer.
  • a polyester resin was obtained in the same manner as in Example 1-1, except that DTP (Di(trimethylolpropane); di(trimethylolpropane)) represented by the following formula 2D was added as a crosslinking agent. do.
  • DTP Di(trimethylolpropane); di(trimethylolpropane)
  • a polyester resin was obtained in the same manner as in Example 3-1, except that the cross-linking agent content was added at 2000 ppm based on 1 kg of final polymer.
  • a polyester resin was obtained in the same manner as in Example 1-1, except that the crosslinking agent was not added.
  • a polyester resin was obtained in the same manner as in Example 1-1, except that a cross-linking agent was not added and the type of catalyst was added at 300 ppm based on Sb 2 O 3 chraofmf Sb-based metal.
  • cross-linking agent added was the same as Example 1-1, except that Pentaerythritol, Glycerin, and Trimethylolpropane were used instead of ether-based cross-linking agents. This is carried out to obtain a polyester resin.
  • Polyester terminal acid value can be measured by a titrimetric method according to modified ASTM D7409. Specifically, 1 g of sample is accurately weighed and placed in a vial. Add 20 ml of O-cresol reagent using a pipette. Dissolve by stirring in a 100°C dissolution bath for 1 hour. After transferring the dissolved solution to a 100 ml beaker, wash the inner wall of the vial with 50 ml of chloroform and add it to the beaker. Add 2 to 3 drops of methylene blue and methylene red reagents and titrate with 0.04 N KOH (alcoholic) solution.
  • Tg Glass transition temperature
  • DEG diethylene glycol
  • Measurement of DEG (diethylene glycol) content Measured using Agilent GC-MS column Rtx-5MS (0.25 ⁇ m x 0.25mm x 30m) and expressed in %.
  • the DEG content refers to a processing influence factor. The higher the content, the lower the Tm and the poorer the processability because thermal decomposition easily occurs during processing.
  • Mn is measured using gel permeation chromatography (GPC).
  • the polyester resin according to the example has a low terminal acid value of 8 meq/kg to 10 meq/kg and a b* value of 5.0 or less, so the terminal acid value is reduced and heat discoloration is suppressed. You can.
  • the polyester resins according to Comparative Examples 1 and 2 had a terminal acid value exceeding 25 meq/kg and a b* value exceeding 5.5, and in the case of the polyester resins according to Comparative Examples 3 to 5, the terminal acid value was 11 meq. Since it exceeds /kg and the b* value is 4.9 or more, it can be confirmed that the effect of reducing terminal acid value or suppressing heat discoloration cannot be achieved.
  • the polyester resin according to the example has a significantly higher elongation than the comparative example, it can be confirmed that the mechanical properties are also significantly superior.
  • the present disclosure relates to a polyester resin and a method for manufacturing the same.
  • the polyester resin has a reduced terminal acid value, suppressed heat discoloration, and improved mechanical properties.
  • a method for producing a polyester resin according to another embodiment can improve physical properties by reducing the terminal acid value, suppress thermal discoloration of the polymer, and improve mechanical properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne une résine de polyester qui comprend un copolymère contenant une unité de répétition représentée par la formule chimique 1, qui est réticulée par un agent de réticulation à base d'éther représenté par la formule chimique 2, et qui a une valeur d'acide terminal de 5 meq/kg à 20 meq/kg. La formule chimique 1 et la formule chimique 2 sont telles que décrites ci-dessus.
PCT/KR2023/020575 2022-12-14 2023-12-13 Résine de polyester et son procédé de préparation Ceased WO2024128811A1 (fr)

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CN108774314A (zh) * 2018-05-10 2018-11-09 中国科学院长春应用化学研究所 一种呋喃生物基聚醚酯共聚物的制备方法、新型呋喃生物基聚醚酯共聚物
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KR20140088972A (ko) * 2012-12-31 2014-07-14 주식회사 휴비스 공중합 폴리에스테르 조성물 및 열접착성 바인더용 단섬유 및 그 제조방법
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