TW202325791A - Polymer resin and manufacturing method thereof - Google Patents
Polymer resin and manufacturing method thereof Download PDFInfo
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- TW202325791A TW202325791A TW110149305A TW110149305A TW202325791A TW 202325791 A TW202325791 A TW 202325791A TW 110149305 A TW110149305 A TW 110149305A TW 110149305 A TW110149305 A TW 110149305A TW 202325791 A TW202325791 A TW 202325791A
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- 239000002952 polymeric resin Substances 0.000 title claims abstract description 19
- 229920003002 synthetic resin Polymers 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 54
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 54
- 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 53
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 49
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 107
- 239000000126 substance Substances 0.000 claims description 106
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 125000001424 substituent group Chemical group 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 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
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 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
- 238000001746 injection moulding Methods 0.000 claims description 8
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000004626 polylactic acid Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 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
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims 2
- 150000003504 terephthalic acids Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- 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 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 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
- 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 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- KVZLHPXEUGJPAH-UHFFFAOYSA-N 2-oxidanylpropanoic acid Chemical compound CC(O)C(O)=O.CC(O)C(O)=O KVZLHPXEUGJPAH-UHFFFAOYSA-N 0.000 description 1
- SENMPMXZMGNQAG-UHFFFAOYSA-N 3,4-dihydro-2,5-benzodioxocine-1,6-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC=C12 SENMPMXZMGNQAG-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003786 synthesis 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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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
- C08G63/12—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
Description
本發明是有關於一種聚合物樹脂，且特別是有關於一種聚對苯二甲酸乙二酯的共聚物及其製造方法。The present invention relates to a polymer resin, and in particular to a polyethylene terephthalate copolymer and its manufacturing method.
聚對苯二甲酸乙二酯（polyethylene terephthalate, PET）具有優秀的耐化學性，且具有堅硬、抗壓等特性，因此常被應用於紡織產品、電子產品和塑料瓶中。Polyethylene terephthalate (PET) has excellent chemical resistance, and has properties such as hardness and compression resistance, so it is often used in textile products, electronic products and plastic bottles.
一般而言，聚對苯二甲酸乙二酯是利用乙二醇與對苯二甲酸經過縮合反應而製成。由於聚對苯二甲酸乙二酯的結晶速率太慢，因此，聚對苯二甲酸乙二酯不適用於高速加工的技術（例如射出成型技術）。為了使聚對苯二甲酸乙二酯能夠適用於高速加工的技術，一般會於聚對苯二甲酸乙二酯中加入成核劑，藉此調整聚對苯二甲酸乙二酯的結晶速率。然而，雖著放置時間的增加，聚對苯二甲酸乙二酯中中的成核劑容易出現沉澱或析出的問題，進而影響了後續形成之產品的品質。Generally speaking, polyethylene terephthalate is made by condensation reaction of ethylene glycol and terephthalic acid. Since the crystallization rate of polyethylene terephthalate is too slow, polyethylene terephthalate is not suitable for high-speed processing technology (such as injection molding technology). In order to make polyethylene terephthalate suitable for high-speed processing technology, a nucleating agent is generally added to polyethylene terephthalate to adjust the crystallization rate of polyethylene terephthalate. However, as the storage time increases, the nucleating agent in the polyethylene terephthalate is prone to precipitation or precipitation, which affects the quality of subsequent products.
本發明提供一種聚合物樹脂，能改善聚對苯二甲酸乙二酯結晶速率過慢的問題。The invention provides a polymer resin, which can improve the problem that the crystallization rate of polyethylene terephthalate is too slow.
本發明提供一種聚合物樹脂的製造方法，能改善聚對苯二甲酸乙二酯結晶速率過慢的問題。The invention provides a method for producing a polymer resin, which can improve the problem that the crystallization rate of polyethylene terephthalate is too slow.
本發明的至少一實施例提供一種聚合物樹脂，包括以下化學式1表示的聚對苯二甲酸乙二酯的共聚物： [化學式1] ， 其中R 1包含聚乙二醇的殘基、乳酸的殘基、聚乳酸的殘基或單鍵，R包含苯環基、直鏈碳基、5元環碳基或6元環碳基，其中當R 1為單鍵時R不為苯環基，Y介於0至1。 At least one embodiment of the present invention provides a polymer resin comprising a copolymer of polyethylene terephthalate represented by the following chemical formula 1: [chemical formula 1] , wherein R 1 comprises a residue of polyethylene glycol, a residue of lactic acid, a residue of polylactic acid or a single bond, R comprises a phenyl ring group, a straight-chain carbon group, a 5-membered ring carbon group or a 6-membered ring carbon group, Wherein when R 1 is a single bond, R is not a phenyl ring group, and Y is between 0 and 1.
在一些實施例中，R 1為化學式2至化學式4中的其中一者： [化學式2] ； [化學式3] ， 其中在化學式3中n為5至25；以及 [化學式4] ， 其中在化學式4中n為10至50。 In some embodiments, R 1 is one of Chemical Formula 2 to Chemical Formula 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.
在一些實施例中，R為化學式5至化學式9中的其中一者： [化學式5] ； [化學式6] ； [化學式7] ， 其中在化學式7中X為碳、氮、氧或硫； [化學式8] ， 其中在化學式8中X為碳、氮、氧或硫；以及 [化學式9] ， 其中在化學式9中X為碳、氮、氧或硫。 In some embodiments, R is one of Chemical Formula 5 to Chemical Formula 9: [Chemical Formula 5] ; [chemical formula 6] ; [chemical formula 7] , wherein X is carbon, nitrogen, oxygen or sulfur in chemical formula 7; [chemical formula 8] , wherein in Chemical Formula 8 X is carbon, nitrogen, oxygen or sulfur; and [Chemical Formula 9] , wherein X in Chemical Formula 9 is carbon, nitrogen, oxygen or sulfur.
在一些實施例中，聚對苯二甲酸乙二酯的共聚物的熔點與結晶溫度之間的差值小於攝氏100度。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.
在一些實施例中，聚對苯二甲酸乙二酯的共聚物包括以下化學式10至化學式13中的其中一者： [化學式10] ； [化學式11] ， 其中在化學式11中n為10至50； [化學式12] ；以及 [化學式13] ， 其中在化學式13中n為5至25。 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] ; and [Chemical Formula 13] , wherein n is 5 to 25 in Chemical Formula 13.
在一些實施例中，聚對苯二甲酸乙二酯的共聚物的特性黏度達到0.6 dL/g至1.2 dL/g。In some embodiments, the intrinsic viscosity of the copolymer of polyethylene terephthalate ranges from 0.6 dL/g to 1.2 dL/g.
本發明的至少一實施例提供一種聚合物樹脂的製造方法，包括：將乙二醇和對苯二甲酸加入反應槽中，並於反應槽中加入對苯二甲酸之第一取代物及/或乙二醇之第二取代物；以及對反應槽中的乙二醇、對苯二甲酸與第二取代物及/或第一取代物進行酯化製程，並獲得聚合物樹脂。At least one embodiment of the present invention provides a method for producing a polymer resin, comprising: adding ethylene glycol and terephthalic acid into a reaction tank, and adding the first substitute of terephthalic acid and/or ethyl alcohol into the reaction tank. the second substituent of diol; and performing an esterification process on the ethylene glycol, terephthalic acid and the second substituent and/or the first substituent in the reaction tank to obtain a polymer resin.
在一些實施例中，酯化製程包括：在一大氣壓的環境下將反應槽中的乙二醇、對苯二甲酸與第二取代物及/或第一取代物加溫至攝氏190度至攝氏210度，並脫出多餘的水分；以及減少反應槽中的氣壓，並脫出多餘的水分。In some embodiments, the esterification process includes: heating the ethylene glycol, terephthalic acid, and the second substituent and/or the first substituent in the reaction tank to 190 degrees Celsius to 190 degrees Celsius under an atmosphere of atmospheric pressure 210 degrees, and remove excess moisture; and reduce the air pressure in the reaction tank, and remove excess moisture.
在一些實施例中，製造方法更包括：減少反應槽中的氣壓，並脫出多餘的醇類，直到反應槽中的聚對苯二甲酸乙二酯的共聚物的特性黏度達到0.6 dL/g至1.2 dL/g；將反應槽降溫，並使反應槽破真空；以及以射出成型製程使聚對苯二甲酸乙二酯的共聚物成型。In some embodiments, the manufacturing method further includes: reducing the air pressure in the reaction tank, and releasing excess alcohols until the intrinsic viscosity of the polyethylene terephthalate copolymer in the reaction tank reaches 0.6 dL/g to 1.2 dL/g; the temperature of the reaction tank was lowered, and the vacuum of the reaction tank was broken; and the copolymer of polyethylene terephthalate was molded by an injection molding process.
在一些實施例中，在進行射出成型製程時，不於聚對苯二甲酸乙二酯的共聚物中加入成核劑。In some embodiments, no nucleating agent is added to the polyethylene terephthalate copolymer during the injection molding process.
基於上述，聚對苯二甲酸乙二酯的共聚物具有較高的結晶速率，因此不需要額外添加成核劑就可以適用於高速加工的技術。Based on the above, the copolymer of polyethylene terephthalate has a high crystallization rate, so it can be applied to high-speed processing technology without additional nucleating agent.
在本文中，由「一數值至另一數值」表示的範圍，是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此，某一特定數值範圍的記載，涵蓋該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍，如同在說明書中說明文寫出該任意數值和該較小數值範圍一樣。Herein, a range indicated by "one value to another value" is a general representation which avoids enumerating all values in the range in the specification. Therefore, the description of a specific numerical range covers any numerical value in the numerical range and the smaller numerical range defined by any numerical value in the numerical range, as if the arbitrary numerical value and the smaller numerical range are written in the specification. The value range is the same.
圖1是依照本發明的一實施例的一種聚合物樹脂的製造方法的流程圖。FIG. 1 is a flowchart of a method for manufacturing a polymer resin according to an embodiment of the present invention.
請參考圖1，在步驟S1中，將乙二醇（Ethylene glycol）和對苯二甲酸（Terephthalic Acid）加入反應槽中，並於反應槽中加入對苯二甲酸之第一取代物及/或乙二醇之第二取代物。Please refer to Figure 1, in step S1, add ethylene glycol (Ethylene glycol) and terephthalic acid (Terephthalic Acid) into the reaction tank, and add the first substitute of terephthalic acid and/or A second substitute for ethylene glycol.
在一些實施例中，對苯二甲酸之第一取代物包括二羧酸。舉例來說，第一取代物如化學式14所示； [化學式14] ， 其中R包含直鏈碳基、5元環碳基或6元環碳基。舉例來說，化學式14中的R為化學式5至化學式9中的其中一者。 [化學式5] ； [化學式6] ； [化學式7] ， 其中在化學式7中X為碳、氮、氧或硫； [化學式8] ， 其中在化學式8中X為碳、氮、氧或硫；以及 [化學式9] ， 其中在化學式9中X為碳、氮、氧或硫。 In some embodiments, the first substitute for terephthalic acid includes 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 Formula 5 to Chemical Formula 9. [chemical formula 5] ; [chemical formula 6] ; [chemical formula 7] , wherein X is carbon, nitrogen, oxygen or sulfur in chemical formula 7; [chemical formula 8] , wherein in Chemical Formula 8 X is carbon, nitrogen, oxygen or sulfur; and [Chemical Formula 9] , wherein X in Chemical Formula 9 is carbon, nitrogen, oxygen or sulfur.
在一些實施例中，乙二醇之第二取代物包括聚乙二醇（Polyethylene glycol）、乳酸（Lactic acid）或聚乳酸（Polylactic acid, PLA）。In some embodiments, the second substituent of ethylene glycol includes polyethylene glycol (Polyethylene glycol), lactic acid (Lactic acid) or polylactic acid (Polylactic acid, PLA).
在一些實施例中，在步驟S1中，將第一取代物及第二取代物中的其中一者與乙二醇以及對苯二甲酸一起加入反應槽中，但本發明不以此為限。在其他實施例中，將第一取代物、第二取代物、乙二醇以及對苯二甲酸一起加入反應槽中。In some embodiments, in step S1, one of the first substituent and the second substituent is added into 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 into the reaction tank.
請繼續參考圖1，在步驟S2中，對反應槽中的乙二醇、對苯二甲酸與第一取代物及/或第二取代物進行酯化製程。Please continue to refer to FIG. 1 , in step S2 , an esterification process is performed on the ethylene glycol, terephthalic acid and the first substituent and/or the second substituent in the reaction tank.
在一些實施例中，前述酯化製程包括第一階段以及第二階段。第一階段包括在常壓（一大氣壓）的環境下將反應槽中的乙二醇、對苯二甲酸與第一取代物及/或第二取代物加溫至攝氏190度至攝氏210度，並脫出多餘的水分。在一些實施例中，在反應槽中的溫度約攝氏160度時，反應槽內即開始出現脫水縮合聚合反應所產生之多餘的水分。在反應槽中的溫度約攝氏190度時，開始於反應槽中加入催化劑和抗氧化劑，其中加入催化劑的目的在於使聚合反應可以持續進行，而加入抗氧化劑的目的則在於避免所合成之聚對苯二甲酸乙二酯的共聚物出現黃化的問題。在一些實施例中，聚合反應會生成之水分可以基於原料的莫耳數進行推算，當脫出之水分達到聚合反應完全所應產生之水分的約80%之後，進行酯化製程的第二階段。In some embodiments, the aforementioned esterification process includes a first stage and a second stage. The first stage includes heating the ethylene glycol, terephthalic acid and the first substituent and/or the second substituent in the reaction tank to 190 degrees Celsius to 210 degrees Celsius under normal pressure (atmospheric pressure), and remove excess moisture. In some embodiments, when the temperature in the reaction tank is about 160 degrees Celsius, excess moisture generated by the dehydration condensation polymerization reaction begins to appear in the reaction tank. When the temperature in the reaction tank is about 190 degrees Celsius, the catalyst and antioxidant are added to the reaction tank. The purpose of adding the catalyst is to make the polymerization reaction continue, and the purpose of adding the antioxidant is to prevent the synthesis of the polymer. Copolymers of ethylene phthalate suffer from yellowing problems. In some embodiments, the moisture generated by the polymerization reaction can be calculated based on the moles of raw materials. When the moisture released reaches about 80% of the moisture that should be generated by the polymerization reaction, the second stage of the esterification process is carried out. .
酯化製程的第二階段包括減少反應槽中的氣壓，並繼續脫出多餘的水分。在一些實施例中，緩慢將反應槽內的氣壓減少，以進行負壓脫水。在酯化製程的第二階段中，需要控制負壓的程度，若降壓太快容易導致反應槽內的醇類被脫出。The second stage of the esterification process involves 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. If the pressure is reduced too quickly, the alcohols in the reaction tank will be released.
在步驟S3中，在酯化製程之後，繼續減少反應槽中的氣壓，並脫出多餘的醇類，使反應槽內的預聚物分子聚合，並提高反應物的黏度與分子量。在一些實施例中，脫出多餘的醇類直到反應槽中的聚對苯二甲酸乙二酯的共聚物的特性黏度達到0.6 dL/g至1.2 dL/g，例如0.8 dL/g。In step S3, after the esterification process, continue to reduce the air pressure in the reaction tank, and remove excess alcohols, polymerize the prepolymer molecules in the reaction tank, and increase the viscosity and molecular weight of the reactants. In some embodiments, excess alcohol is removed until the intrinsic viscosity of the polyethylene terephthalate copolymer in the reaction tank reaches 0.6 dL/g to 1.2 dL/g, such as 0.8 dL/g.
接著，在步驟S4中，將反應槽降溫（例如降至攝氏120度），並將氮氣或其他氣體通入反應槽內，使反應槽破真空。Next, in step S4, the temperature of the reaction tank is lowered (for example, to 120 degrees Celsius), and nitrogen or other gases are passed into the reaction tank to break the vacuum of the reaction tank.
在完成上述步驟後獲得之聚合物樹脂包括以下化學式1表示的聚對苯二甲酸乙二酯的共聚物： [化學式1] 。 The polymer resin obtained after completing the above steps includes a copolymer of polyethylene terephthalate represented by the following Chemical Formula 1: [Chemical Formula 1] .
在一些實施例中，化學式1中R 1包含聚乙二醇的殘基、乳酸的殘基、聚乳酸的殘基或單鍵。舉例來說，化學式1中的R 1為化學式2至化學式4中的其中一者： [化學式2] ； [化學式3] ， 其中在化學式3中n為5至25；以及 [化學式4] ， 其中在化學式4中n為10至50。 In some embodiments, R 1 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, R in Chemical Formula 1 is one of Chemical Formula 2 to Chemical Formula 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.
在一些實施例中，化學式1中的R包含苯環基、直鏈碳基、5元環碳基或6元環碳基。舉例來說，化學式1中的R為化學式5至化學式9中的其中一者。 [化學式5] ； [化學式6] ； [化學式7] ， 其中在化學式7中X為碳、氮、氧或硫； [化學式8] ， 其中在化學式8中X為碳、氮、氧或硫；以及 [化學式9] ， 其中在化學式9中X為碳、氮、氧或硫。 In some embodiments, R in Chemical Formula 1 includes a phenyl ring group, a linear 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 Formula 5 to Chemical Formula 9. [chemical formula 5] ; [chemical formula 6] ; [chemical formula 7] , wherein X is carbon, nitrogen, oxygen or sulfur in chemical formula 7; [chemical formula 8] , wherein in Chemical Formula 8 X is carbon, nitrogen, oxygen or sulfur; and [Chemical Formula 9] , wherein X in Chemical Formula 9 is carbon, nitrogen, oxygen or sulfur.
在化學式1中，當R 1為單鍵時R不為苯環基，且Y介於0至1。 In Chemical Formula 1, when R 1 is a single bond, R is not a phenyl ring group, and Y is between 0 and 1.
在一實施例中，使用第一取代物取代部分對苯二甲酸，其中以對苯二甲酸與第一取代物的總合為1，對苯二甲酸的莫爾分率為0.7，且第一取代物（如化學式14所示的二羧酸）的莫爾分率為0.3。同時，以乙二醇作為過量式劑，以合成化學式10所示之聚對苯二甲酸乙二酯的共聚物： [化學式10] ， 化學式10中的R包含苯環基、直鏈碳基、5元環碳基或6元環碳基。舉例來說，化學式10中的R為化學式5至化學式9中的其中一者。 In one embodiment, the first substituent is used to replace part of the terephthalic acid, wherein the sum of the terephthalic acid and the first substituent is 1, the mole fraction of the terephthalic acid is 0.7, and the first The mole fraction of the substituent (such as the dicarboxylic acid shown in Chemical Formula 14) is 0.3. Simultaneously, with ethylene glycol as excess formulation agent, to synthesize the copolymer of polyethylene terephthalate shown in chemical formula 10: [chemical formula 10] , R in Chemical Formula 10 includes 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 10 is one of Chemical Formula 5 to Chemical Formula 9.
在一實施例中，使用聚乙二醇取代部分乙二醇，其中以乙二醇與聚乙二醇的總合為1，乙二醇的莫爾分率為0.95，且聚乙二醇的莫爾分率為0.05。同時，以對苯二甲酸作為過量式劑，以合成化學式11所示之聚對苯二甲酸乙二酯的共聚物： [化學式11] ， 化學式11中n為10至50。 In one embodiment, polyethylene glycol is used to replace part of ethylene glycol, wherein the total of ethylene glycol and polyethylene glycol is 1, the mole fraction of ethylene glycol is 0.95, and the mole fraction of polyethylene glycol is The molar fraction is 0.05. Simultaneously, use terephthalic acid as excess formula agent, to synthesize the copolymer of polyethylene terephthalate shown in chemical formula 11: [chemical formula 11] , n in Chemical Formula 11 is 10 to 50.
在一實施例中，使用乳酸取代部分乙二醇，其中以對苯二甲酸的莫爾分率為1，乳酸的莫爾分率為0.3。同時，以乙二醇作為過量式劑，以合成化學式12所示之聚對苯二甲酸乙二酯的共聚物： [化學式12] 。 In one embodiment, lactic acid is used to replace part of ethylene glycol, wherein the mole fraction of terephthalic acid is 1, and the mole fraction of lactic acid is 0.3. Simultaneously, with ethylene glycol as excess formulation agent, to synthesize the copolymer of polyethylene terephthalate shown in chemical formula 12: [chemical formula 12] .
在一實施例中，使用聚乳酸取代部分乙二醇，其中以對苯二甲酸的莫爾分率為1，聚乳酸的莫爾分率為0.05。同時，以乙二醇作為過量式劑，以合成化學式13所示之聚對苯二甲酸乙二酯的共聚物： [化學式13] ， 化學式13中n為5至25。 In one embodiment, polylactic acid is used to replace part of ethylene glycol, wherein the molar fraction of terephthalic acid is 1, and the molar fraction of polylactic acid is 0.05. Simultaneously, with ethylene glycol as excess formulation agent, to synthesize the copolymer of polyethylene terephthalate shown in chemical formula 13: [chemical formula 13] , n in Chemical Formula 13 is 5 to 25.
在一些實施例中，聚對苯二甲酸乙二酯的共聚物的熔點（Tm）與結晶溫度（Tc）之間的差值小於攝氏100度，藉此使聚對苯二甲酸乙二酯的共聚物具有較高的結晶速率。因此，聚對苯二甲酸乙二酯的共聚物適用於高速加工的技術（例如射出成型），且不需要額外添加成核劑。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 making the polyethylene terephthalate Copolymers have a higher crystallization rate. Therefore, polyethylene terephthalate copolymers are suitable for high-speed processing techniques (such as injection molding) and do not require additional nucleating agents.
在一些實施例中，以射出成型製程使聚對苯二甲酸乙二酯的共聚物成型，且在進行射出成型製程時，不於聚對苯二甲酸乙二酯的共聚物中加入成核劑。在一些實施例中，聚對苯二甲酸乙二酯的共聚物適用於包裝瓶、纖維、各類薄膜或其他塑料產品。In some embodiments, the polyethylene terephthalate copolymer is molded by an injection molding process, and no nucleating agent is added to the polyethylene terephthalate copolymer during the injection molding process . In some embodiments, the copolymer of polyethylene terephthalate is suitable for packaging bottles, fibers, various films or other plastic products.
基於上述，聚對苯二甲酸乙二酯的共聚物具有較高的結晶速率，因此不需要額外添加成核劑就可以適用於高速加工的技術。Based on the above, the copolymer of polyethylene terephthalate has a high crystallization rate, so it can be applied to high-speed processing technology without additional nucleating agent.
以下，提供本發明的一些聚對苯二甲酸乙二酯的共聚物的實施例，然而，這些實施例為例示性，且本發明不限於這些實施例。Hereinafter, some examples of 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.
實施例Example 11
將0.7莫爾的對苯二甲酸、1.05莫爾的乙二醇和0.3莫爾的己二酸加入反應槽中。接著，在一大氣壓下將反應槽加熱至攝氏200度。在升溫的過程中，當反應槽的溫度加熱至約攝氏160時，反應槽內即開始出現水分。此外，當反應槽的溫度加熱至約攝氏190度時，於反應槽中加入0.05g的催化劑和0.5g的抗氧化劑，並進行常壓聚合反應。0.7 mol of terephthalic acid, 1.05 mol of ethylene glycol and 0.3 mol of adipic acid were added to the reaction tank. Next, the reaction tank was heated to 200 degrees Celsius under atmospheric pressure. During the heating process, when the temperature of the reaction tank is heated to about 160 degrees Celsius, moisture will start to appear in the reaction tank. In addition, when the temperature of the reaction tank was heated to about 190 degrees centigrade, 0.05 g of catalyst and 0.5 g of antioxidant were added into the reaction tank, and polymerization was carried out at normal pressure.
在反應槽中脫出之水分達到聚合反應完全所應產生之水分的約80%之後，逐漸減少反應槽中的壓力，以進行負壓脫水。在本實施例中，反應槽中的壓力約每20分鐘下降50 torr。在反應槽中的壓力降至200 torr後，將反應槽抽真空至約0 torr，並進行負壓脫醇2小時。接著，測量反應槽中之聚合物（即，聚對苯二甲酸乙二酯的共聚物）的黏度。在反應槽中之聚合物的黏度達目標值後，將反應槽降溫至攝氏120度，接著以氮氣破真空得到成品。After the moisture released from the reaction tank reaches about 80% of the moisture that should be produced by the complete polymerization reaction, gradually reduce the pressure in the reaction tank to carry out negative pressure dehydration. In this example, the pressure in the reaction tank was decreased by 50 torr approximately every 20 minutes. After the pressure in the reaction tank dropped to 200 torr, the reaction tank was evacuated to about 0 torr, and dealcoholized under negative pressure for 2 hours. Next, the viscosity of the polymer (ie, the copolymer of polyethylene terephthalate) in the reaction tank was measured. After the viscosity of the polymer in the reaction tank reaches the target value, the temperature of the reaction tank is lowered to 120 degrees Celsius, and then the vacuum is broken with nitrogen to obtain the finished product.
實施例Example 22
將0.7莫爾的對苯二甲酸、1.05莫爾的乙二醇和0.3莫爾的葵二酸加入反應槽中。接著，在一大氣壓下將反應槽加熱至攝氏200度。在升溫的過程中，當反應槽的溫度加熱至約攝氏160時，反應槽內即開始出現水分。此外，當反應槽的溫度加熱至約攝氏190度時，於反應槽中加入0.05g的催化劑和0.5g的抗氧化劑，並進行常壓聚合反應。0.7 mol of terephthalic acid, 1.05 mol of ethylene glycol and 0.3 mol of sebacic acid were added to the reaction tank. Next, the reaction tank was heated to 200 degrees Celsius under atmospheric pressure. During the heating process, when the temperature of the reaction tank is heated to about 160 degrees Celsius, moisture will start to appear in the reaction tank. In addition, when the temperature of the reaction tank was heated to about 190 degrees centigrade, 0.05 g of catalyst and 0.5 g of antioxidant were added into the reaction tank, and polymerization was carried out at normal pressure.
在反應槽中脫出之水分達到聚合反應完全所應產生之水分的約80%之後，逐漸減少反應槽中的壓力，以進行負壓脫水。在本實施例中，反應槽中的壓力約每20分鐘下降50 torr。在反應槽中的壓力降至200 torr後，將反應槽抽真空至約0 torr，並進行負壓脫醇2小時。接著，測量反應槽中之聚合物（即，聚對苯二甲酸乙二酯的共聚物）的黏度。在反應槽中之聚合物的黏度達目標值後，將反應槽降溫至攝氏120度，接著以氮氣破真空得到成品。After the moisture released from the reaction tank reaches about 80% of the moisture that should be produced by the complete polymerization reaction, gradually reduce the pressure in the reaction tank to carry out negative pressure dehydration. In this example, the pressure in the reaction tank was decreased by 50 torr approximately every 20 minutes. After the pressure in the reaction tank dropped to 200 torr, the reaction tank was evacuated to about 0 torr, and dealcoholized under negative pressure for 2 hours. Next, the viscosity of the polymer (ie, the copolymer of polyethylene terephthalate) in the reaction tank was measured. After the viscosity of the polymer in the reaction tank reaches the target value, the temperature of the reaction tank is lowered to 120 degrees Celsius, and then the vacuum is broken with nitrogen to obtain the finished product.
實施例Example 33
將1莫爾的對苯二甲酸、1.05莫爾的乙二醇和0.3莫爾的乳酸加入反應槽中。接著，在一大氣壓下將反應槽加熱至攝氏200度。在升溫的過程中，當反應槽的溫度加熱至約攝氏160時，反應槽內即開始出現水分。此外，當反應槽的溫度加熱至約攝氏190度時，於反應槽中加入0.05g的催化劑和0.5g的抗氧化劑，並進行常壓聚合反應。1 mol of terephthalic acid, 1.05 mol of ethylene glycol and 0.3 mol of lactic acid were added to the reaction tank. Next, the reaction tank was heated to 200 degrees Celsius under atmospheric pressure. During the heating process, when the temperature of the reaction tank is heated to about 160 degrees Celsius, moisture will start to appear in the reaction tank. In addition, when the temperature of the reaction tank was heated to about 190 degrees centigrade, 0.05 g of catalyst and 0.5 g of antioxidant were added into the reaction tank, and polymerization was carried out at normal pressure.
在反應槽中脫出之水分達到聚合反應完全所應產生之水分的約80%之後，逐漸減少反應槽中的壓力，以進行負壓脫水。在本實施例中，反應槽中的壓力約每20分鐘下降50 torr。在反應槽中的壓力降至200 torr後，將反應槽抽真空至約0 torr，並進行負壓脫醇2小時。接著，測量反應槽中之聚合物（即，聚對苯二甲酸乙二酯的共聚物）的黏度。在反應槽中之聚合物的黏度達目標值後，將反應槽降溫至攝氏120度，接著以氮氣破真空得到成品。After the moisture released from the reaction tank reaches about 80% of the moisture that should be produced by the complete polymerization reaction, gradually reduce the pressure in the reaction tank to carry out negative pressure dehydration. In this example, the pressure in the reaction tank was decreased by 50 torr approximately every 20 minutes. After the pressure in the reaction tank dropped to 200 torr, the reaction tank was evacuated to about 0 torr, and dealcoholized under negative pressure for 2 hours. Next, the viscosity of the polymer (ie, the copolymer of polyethylene terephthalate) in the reaction tank was measured. After the viscosity of the polymer in the reaction tank reaches the target value, the temperature of the reaction tank is lowered to 120 degrees Celsius, and then the vacuum is broken with nitrogen to obtain the finished product.
實施例Example 44
將0.7莫爾的對苯二甲酸、1.05莫爾的乙二醇和0.3莫爾的2, 5-噻吩二甲酸（2, 5-TDCA）加入反應槽中。接著，在一大氣壓下將反應槽加熱至攝氏200度。在升溫的過程中，當反應槽的溫度加熱至約攝氏160時，反應槽內即開始出現水分。此外，當反應槽的溫度加熱至約攝氏190度時，於反應槽中加入0.05g的催化劑和0.5g的抗氧化劑，並進行常壓聚合反應。Add 0.7 mol of terephthalic acid, 1.05 mol of ethylene glycol and 0.3 mol of 2,5-thiophenedicarboxylic acid (2,5-TDCA) into the reaction tank. Next, the reaction tank was heated to 200 degrees Celsius under atmospheric pressure. During the heating process, when the temperature of the reaction tank is heated to about 160 degrees Celsius, moisture will start to appear in the reaction tank. In addition, when the temperature of the reaction tank was heated to about 190 degrees centigrade, 0.05 g of catalyst and 0.5 g of antioxidant were added into the reaction tank, and polymerization was carried out at normal pressure.
在反應槽中脫出之水分達到聚合反應完全所應產生之水分的約80%之後，逐漸減少反應槽中的壓力，以進行負壓脫水。在本實施例中，反應槽中的壓力約每20分鐘下降50 torr。在反應槽中的壓力降至200 torr後，將反應槽抽真空至約0 torr，並進行負壓脫醇2小時。接著，測量反應槽中之聚合物（即，聚對苯二甲酸乙二酯的共聚物）的黏度。在反應槽中之聚合物的黏度達目標值後，將反應槽降溫至攝氏120度，接著以氮氣破真空得到成品。After the moisture released from the reaction tank reaches about 80% of the moisture that should be produced by the complete polymerization reaction, gradually reduce the pressure in the reaction tank to carry out negative pressure dehydration. In this example, the pressure in the reaction tank was decreased by 50 torr approximately every 20 minutes. After the pressure in the reaction tank dropped to 200 torr, the reaction tank was evacuated to about 0 torr, and dealcoholized under negative pressure for 2 hours. Next, the viscosity of the polymer (ie, the copolymer of polyethylene terephthalate) in the reaction tank was measured. After the viscosity of the polymer in the reaction tank reaches the target value, the temperature of the reaction tank is lowered to 120 degrees Celsius, and then the vacuum is broken with nitrogen to obtain the finished product.
實施例Example 55
將0.7莫爾的對苯二甲酸、1.05莫爾的乙二醇和0.3莫爾的雙環[2.2.1]庚-2 ,3-二甲酸（Bicyclo[2.2.1]hepta-2,5-diene-2,3-dicarboxylic acid）加入反應槽中。接著，在一大氣壓下將反應槽加熱至攝氏200度。在升溫的過程中，當反應槽的溫度加熱至約攝氏160時，反應槽內即開始出現水分。此外，當反應槽的溫度加熱至約攝氏190度時，於反應槽中加入0.05g的催化劑和0.5g的抗氧化劑，並進行常壓聚合反應。Add 0.7 moles of terephthalic acid, 1.05 moles of ethylene glycol and 0.3 moles of bicyclo[2.2.1]hepta-2,3-dicarboxylic acid (Bicyclo[2.2.1]hepta-2,5-diene- 2,3-dicarboxylic acid) into the reaction tank. Next, the reaction tank was heated to 200 degrees Celsius under atmospheric pressure. During the heating process, when the temperature of the reaction tank is heated to about 160 degrees Celsius, moisture will start to appear in the reaction tank. In addition, when the temperature of the reaction tank was heated to about 190 degrees centigrade, 0.05 g of catalyst and 0.5 g of antioxidant were added into the reaction tank, and polymerization was carried out at normal pressure.
在反應槽中脫出之水分達到聚合反應完全所應產生之水分的約80%之後，逐漸減少反應槽中的壓力，以進行負壓脫水。在本實施例中，反應槽中的壓力約每20分鐘下降50 torr。在反應槽中的壓力降至200 torr後，將反應槽抽真空至約0 torr，並進行負壓脫醇2小時。接著，測量反應槽中之聚合物（即，聚對苯二甲酸乙二酯的共聚物）的黏度。在反應槽中之聚合物的黏度達目標值後，將反應槽降溫至攝氏120度，接著以氮氣破真空得到成品。After the moisture released from the reaction tank reaches about 80% of the moisture that should be produced by the complete polymerization reaction, gradually reduce the pressure in the reaction tank to carry out negative pressure dehydration. In this example, the pressure in the reaction tank was decreased by 50 torr approximately every 20 minutes. After the pressure in the reaction tank dropped to 200 torr, the reaction tank was evacuated to about 0 torr, and dealcoholized under negative pressure for 2 hours. Next, the viscosity of the polymer (ie, the copolymer of polyethylene terephthalate) in the reaction tank was measured. After the viscosity of the polymer in the reaction tank reaches the target value, the temperature of the reaction tank is lowered to 120 degrees Celsius, and then the vacuum is broken with nitrogen to obtain the finished product.
表1顯示了一般的聚對苯二甲酸乙二酯（polyethylene terephthalate, PET）與實施例1至實施例5合成之聚對苯二甲酸乙二酯的共聚物的熔點（Tm）、結晶溫度（Tc）、玻璃轉移溫度（Tg）以及熔點與結晶溫度的差值（△T）。
表1
由表1可以得知，實施例1至實施例5所合成之聚對苯二甲酸乙二酯的共聚物之熔點與結晶溫度的差值皆小於一般的聚對苯二甲酸乙二酯之熔點與結晶溫度的差值。因此，實施例1至實施例5所合成之聚對苯二甲酸乙二酯的共聚物具有較高的結晶速率，且不需要額外添加成核劑就可以適用於高速加工的技術。It can be known from Table 1 that the difference between the melting point and the crystallization temperature of the polyethylene terephthalate copolymers synthesized in Examples 1 to 5 is smaller than the melting point of general polyethylene terephthalate The difference from the crystallization temperature. Therefore, the polyethylene terephthalate copolymers synthesized in Examples 1 to 5 have a relatively high crystallization rate, and can be applied to high-speed processing technology without adding additional nucleating agents.
S1、S2、S3、S4:步驟S1, S2, S3, S4: steps
圖1是依照本發明的一實施例的一種聚合物樹脂的製造方法的流程圖。FIG. 1 is a flowchart of a method for manufacturing a polymer resin according to an embodiment of the present invention.
S1、S2、S3、S4:步驟 S1, S2, S3, S4: steps
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