KR101792873B1 - Method for preparing wholly aromatic polyester resin and wholly aromatic polyester resin prepared by the method - Google Patents
Method for preparing wholly aromatic polyester resin and wholly aromatic polyester resin prepared by the method Download PDFInfo
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- KR101792873B1 KR101792873B1 KR1020150159548A KR20150159548A KR101792873B1 KR 101792873 B1 KR101792873 B1 KR 101792873B1 KR 1020150159548 A KR1020150159548 A KR 1020150159548A KR 20150159548 A KR20150159548 A KR 20150159548A KR 101792873 B1 KR101792873 B1 KR 101792873B1
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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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
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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
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
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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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
In the present invention, an acetylation reaction is carried out using an aromatic hydroxycarboxylic acid, an aromatic diol or an aromatic dicarboxylic acid with an organic catalyst, and then an inorganic catalyst is used in the esterification reaction to prepare a prepolymer by minimizing side reactions A method for producing a wholly aromatic polyester resin capable of reducing an amount of an oligomer discharged and an outgas generated during molding of a resin by reducing the by-products remaining in the resin by producing a wholly aromatic polyester resin by solid phase polycondensation ≪ / RTI >
Description
The present invention relates to a process for producing a wholly aromatic polyester resin and a wholly aromatic polyester produced thereby, and more particularly to a process for producing a wholly aromatic polyester resin by reacting an aromatic hydroxycarboxylic acid, an aromatic diol and an aromatic dicarboxylic acid with an acetyl And then the side reaction is minimized by using an inorganic catalyst in the esterification reaction to prepare a prepolymer and solid-phase polycondensation to produce a wholly aromatic polyester resin, thereby reducing the by-products remaining in the resin, A method for producing a wholly aromatic polyester resin capable of reducing an outgassing amount and minimizing the amount of oligomer flowing out of a molded product, and a wholly aromatic polyester produced thereby.
The wholly aromatic liquid-crystalline polyester resin has high heat resistance and strength because it is made entirely of an aromatic chain, so it is important as a raw material for high-strength fibers and has great commercial applicability.
The wholly aromatic liquid crystal polyester resin is widely used as a material for automobile parts, electric / electronic parts, and small / precision molded parts because of its excellent flow and heat resistance.
The synthesis of these wholly aromatic polyesters will determine which synthesis reaction to use depending on the T g of the final polymer, melting point (in the case of crystalline), thermal stability, solubility, and the like.
Among the synthesis methods of the wholly aromatic polyester, the synthesis method most widely used is to polymerize by a melt method without using a solvent, but employs an ester exchange reaction. The aromatic diol is acetylated and then reacted with an aromatic diacid, or the aromatic diacid is pre-esterified with phenol and reacted with an aromatic diol.
A conventional method for synthesizing a wholly aromatic polyester is as follows.
Korean Patent No. 1111645 discloses a process for synthesizing a wholly aromatic liquid-crystalline polyester prepolymer by polycondensation of raw monomers containing an aromatic hydroxycarboxylic acid, an aromatic diol and an aromatic dicarboxylic acid but not containing an aromatic aminocarboxylic acid Wherein the aromatic diol does not contain an aromatic compound in which two phenylene is bonded to an element other than carbon, and the content of the aromatic dicarboxylic acid in the starting monomer is 1.02 to 1.08 moles per mole of the aromatic diol Discloses a method for producing a non-aromatic liquid-crystalline polyester resin.
Korean Patent Laid-Open No. 2010-0102923 discloses a process for producing a wholly aromatic liquid-crystalline polyester prepolymer, comprising: (a) synthesizing a wholly aromatic liquid-crystalline polyester prepolymer by polycondensation of at least two raw monomers using a metal acetate catalyst; And (b) synthesizing the wholly aromatic liquid-crystalline polyester resin by solid-phase polycondensation of the prepolymer.
A conventional process for producing a wholly aromatic liquid-crystalline polyester resin is a process for synthesizing a wholly aromatic liquid-crystalline polyester prepolymer by intensively polymerizing raw monomers including an aromatic hydroxycarboxylic acid, an aromatic diol and an aromatic dicarboxylic acid, Benzoic acid, hydroxynaphthoic acid, and the like may remain in the resin, causing outgas during molding to cause blistering. In addition, the conventional method for producing a wholly aromatic liquid-crystalline polyester resin is a method in which only the organic catalyst is used in the acetylation process of the raw monomers containing an aromatic hydroxycarboxylic acid, an aromatic diol and an aromatic dicarboxylic acid, There is a problem in that the amount of oligomer outflow of a low molecular weight is large when a resin produced in an insufficient amount is molded.
[Prior Art Literature]
[Patent Literature]
Korea Patent Publication No. 2010-0102923
Korean Patent No. 0929383
Japanese Laid-Open Patent Publication No. 10-158482
In order to solve the problems of the prior art described above, the inventors of the present invention have found that the amount of outgas and the amount of low molecular weight oligomers produced during the molding of the wholly aromatic polyester resin produced according to the conventional method for producing a wholly aromatic polyester resin The inventors of the present invention have conducted researches to develop a technique capable of minimizing the amount of water, and as a result, they have completed the present invention.
Accordingly, it is an object of the present invention to provide a method for producing a wholly aromatic polyester resin capable of minimizing the amount of outgas and low molecular weight oligomers generated during molding of the produced resin, and a wholly aromatic polyester produced thereby .
Another object of the present invention is to provide a method for producing a wholly aromatic polyester resin compound including a method for producing a wholly aromatic polyester resin.
In order to accomplish the above object, the present invention provides a process for producing a polyimide resin, which comprises the steps of charging an aromatic hydroxycarboxylic acid, an aromatic diol and an aromatic dicarboxylic acid into a stirrer and introducing a reactive solvent and an organic catalyst to carry out an acetylation reaction ); After the acetylation reaction is performed, an inorganic catalyst is added to carry out an esterification reaction and polycondensation to prepare a prepolymer (step S2); And solid phase polycondensation of the prepolymer (step S3). The present invention also provides a method for producing a wholly aromatic polyester resin.
In one embodiment of the present invention, the aromatic hydroxycarboxylic acid includes at least one compound of parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid.
In one embodiment of the present invention, the aromatic diol comprises at least one compound selected from biphenol and hydroquinone.
In one embodiment of the present invention, the aromatic dicarboxylic acid includes at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid.
In one embodiment of the present invention, the reactive solvent is at least one selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, isobutyrate anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride, , Trichloroacetic anhydride, monobromoacetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride , Succinic anhydride and? -Bromopropionic acid anhydride.
In one embodiment of the present invention, the organic catalyst is at least one selected from the group consisting of sulfuric acid, methylene diphosphonic acid, poly (N-vinylimidazole), imidazole compound, triazole compound, dipyridyl compound, phenanthroline compound, A phenanthroline compound, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane and N, N-dimethylaminopyridine At least one kind of compound.
In one embodiment of the present invention, the inorganic catalyst is at least one selected from the group consisting of potassium acetate, calcium acetate, magnesium acetate, NaHCO 3 , phosphorylated acid, silver triflate, copper perchlorate, CuSO 4 5H 2 O ≪ / RTI >
The present invention also provides a process for producing a wholly aromatic polyester resin compound comprising a process for producing a wholly aromatic polyester resin according to the present invention.
The present invention also provides a wholly aromatic polyester resin produced according to the present invention.
In the method for producing a wholly aromatic polyester resin according to the present invention, an organic catalyst is used in an acetylation reaction to prevent a side reaction such as decarbonation reaction of hydroxybenzoic acid or hydroxynaphthoic acid with an acid, , It is possible to prevent the problem of generating blister due to generation of outgas during molding by manufacturing a resin by promoting the condensation polymerization reaction using an inorganic catalyst and minimizing the outflow amount of low molecular weight oligomer .
The wholly aromatic polyester resin produced according to the present invention has an outgassing amount of not more than 20 ppm and an outflow amount of the oligomer having a low molecular weight of not more than 100 ppm.
When the molded product contains a large amount of low molecular weight oligomers, the oligomer may leak out during use under high temperature and harsh conditions. However, the wholly aromatic polyester resin according to the present invention may cause degradation of the product It is possible to minimize the amount of the oligomer having a molecular weight to be discharged so as to prevent deformation of the molded article.
BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish them, will become apparent by reference to the embodiments described in detail below with reference to the accompanying drawings.
However, the present invention is not limited to the embodiments described below, but may be embodied in various other forms.
The present embodiments are provided so that the disclosure of the present invention is thoroughly disclosed and that those skilled in the art will fully understand the scope of the present invention.
And the present invention is only defined by the scope of the claims.
Thus, in some embodiments, well known components, well known operations, and well-known techniques are not specifically described to avoid an undesirable interpretation of the present invention.
In this specification, the singular forms include plural forms unless the context clearly dictates otherwise, and the constituents and acts referred to as " comprising (or comprising) " do not exclude the presence or addition of one or more other constituents and actions .
Unless defined otherwise, all terms (including technical and scientific terms) used herein may be used in a sense commonly understood by one of ordinary skill in the art to which this invention belongs.
Also, commonly used predefined terms are not ideally or excessively interpreted unless they are defined.
Hereinafter, a method for producing a wholly aromatic polyester resin according to the present invention will be described in detail.
First, an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic dicarboxylic acid are added to a stirrer, and a reactive solvent and an organic catalyst are added to carry out an acetylation reaction (Step S1).
An acetylation reaction is carried out using a reactive solvent and an organic catalyst to promote polycondensation of an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic dicarboxylic acid to prepare a raw monomer having increased reactivity.
The acetylation reaction in the step S1 is a step of first converting the hydroxyl group into the acetyl group in order to facilitate the condensation polymerization of the esterification reaction at a lower temperature without side reaction. When the esterification reaction is carried out without converting it into an acetyl group, more energy and time are required, and side reaction may proceed a lot.
The aromatic hydroxycarboxylic acid as the raw material monomer may include at least one compound selected from the group consisting of parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, and the aromatic diol may be at least one of biphenol and hydroquinone The aromatic dicarboxylic acid may include at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid. In the production of the wholly aromatic polyester resin And may further contain known raw material monomers that can be used.
Preferably, the reactive solvent is used in an amount of 1.0 to 1.3 equivalents of an acetylated solvent in excess of the total alcohol group equivalent of the starting monomer composed of an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic dicarboxylic acid, It is preferable to use 1.02 to 1.03 equivalents as a standard.
When the reactive solvent is used in an amount less than the equivalent amount range, the acetylation reaction does not proceed, so that the condensation occurs. After that, condensation polymerization does not proceed and residual monomers may be generated. Can be accompanied by a lot of effort
More specifically, examples of the reactive solvent include acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic acid The anionic surfactant may be selected from the group consisting of anhydrides, monobromoacetic anhydrides, dibromoacetic anhydrides, tribromoacetic anhydrides, monofluoroacetic anhydrides, difluoroacetic anhydrides, trifluoroacetic anhydrides, glutaric anhydrides, maleic anhydrides, β-bromopropionic acid anhydride, and the like, but the present invention is not limited thereto.
In the present invention, an organic catalyst is added during the acetylation reaction of the starting monomers, and the reaction is constantly carried out at a temperature of 150 ° C or lower, thereby preventing side reactions such as decarboxylation.
In the present invention, examples of the organic catalyst include sulfuric acid, methylene diphosphonic acid, poly (N-vinylimidazole), imidazole compound, triazole compound, dipyridyl compound, phenanthroline compound, diazaphenanthroline compound, At least one compound selected from the group consisting of 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane and N, N- Can be used.
In one embodiment of the present invention, the imidazole compound includes, for example, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, 4-ethylimidazole, 1,2-dimethylimidazole, 1,4-dimethylimidazole, 2,4-dimethylimidazole, Ethyl-2-ethylimidazole, 1-ethyl-2-phenylimidazole, 2-ethyl-2-methylimidazole, 4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 4-cyanoethyl-2-ethyl- Methylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, N- [2- (2-methyl-1- imidazolyl) ethyl] urea, 1- 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole 1-cyanoethyl-2-phenylimidazole trimellitate, 1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate, 1-cyanoethyl-2-undecyl Imidazole trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] - ethyl- (1 ')) ethyl-S-triazine], 2,4-diamino-6- [2-ethyl-4-methylimidazolyl- (2-methyl-1-imidazolylethyl) urea, N, N '- (2- Methyl-1-imidazolylethyl) adipoamide, 2,4-dialkylimidazole-dithiocarboxylic acid, 1,3-dibenzyl-2-methylimidazolium chloride, Phenyl-4,5-dihydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-bis (cyanoethoxymethyl) Methylimidazole isocyanuric acid adduct, 2-phenylimidazole iso (2'-methylimidazolyl- (1 ')] ethyl-S-triazine isocyanuric acid adduct, 2,4-diamino-6- [ Imidazole, 2,4-dialkyl-5-formylimidazole, 1-benzyl-2-phenylimidazole, imidazole-4-dithiocarboxylic acid, 2- Dithiocarboxylic acid, 2-undecylimidazole-4-dithiocarboxylic acid, 2-heptadecylimidazole-4-dithiocarboxylic acid, 2-phenylimidazole- 4-methylimidazole-5-dithiocarboxylic acid, 4-methylimidazole-5-dithiocarboxylic acid, 4-methylimidazole- 4-methylimidazole-5-dithiocarboxylic acid, 2-phenyl-4-methylimidazole-5-dithiocarboxylic acid, 1-aminoethyl- (2-methylimidazol-1-yl) urea, N, N '- [2-methylimidazolyl ) -Ethyl] -adipoyldiamide, 1-aminoethyl-2-ethyl imide Sol, 4-formylimidazole, 2-methyl-4-formylimidazole, 4-methyl-5-formylimidazole, 2-phenyl-4-methyl-4-formylimidazole, and the like.
In one embodiment of the present invention, the triazole compound may include, for example, 1,2,4-triazole, 1,2,3-triazole, benzotriazole, and the like.
In one embodiment of the present invention, the dipyridyl compound may include, for example, 2,2'-dipyridyl, 4,4'-dipyridyl, and the like.
In one embodiment of the present invention, the phenanthroline compound may include, for example, pyrimidine, purine, 1,7-phenanthroline, 1,10-phenanthroline, and the like.
In one embodiment of the present invention, the diazaphenanthroline may include, for example, pyridazine, triazine, pyrazine, 1,8-diazaphenanthroline, and the like.
The organic catalyst is preferably used in an amount of 0.001 to 0.1 part by weight based on 100 parts by weight of the total amount of raw monomers comprising an aromatic hydroxycarboxylic acid, an aromatic diol, and an aromatic dicarboxylic acid.
When the organic catalyst is used in an amount of less than 0.001 part by weight based on 100 parts by weight of the total amount of the raw material monomers, the reaction may not proceed smoothly. When the organic catalyst is used in an amount exceeding 0.1 part by weight based on 100 parts by weight of the total amount of the raw monomers A side reaction such as a decarboxylation reaction may proceed.
Next, after the acetylation reaction is performed, an inorganic catalyst is added to carry out an esterification reaction and polycondensation to prepare a prepolymer (step S2).
In the present invention, the esterification reaction of the raw monomers after the acetylation reaction is carried out using an inorganic catalyst to minimize the side reaction, and the polycondensation reaction can proceed.
In one embodiment of the present invention, after the acetylation reaction is completed at 150 ° C or lower, the inorganic catalyst may be added and the temperature may be raised to 330 ° C to allow the esterification reaction to proceed to polycondensation.
When the inorganic catalyst is used in the acetylation reaction step, the reactivity is increased, the side reaction can be promoted and the use thereof is restricted. In the esterification step, the inorganic catalyst promotes the condensation polymerization reaction and the low molecular weight oligomer can be efficiently polymerized.
As the inorganic catalyst, at least one compound selected from the group consisting of potassium acetate, calcium acetate, magnesium acetate, NaHCO 3 , phosphorylated acid, silver triflate, copper perchlorate and CuSO 4 5H 2 O can be used.
In the present invention, it is preferable that the inorganic catalyst is added in an amount of 0.001 to 0.1 part by weight based on 100 parts by weight of total amount of raw monomers composed of an aromatic hydroxycarboxylic acid, an aromatic diol and an aromatic dicarboxylic acid.
When the inorganic catalyst is used in an amount of less than 0.001 part by weight based on 100 parts by weight of the total amount of the raw material monomers, it may be difficult to effectively convert the low molecular weight oligomer into a high molecular weight. When the inorganic catalyst is used in an amount of 0.1 It may be difficult to control the reaction rate of the esterification reaction.
Finally, the prepolymer is subjected to solid phase polycondensation to produce a wholly aromatic polyester resin.
For the solid-phase polycondensation reaction in the step of synthesizing the wholly aromatic polyester resin, appropriate heat should be provided to the prepolymer. As the method of providing the heat, a method using a hot plate, a method using hot air, a method using a high- have. In order to remove by-products from the solid-phase polycondensation reaction, it is possible to purge or remove by vacuum using an inert gas.
Example
Example One
Para-hydroxybenzoic acid, biphenol, terephthalic acid and isophthalic acid were charged into a 10-liter reactor equipped with a stirrer, a reflux condenser and a temperature controller according to the weights shown in Table 1 below, and acetic anhydride was added under a nitrogen atmosphere . 1-methylimidazole was added as an organic catalyst while stirring at room temperature for 30 minutes, and the temperature was raised to 150 ° C over 30 minutes, followed by refluxing for about 3 hours to conduct the acetylation reaction. Then, potassium acetate was further added as an inorganic catalyst and the temperature was raised to 330 ° C to carry out the esterification reaction. The acetic acid produced as a byproduct was removed through a condenser. The mixture was polymerized at 330 DEG C for 6 hours to obtain a prepolymer. The prepared prepolymer was discharged from the reactor, cooled and solidified, and then pulverized to have an average particle size of 1 mm through a pulverizer. The homogeneously pulverized prepolymer was charged into a solid-phase reactor, purged with a certain amount of nitrogen, heated to 330 캜 over 5 hours, and maintained at the same temperature for 3 hours to carry out a transesterification reaction. After completion of the condensation polymerization, the solid-phase reactor was cooled for about 1 hour, and the resulting polymer was recovered.
The recovered resin was mixed so as to contain 30% of glass fibers (diameter 10 m, length 120 to 150 m), and then melt-kneaded using a twin-screw extruder to evaluate the physical properties of the pellets.
Example 2 to 4
A pellet of a wholly aromatic polyester resin was prepared in the same manner as in Example 1 except that the composition of the starting monomer shown in Table 1 was used.
Comparative Example One
A pellet of a wholly aromatic polyester resin was prepared in the same manner as in Example 1 except that only 1-methylimidazole was used as the organic catalyst in the acetylation reaction.
Comparative Example 2
A pellet of a wholly aromatic polyester resin was prepared in the same manner as in Example 1 except that potassium acetate alone was used as an inorganic catalyst in the acetylation reaction.
[Table 1]
HBA: 2-hydroxy-6-naphthoic acid, BP: biphenol, TPA: terephthalic acid, IPA: isophthalic acid, APAP: paracetamol (acetaminophen)
Test Example One
The pellets of the wholly aromatic polyester resin prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were measured for outgas component and content and oligomer outlet amount according to the following method.
(1) Method of analyzing outgas component and content: 5 g of the prepared resin pellets were placed in a Pyrolizer (PY3030D, Frontier Lab), the temperature was raised to 230 ° C at a rate of 10 ° C / min, Were collected and analyzed for outgass content and content with a GC (7890B, Agilent) device.
(2) Method of measuring oligomer flow rate: The produced resin pellets were heated at 130 ° C in a refrigerant / refrigerator oil environment used in a refrigerator compressor for home appliances, Fe catalyst for 21 days, the oligomer precipitated was filtered with a filter (0.45 탆 pore), and the weight was measured.
[Table 2]
* Oligomer effluent: the total amount of organic and oligomers released after immersing the specimen in oil
Table 2 shows that the content of the outgas and the amount of the oligomer in the case of forming the wholly aromatic polyester resin of Examples 1 to 4, in which the organic catalyst was used in the acetylation reaction and the inorganic catalyst was used in the esterification reaction, Which is significantly smaller than that of Example 1 and Comparative Example 2.
The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.
Claims (14)
After the acetylation reaction is performed, an inorganic catalyst is added to carry out an esterification reaction and polycondensation to prepare a prepolymer (step S2); And
Solid-phase polycondensation of the prepolymer (step S3);
Lt; / RTI >
here,
The organic catalyst is added in an amount of 0.001 to 0.1 part by weight based on 100 parts by weight of the total amount of raw monomers composed of an aromatic hydroxycarboxylic acid, an aromatic diol and an aromatic dicarboxylic acid,
Wherein the inorganic catalyst is added in an amount of 0.001 to 0.1 part by weight based on 100 parts by weight of the total amount of raw monomers comprising an aromatic hydroxycarboxylic acid, an aromatic diol and an aromatic dicarboxylic acid.
Wherein the aromatic hydroxycarboxylic acid comprises at least one compound selected from the group consisting of parahydroxybenzoic acid and 2-hydroxy-6-naphthoic acid.
Wherein the aromatic diol comprises at least one compound selected from the group consisting of biphenol and hydroquinone.
Wherein the aromatic dicarboxylic acid comprises at least one compound selected from the group consisting of isophthalic acid, naphthalene dicarboxylic acid and terephthalic acid.
The reactive solvent is selected from the group consisting of acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, pivalic anhydride, 2-ethylhexanoic anhydride, monochloroacetic anhydride, dichloroacetic anhydride, trichloroacetic anhydride, But are not limited to, acetic anhydride, dibromoacetic anhydride, tribromoacetic anhydride, monofluoroacetic anhydride, difluoroacetic anhydride, trifluoroacetic anhydride, glutaric anhydride, maleic anhydride, Propionic acid anhydride; and at least one compound selected from the group consisting of propionic acid anhydride and propionic acid anhydride.
The organic catalyst may be selected from the group consisting of sulfuric acid, methylene diphosphonic acid, poly (N-vinylimidazole), imidazole compound, triazole compound, dipyridyl compound, phenanthroline compound, diazaphenanthroline compound, At least one compound selected from the group consisting of diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane and N, N-dimethylaminopyridine Wherein said polyester resin is a polyester resin.
Wherein the inorganic catalyst comprises at least one compound selected from the group consisting of potassium acetate, calcium acetate, magnesium acetate, NaHCO 3 , phosphorylated acid, silver triflate, copper perchlorate and CuSO 4 5H 2 O A method for producing a wholly aromatic polyester resin.
Wherein the acetylation reaction is carried out at 150 ° C or lower.
Wherein the acetylation reaction is performed in step S2, the inorganic catalyst is added, and the temperature is raised to 330 DEG C to perform the esterification reaction.
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| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US12035467B2 (en) | 2023-06-27 | 2024-07-09 | Ticona Llc | Circuit structure |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0656385A1 (en) | 1993-06-15 | 1995-06-07 | Nippon Petrochemicals Co., Ltd. | Wholly aromatic polyester, composition thereof, and molded article made therefrom |
| EP2524955A2 (en) | 2010-01-12 | 2012-11-21 | Samsung Fine Chemicals Co., Ltd. | Production method for a wholly aromatic liquid-crystal polyester resin, a wholly aromatic liquid-crystal polyester resin produced by means of the method, and a compound of the wholly aromatic liquid-crystal polyester resin |
-
2015
- 2015-11-13 KR KR1020150159548A patent/KR101792873B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0656385A1 (en) | 1993-06-15 | 1995-06-07 | Nippon Petrochemicals Co., Ltd. | Wholly aromatic polyester, composition thereof, and molded article made therefrom |
| EP2524955A2 (en) | 2010-01-12 | 2012-11-21 | Samsung Fine Chemicals Co., Ltd. | Production method for a wholly aromatic liquid-crystal polyester resin, a wholly aromatic liquid-crystal polyester resin produced by means of the method, and a compound of the wholly aromatic liquid-crystal polyester resin |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11912817B2 (en) | 2019-09-10 | 2024-02-27 | Ticona Llc | Polymer composition for laser direct structuring |
| US11917753B2 (en) | 2019-09-23 | 2024-02-27 | Ticona Llc | Circuit board for use at 5G frequencies |
| US12035467B2 (en) | 2023-06-27 | 2024-07-09 | Ticona Llc | Circuit structure |
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| Publication number | Publication date |
|---|---|
| KR20170056204A (en) | 2017-05-23 |
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