CN116410449A - Polymer resin and method for producing same - Google Patents
Polymer resin and method for producing same Download PDFInfo
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- CN116410449A CN116410449A CN202210088766.4A CN202210088766A CN116410449A CN 116410449 A CN116410449 A CN 116410449A CN 202210088766 A CN202210088766 A CN 202210088766A CN 116410449 A CN116410449 A CN 116410449A
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- 239000002952 polymeric resin Substances 0.000 title claims abstract description 20
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 91
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 59
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 59
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 56
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920001577 copolymer Polymers 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 107
- 239000000126 substance Substances 0.000 claims description 96
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 125000001424 substituent group Chemical group 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Chemical group 0.000 claims description 12
- 229910052717 sulfur Chemical group 0.000 claims description 12
- 239000011593 sulfur Chemical group 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 239000002667 nucleating agent Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 7
- 235000014655 lactic acid Nutrition 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000004626 polylactic acid Substances 0.000 claims description 6
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- BDVLRSSEIZGSPZ-UHFFFAOYSA-N 2-but-2-enyl-3-methylbut-2-enedioic acid Chemical compound CC=CCC(C(O)=O)=C(C)C(O)=O BDVLRSSEIZGSPZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- NRIMHVFWRMABGJ-UHFFFAOYSA-N bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylic acid Chemical compound C1C2C(C(=O)O)=C(C(O)=O)C1C=C2 NRIMHVFWRMABGJ-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ZWPWUVNMFVVHHE-UHFFFAOYSA-N terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1.OC(=O)C1=CC=C(C(O)=O)C=C1 ZWPWUVNMFVVHHE-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- YCGAZNXXGKTASZ-UHFFFAOYSA-N thiophene-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)S1 YCGAZNXXGKTASZ-UHFFFAOYSA-N 0.000 description 1
- 229950005578 tidiacic Drugs 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- 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
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy 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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
-
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—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
Abstract
The present invention provides a polymer resin comprising a copolymer of polyethylene terephthalate. In the process of preparing polyethylene terephthalate, a part of terephthalic acid and/or a part of ethylene glycol is substituted with other components to obtain a copolymer of polyethylene terephthalate.
Description
Technical Field
The present invention relates to a polymer resin, and more particularly, to a copolymer of polyethylene terephthalate and a method for manufacturing the same.
Background
Polyethylene terephthalate (polyethylene terephthalate, PET) has excellent chemical resistance and has properties of rigidity, compression resistance, etc., and thus is often used in textile products, electronic products, and plastic bottles.
In general, polyethylene terephthalate is produced by condensation reaction of ethylene glycol with terephthalic acid. Since the crystallization rate of polyethylene terephthalate is too slow, polyethylene terephthalate is not suitable for high-speed processing techniques (e.g., injection molding techniques). In order to make polyethylene terephthalate suitable for high-speed processing technology, a nucleating agent is generally added to polyethylene terephthalate, thereby adjusting the crystallization rate of the polyethylene terephthalate. However, the nucleating agent in polyethylene terephthalate is liable to precipitate or separate out with increasing standing time, thereby affecting the quality of the product formed later.
Disclosure of Invention
The invention provides a polymer resin capable of improving the problem of too slow crystallization rate of polyethylene terephthalate.
The invention provides a method for producing a polymer resin, which can solve the problem of too slow crystallization rate of polyethylene terephthalate.
At least one embodiment of the present invention provides a polymer resin including a copolymer of polyethylene terephthalate represented by the following chemical formula 1:
[ chemical formula 1]
Wherein R1 comprises a residue of polyethylene glycol, a residue of lactic acid, a residue of polylactic acid, or a single bond, R comprises a benzene ring group, a straight chain carbon group, a 5-membered ring carbon group, or a 6-membered ring carbon group, wherein R is not a benzene ring group when R1 is a single bond, and Y is from 0to 1.
In some embodiments, R1 is one of chemical formulas 2 to 4:
[ chemical formula 2]
[ chemical formula 3]
Wherein n is 5 to 25 in chemical formula 3; and
[ chemical formula 4]
Wherein n is 10 to 50 in chemical formula 4.
In some embodiments, R is one of formulas 5-9:
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
Wherein in chemical formula 7X is carbon, nitrogen, oxygen or sulfur;
[ chemical formula 8]
Wherein in chemical formula 8X is carbon, nitrogen, oxygen or sulfur; and
[ chemical formula 9]
Wherein X in chemical formula 9 is carbon, nitrogen, oxygen or sulfur.
In some embodiments, the difference between the melting point and the crystallization temperature of the copolymer of polyethylene terephthalate is less than 100 degrees celsius.
In some embodiments, the copolymer of polyethylene terephthalate includes one of the following chemical formulas 10 to 13:
[ chemical formula 10]
[ chemical formula 11]
Wherein n is 10 to 50 in chemical formula 11;
[ chemical formula 12]
The method comprises the steps of carrying out a first treatment on the surface of the And
[ chemical formula 13]
Wherein n is 5 to 25 in chemical formula 13.
In some embodiments, the copolymer of polyethylene terephthalate has an intrinsic viscosity of from 0.6dL/g to 1.2dL/g.
At least one embodiment of the present invention provides a method for manufacturing a polymer resin, including: adding ethylene glycol and terephthalic acid into a reaction tank, and adding a first substituent of terephthalic acid and/or a second substituent of ethylene glycol into the reaction tank; and carrying out an esterification process on the ethylene glycol, the terephthalic acid, the second substituent and/or the first substituent in the reaction tank to obtain the polymer resin.
In some embodiments, the esterification process includes: heating glycol, terephthalic acid, the second substituent and/or the first substituent in the reaction tank to 190-210 ℃ under the environment of one atmosphere, and removing redundant water; and reducing the air pressure in the reaction tank and removing excessive water.
In some embodiments, the method of manufacturing further comprises: reducing the air pressure in the reaction tank and removing excessive alcohols until the intrinsic viscosity of the polyethylene terephthalate copolymer in the reaction tank reaches 0.6dL/g to 1.2dL/g; cooling the reaction tank and breaking vacuum in the reaction tank; and molding the copolymer of polyethylene terephthalate by an injection molding process.
In some embodiments, no nucleating agent is added to the copolymer of polyethylene terephthalate during the injection molding process.
Based on the above, the copolymer of polyethylene terephthalate has a high crystallization rate, so that it can be applied to a high-speed processing technology without adding a nucleating agent.
Drawings
Fig. 1 is a flow chart of a method of manufacturing a polymer resin according to an embodiment of the present invention.
Detailed Description
Reference will now be made in detail to the exemplary embodiments of the present invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the description to refer to the same or like parts.
In this document, a range from "one value to another value" is a shorthand way of referring individually to all the values in the range, which are avoided in the specification. Thus, recitation of a particular numerical range includes any numerical value within that range, as well as the smaller numerical range bounded by any numerical value within that range, as if the any numerical value and the smaller numerical range were written in the specification.
Fig. 1 is a flow chart of a method of manufacturing a polymer resin according to an embodiment of the present invention.
Referring to fig. 1, in step S1, ethylene glycol (Ethylene glycol) and terephthalic acid (Terephthalic Acid) are added to a reaction tank, and a first substituent of terephthalic acid and/or a second substituent of Ethylene glycol are added to the reaction tank.
In some embodiments, the first substituent of terephthalic acid comprises a dicarboxylic acid. For example, the first substituent is shown in chemical formula 14;
[ chemical formula 14]
Wherein R comprises a straight chain carbon group, a 5-membered ring carbon group or a 6-membered ring carbon group. For example, R in chemical formula 14 is one of chemical formulas 5 to 9.
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
Wherein in chemical formula 7X is carbon, nitrogen, oxygen or sulfur;
[ chemical formula 8]
Wherein in chemical formula 8X is carbon, nitrogen, oxygen or sulfur; and
[ chemical formula 9]
Wherein X in chemical formula 9 is carbon, nitrogen, oxygen or sulfur.
In some embodiments, the second substituent of ethylene glycol comprises polyethylene glycol (polyethylene glycol), lactic acid (lac acid), or Polylactic acid (PLA).
In some embodiments, in step S1, one of the first substituent and the second substituent is added to the reaction tank together with ethylene glycol and terephthalic acid, but the invention is not limited thereto. In other embodiments, the first substituent, the second substituent, ethylene glycol, and terephthalic acid are added together to the reaction tank.
Referring to fig. 1, in step S2, an esterification process is performed on the ethylene glycol, the terephthalic acid, and the first substituent and/or the second substituent in the reaction tank.
In some embodiments, the esterification process includes a first stage and a second stage. The first stage comprises heating the ethylene glycol, terephthalic acid and the first substituent and/or the second substituent in the reaction tank to 190-210 ℃ under normal pressure (one atmosphere), and removing excessive water. In some embodiments, excess moisture from the dehydrocondensation polymerization begins to occur in the reaction tank at a temperature of about 160 degrees celsius in the reaction tank. At a temperature of about 190 degrees celsius in the reaction tank, a catalyst and an antioxidant are initially introduced into the reaction tank, wherein the catalyst is added for the purpose of allowing the polymerization to continue and the antioxidant is added for the purpose of avoiding yellowing of the synthesized polyethylene terephthalate copolymer. In some embodiments, the amount of moisture that is generated by the polymerization reaction may be estimated based on the mole number of the starting materials, and the second stage of the esterification process may be performed after the amount of moisture removed reaches about 80% of the amount of moisture that would be generated by the polymerization reaction.
The second stage of the esterification process includes reducing the air pressure in the reaction tank and continuing to remove excess water. In some embodiments, the air pressure in the reaction tank is slowly reduced to perform negative pressure dehydration. In the second stage of the esterification process, the degree of negative pressure needs to be controlled, and if the pressure is reduced too fast, alcohols in the reaction tank are easily removed.
In step S3, after the esterification process, the air pressure in the reaction tank is continuously reduced, and excessive alcohols are removed, so that prepolymer molecules in the reaction tank are polymerized, and the viscosity and the molecular weight of the reactant are improved. In some embodiments, excess alcohol is removed until the intrinsic viscosity of the polyethylene terephthalate copolymer in the reaction tank reaches 0.6dL/g to 1.2dL/g, for example 0.8dL/g.
Next, in step S4, the reaction tank is cooled (e.g., to 120 degrees celsius), and nitrogen or other gas is introduced into the reaction tank to break the vacuum in the reaction tank.
The polymer resin obtained after the above steps are completed includes a copolymer of polyethylene terephthalate represented by the following chemical formula 1:
[ chemical formula 1]
In some embodiments, R1 in chemical formula 1 comprises a residue of polyethylene glycol, a residue of lactic acid, a residue of polylactic acid, or a single bond. For example, R1 in chemical formula 1 is one of chemical formulas 2 to 4:
[ chemical formula 2]
[ chemical formula 3]
Wherein n is 5 to 25 in chemical formula 3; and
[ chemical formula 4]
Wherein n is 10 to 50 in chemical formula 4.
In some embodiments, R in chemical formula 1 comprises a phenyl ring group, a straight chain carbon group, a 5-membered ring carbon group, or a 6-membered ring carbon group. For example, R in chemical formula 1 is one of chemical formulas 5 to 9.
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
Wherein in chemical formula 7X is carbon, nitrogen, oxygen or sulfur;
[ chemical formula 8]
Wherein in chemical formula 8X is carbon, nitrogen, oxygen or sulfur; and
[ chemical formula 9]
Wherein X in chemical formula 9 is carbon, nitrogen, oxygen or sulfur.
In chemical formula 1, R is not a benzene ring group when R1 is a single bond, and Y is between 0 and 1.
In one embodiment, a first substituent is used to replace a portion of the terephthalic acid, wherein the total of terephthalic acid and the first substituent is 1, the mole fraction of terephthalic acid is 0.7, and the mole fraction of the first substituent (e.g., dicarboxylic acid of chemical formula 14) is 0.3. Meanwhile, ethylene glycol is used as an excessive amount agent to synthesize a copolymer of polyethylene terephthalate represented by chemical formula 10:
[ chemical formula 10]
R in chemical formula 10 contains a benzene ring group, a straight chain carbon group, a 5-membered ring carbon group or a 6-membered ring carbon group. For example, R in chemical formula 10 is one of chemical formulas 5 to 9.
In one embodiment, polyethylene glycol is used to replace a portion of the ethylene glycol, wherein the sum of the ethylene glycol and the polyethylene glycol is 1, the Moir fraction of the ethylene glycol is 0.95, and the Moir fraction of the polyethylene glycol is 0.05. Meanwhile, terephthalic acid is used as an excessive amount agent to synthesize a copolymer of polyethylene terephthalate represented by chemical formula 11:
[ chemical formula 11]
In chemical formula 11, n is 10 to 50.
In one embodiment, lactic acid is used to replace a portion of the ethylene glycol, wherein the molar fraction of lactic acid is 0.3 with a molar fraction of terephthalic acid of 1. Meanwhile, ethylene glycol is used as an excessive amount agent to synthesize a copolymer of polyethylene terephthalate represented by chemical formula 12:
[ chemical formula 12]
In one embodiment, polylactic acid is used to replace a portion of the ethylene glycol, wherein the molar fraction of polylactic acid is 0.05 at a molar fraction of terephthalic acid of 1. Meanwhile, ethylene glycol is used as an excessive amount agent to synthesize a copolymer of polyethylene terephthalate represented by chemical formula 13:
[ chemical formula 13]
In chemical formula 13, n is 5 to 25.
In some embodiments, the difference between the melting point (Tm) and the crystallization temperature (Tc) of the copolymer of polyethylene terephthalate is less than 100 degrees celsius, thereby providing a higher crystallization rate of the copolymer of polyethylene terephthalate. Thus, copolymers of polyethylene terephthalate are suitable for high speed processing techniques (e.g., injection molding) and do not require the addition of a nucleating agent.
In some embodiments, the copolymer of polyethylene terephthalate is molded by an injection molding process, and no nucleating agent is added to the copolymer of polyethylene terephthalate during the injection molding process. In some embodiments, the copolymers of polyethylene terephthalate are suitable for use in packaging bottles, fibers, various types of films, or other plastic products.
Based on the above, the copolymer of polyethylene terephthalate has a high crystallization rate, so that it can be applied to a high-speed processing technology without adding a nucleating agent.
Hereinafter, examples of some of the copolymers of polyethylene terephthalate of the present invention are provided, however, these examples are illustrative and the present invention is not limited to these examples.
Example 1
0.7 mole of terephthalic acid, 1.05 mole of ethylene glycol, and 0.3 mole of adipic acid were added to the reaction tank. The reaction tank was then heated to 200 degrees celsius at one atmosphere. During the heating process, when the temperature of the reaction tank is heated to about 160 ℃, moisture begins to appear in the reaction tank. In addition, when the temperature of the reaction tank was heated to about 190 degrees celsius, 0.05g of a catalyst and 0.5g of an antioxidant were added to the reaction tank, and an atmospheric polymerization reaction was performed.
After the water removed from the reaction tank reached about 80% of the water to be produced by the completion of the polymerization reaction, the pressure in the reaction tank was gradually reduced to conduct negative pressure dehydration. In this example, the pressure in the reaction tank was reduced by about 50torr every 20 minutes. After the pressure in the reaction tank was reduced to 200torr, the reaction tank was evacuated to about 0torr and subjected to negative pressure dealcoholization for 2 hours. Next, the viscosity of the polymer (i.e., the copolymer of polyethylene terephthalate) in the reaction tank was measured. And after the viscosity of the polymer in the reaction tank reaches a target value, cooling the reaction tank to 120 ℃, and then breaking vacuum by nitrogen to obtain a finished product.
Example 2
0.7 mole of terephthalic acid, 1.05 mole of ethylene glycol, and 0.3 mole of sebacic acid were added to the reaction tank. The reaction tank was then heated to 200 degrees celsius at one atmosphere. During the heating process, when the temperature of the reaction tank is heated to about 160 ℃, moisture begins to appear in the reaction tank. In addition, when the temperature of the reaction tank was heated to about 190 degrees celsius, 0.05g of a catalyst and 0.5g of an antioxidant were added to the reaction tank, and an atmospheric polymerization reaction was performed.
After the water removed from the reaction tank reached about 80% of the water to be produced by the completion of the polymerization reaction, the pressure in the reaction tank was gradually reduced to conduct negative pressure dehydration. In this example, the pressure in the reaction tank was reduced by about 50torr every 20 minutes. After the pressure in the reaction tank was reduced to 200torr, the reaction tank was evacuated to about 0torr and subjected to negative pressure dealcoholization for 2 hours. Next, the viscosity of the polymer (i.e., the copolymer of polyethylene terephthalate) in the reaction tank was measured. And after the viscosity of the polymer in the reaction tank reaches a target value, cooling the reaction tank to 120 ℃, and then breaking vacuum by nitrogen to obtain a finished product.
Example 3
1 mole of terephthalic acid, 1.05 mole of ethylene glycol, and 0.3 mole of lactic acid were added to the reaction tank. The reaction tank was then heated to 200 degrees celsius at one atmosphere. During the heating process, when the temperature of the reaction tank is heated to about 160 ℃, moisture begins to appear in the reaction tank. In addition, when the temperature of the reaction tank was heated to about 190 degrees celsius, 0.05g of a catalyst and 0.5g of an antioxidant were added to the reaction tank, and an atmospheric polymerization reaction was performed.
After the water removed from the reaction tank reached about 80% of the water to be produced by the completion of the polymerization reaction, the pressure in the reaction tank was gradually reduced to conduct negative pressure dehydration. In this example, the pressure in the reaction tank was reduced by about 50torr every 20 minutes. After the pressure in the reaction tank was reduced to 200torr, the reaction tank was evacuated to about 0torr and subjected to negative pressure dealcoholization for 2 hours. Next, the viscosity of the polymer (i.e., the copolymer of polyethylene terephthalate) in the reaction tank was measured. And after the viscosity of the polymer in the reaction tank reaches a target value, cooling the reaction tank to 120 ℃, and then breaking vacuum by nitrogen to obtain a finished product.
Example 4
0.7 mole of terephthalic acid, 1.05 mole of ethylene glycol, and 0.3 mole of 2, 5-thiophene dicarboxylic acid (2, 5-TDCA) were added to the reaction tank. The reaction tank was then heated to 200 degrees celsius at one atmosphere. During the heating process, when the temperature of the reaction tank is heated to about 160 ℃, moisture begins to appear in the reaction tank. In addition, when the temperature of the reaction tank was heated to about 190 degrees celsius, 0.05g of a catalyst and 0.5g of an antioxidant were added to the reaction tank, and an atmospheric polymerization reaction was performed.
After the water removed from the reaction tank reached about 80% of the water to be produced by the completion of the polymerization reaction, the pressure in the reaction tank was gradually reduced to conduct negative pressure dehydration. In this example, the pressure in the reaction tank was reduced by about 50torr every 20 minutes. After the pressure in the reaction tank was reduced to 200torr, the reaction tank was evacuated to about 0torr and subjected to negative pressure dealcoholization for 2 hours. Next, the viscosity of the polymer (i.e., the copolymer of polyethylene terephthalate) in the reaction tank was measured. And after the viscosity of the polymer in the reaction tank reaches a target value, cooling the reaction tank to 120 ℃, and then breaking vacuum by nitrogen to obtain a finished product.
Example 5
0.7 mole of terephthalic acid, 1.05 mole of ethylene glycol, and 0.3 mole of Bicyclo [2.2.1] hepta-2, 3-dicarboxylic acid (dicycloheo [2.2.1] hepta-2,5-diene-2,3-dicarboxylic acid) were added to the reaction tank. The reaction tank was then heated to 200 degrees celsius at one atmosphere. During the heating process, when the temperature of the reaction tank is heated to about 160 ℃, moisture begins to appear in the reaction tank. In addition, when the temperature of the reaction tank was heated to about 190 degrees celsius, 0.05g of a catalyst and 0.5g of an antioxidant were added to the reaction tank, and an atmospheric polymerization reaction was performed.
After the water removed from the reaction tank reached about 80% of the water to be produced by the completion of the polymerization reaction, the pressure in the reaction tank was gradually reduced to conduct negative pressure dehydration. In this example, the pressure in the reaction tank was reduced by about 50torr every 20 minutes. After the pressure in the reaction tank was reduced to 200torr, the reaction tank was evacuated to about 0torr and subjected to negative pressure dealcoholization for 2 hours. Next, the viscosity of the polymer (i.e., the copolymer of polyethylene terephthalate) in the reaction tank was measured. And after the viscosity of the polymer in the reaction tank reaches a target value, cooling the reaction tank to 120 ℃, and then breaking vacuum by nitrogen to obtain a finished product.
Table 1 shows the melting point (Tm), crystallization temperature (Tc), glass transition temperature (Tg) and the difference between the melting point and crystallization temperature (Δt) of the general polyethylene terephthalate (polyethylene terephthalate, PET) and the polyethylene terephthalate copolymers synthesized in examples 1 to 5.
TABLE 1
| Tm(℃) | Tc(℃) | Tg(℃) | △T(Tm-Tc)(℃) | |
| PET | 255 | 184 | 83 | 71 |
| Example 1 | 220 | 151 | 58 | 69 |
| Example 2 | 209 | 162 | 37 | 47 |
| Example 3 | 228 | 163 | 55 | 65 |
| Example 4 | 238 | 177 | 80 | 61 |
| Example 5 | 227 | 161 | 78 | 66 |
As can be seen from table 1, the difference between the melting point and the crystallization temperature of the polyethylene terephthalate copolymers synthesized in examples 1 to 5 is smaller than that of the general polyethylene terephthalate. Thus, the polyethylene terephthalate copolymers synthesized in examples 1 to 5 have a high crystallization rate and can be used for high-speed processing without the need of adding a nucleating agent.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A polymer resin comprising a copolymer of polyethylene terephthalate represented by the following chemical formula 1:
[ chemical formula 1]
2. The polymer resin according to claim 1, wherein R1 is one of the following chemical formulas 2 to 4:
[ chemical formula 2]
[ chemical formula 3]
[ chemical formula 4]
3. The polymer resin according to claim 1, wherein R is one of the following chemical formulas 5 to 9:
[ chemical formula 5]
[ chemical formula 6]
[ chemical formula 7]
[ chemical formula 8]
[ chemical formula 9]
4. The polymer resin of claim 1, wherein the difference between the melting point and the crystallization temperature of the copolymer of polyethylene terephthalate is less than 100 degrees celsius.
5. The polymer resin according to claim 1, wherein the copolymer of polyethylene terephthalate includes one of the following chemical formulas 10 to 13:
[ chemical formula 10]
[ chemical formula 11]
Wherein in chemical formula 11, n is 10 to 50;
[ chemical formula 12]
[ chemical formula 13]
Wherein in chemical formula 13, n is 5 to 25.
6. The polymer resin of claim 1, wherein the copolymer of polyethylene terephthalate has an intrinsic viscosity of from 0.6dL/g to 1.2dL/g.
7. A method of manufacturing a polymer resin, comprising:
adding ethylene glycol and terephthalic acid into a reaction tank, and adding a first substituent of terephthalic acid and/or a second substituent of ethylene glycol into the reaction tank; and
and (3) carrying out an esterification process on the ethylene glycol, the terephthalic acid, the second substituent and/or the first substituent in the reaction tank, and obtaining the polymer resin in one of the request items 1 to 5.
8. The method of claim 7, wherein the esterification process comprises:
heating the glycol, terephthalic acid and the second substituent and/or the first substituent in the reaction tank to 190-210 ℃ under the environment of one atmosphere, and removing redundant water; and
reducing the air pressure in the reaction tank and removing redundant water.
9. The method of manufacturing according to claim 7, further comprising:
reducing the air pressure in the reaction tank and removing excessive alcohols until the intrinsic viscosity of the polyethylene terephthalate copolymer in the reaction tank reaches 0.6dL/g to 1.2dL/g;
cooling the reaction tank and breaking vacuum in the reaction tank; and
the copolymer of polyethylene terephthalate is molded by an injection molding process.
10. The method according to claim 9, wherein a nucleating agent is not added to the copolymer of polyethylene terephthalate in the injection molding process.
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