Patent Publication Number: US-2023146000-A1

Title: Copolymer and preparation method thereof

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a National Stage Application of International Application No. PCT/KR2021/013586 filed on Oct. 5, 2021, which claims priority to and the benefits of Korean Patent Application No. 10-2020-0128319, filed on Oct. 5, 2020, and Korean Patent Application No. 10-2021-0131495, filed on Oct. 5, 2021, the disclosures of which are hereby incorporated by reference herein in their entirety. 
    
    
     TECHNICAL FIELD 
     The present invention relates to a copolymer having an improved elongation and a high molecular weight at the same time while maintaining intrinsic properties of polylactic acid, and a preparation method thereof. 
     BACKGROUND 
     Polylactic acid (PLA) is a plant-derived resin obtained from plants such as corn, etc., and is receiving attention as an eco-friendly material having biodegradable properties while having excellent tensile strength and elastic modulus. 
     Unlike petroleum-based resins such as polystyrene resins, polyvinyl chloride resins, polyethylene resins, etc., which are currently used, polylactic acid has effects of preventing depletion of petroleum-based resources and suppressing carbon dioxide emissions, and therefore, causes less environmental pollution, which is a disadvantage of petroleum-based plastic products. As environmental pollution caused by waste plastics and the like has emerged as social problems, efforts have been made to expand the application of polylactic acid to various fields, including food packing materials and containers, cases for electronic products, etc., to which general plastics (petroleum-based resins) have been applied. 
     However, since polylactic acid has poor impact resistance and heat resistance, as compared to the existing petroleum-based resins, there is a limitation in its application. In addition, polylactic acid has a poor elongation to break to exhibit brittleness, which limits its use as a general-purpose resin. 
     To overcome the above disadvantages, studies have been conducted on copolymers including other repeating units in addition to polylactic acid. In particular, to improve the elongation, 3-hydroxypropionic acid (3HP) has attracted attention as a comonomer. Specifically, a lactic acid-3HP block copolymer has received attention, and this copolymer has effects of improving the elongation while maintaining intrinsic properties of polylactic acid. 
     However, the lactic acid-3HP block copolymer has several disadvantages. First, only 3HP needs to be separately polymerized. There is a problem in that it is difficult to polymerize 3HP having a high molecular weight of about 10 kDa or more only by a chemical method. High molecular weight polymerization is possible through biosynthesis, but there is a problem in that the production cost is increased. 
     Accordingly, it is required to prepare a copolymer having an improved elongation and a high molecular weight at the same time while maintaining intrinsic properties of polylactic acid. 
     BRIEF DESCRIPTION 
     Technical Problem 
     Provided is a copolymer having an improved elongation and a high molecular weight at the same time while maintaining intrinsic properties of polylactic acid, and a preparation method thereof. 
     Technical Solution 
     To achieve the above objects, provided is a copolymer comprising an irregularly arranged structure of a repeating unit of the following Chemical Formula 1 and a repeating unit of the following Chemical Formula 2, and a repeating unit of the following Chemical Formula 3 present at least at one end of the structure: 
     
       
         
         
             
             
         
       
     
     To provide a copolymer having an improved elongation and a high molecular weight at the same time while maintaining intrinsic properties of polylactic acid, the present invention provides a copolymer including a repeating unit of Chemical Formula 1, derived from 3HP, a repeating unit of Chemical Formula 2, derived from lactic acid, and a repeating unit of Chemical Formula 3, derived from lactide. 
     In particular, the copolymer according to the present invention can have a structure, in which the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2 are irregularly arranged, and the repeating unit of Chemical Formula 3 is present at least at one end or at both ends of the structure. In other words, the copolymer according to the present invention can have a structure of A-B or B-A-B, wherein A has a random arrangement of the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2, and the B′s have an arrangement of the repeating unit of Chemical Formula 3, respectively. 
     Hereinafter, each repeating unit will be described in detail. 
     Repeating Unit of Chemical Formula 1 and Repeating Unit of Chemical Formula 2 
     The repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2 can form a central structure of the copolymer according to the present invention, and can be derived from 3HP and lactic acid, respectively, and the central structure can be prepared by copolymerizing 3HP and lactic acid, as described below. 
     When 3HP is used as a comonomer of polylactic acid, elongation can be improved while maintaining intrinsic physical properties of polylactic acid, but there is a problem in that polymerization of 3HP does not occur well. Therefore, there has been a limitation in the preparation of a copolymer having a high molecular weight by using a lactic acid-3HP block copolymer. However, in the present invention, a copolymer having a high molecular weight can be prepared by polymerization of 3HP with lactic acid, rather than separate polymerization of only 3HP. 
     Preferably, a weight ratio of the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2 is 20:80 to 80:20. More preferably, the weight ratio is 30:70 to 70:30, 40:60 to 60:40. The weight ratio can be adjusted according to the amount of each material used during the copolymerization of lactic acid and 3HP. 
     Further, since the copolymer according to the present invention is prepared by preparing a copolymer including the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2, i.e., a random copolymer of the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2, and then preparing a copolymer including the repeating unit of Chemical Formula 3, as described below, it is possible to measure the weight average molecular weight of the random copolymer. 
     Preferably, a weight average molecular weight of the random copolymer of the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2 is 10,000 g/mol to 30,000 g/mol. This weight average molecular weight is higher than that of the known lactic acid-3HP block copolymer, and therefore, in the present invention, it is possible to prepare a copolymer having a high molecular weight even using 3HP as the comonomer of polylactic acid. 
     Meanwhile, as used herein, the ‘lactic acid’ refers to L-lactic acid, D-lactic acid, or a mixture thereof. 
     Repeating Unit of Chemical Formula 3 
     As described above, the copolymer according to the present invention has a structure of A-B or B-A-B, wherein B has a structure having an arrangement of the repeating unit of Chemical Formula 3. 
     Specifically, the arrangement of the repeating unit of Chemical Formula 3 can be further included at least at one end or at both ends of the above-described random copolymer of the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2 through lactide ring-opening polymerization, as described below. 
     The repeating unit of Chemical Formula 3 is derived from lactide, and is to additionally introduce a repeating unit such as Chemical Formula 2 to the copolymer according to the present invention, whereby the weight average molecular weight of the copolymer according to the present invention can be increased, and intrinsic physical properties of polylactic acid can be manifested. 
     Preferably, the repeating unit of Chemical Formula 3 is included in an amount of 60 wt % to 99 wt % with respect to the total weight of the copolymer according to the present invention. In other words, the total weight of the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2 is preferably 1 wt % to 40 wt % with respect to the total weight of the copolymer according to the present invention. More preferably, the total weight of the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2 is 2 wt % or more, 3 wt % or more, 4 wt % or more, or 5 wt % or more, and 35 wt % or less, 30 wt % or less, 25 wt % or less, 20 wt % or less, or 15 wt % or less with respect to the total weight of the copolymer according to the present invention. 
     The content of the repeating unit of Chemical Formula 3 can be adjusted according to the amount of lactide used during the copolymerization of lactide. 
     Meanwhile, as used herein, the ‘lactide’ refers to L-lactide, D-lactide, meso-lactide consisting of each one of L-form and D-form, or D,L-lactide or rac-lactide, in which L-lactide and D-lactide are mixed at a weight ratio of 50:50. 
     Copolymer 
     The above-described copolymer according to the present invention employs, as an initiator, the random copolymer of the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2, and thus there is an advantage in that various physical properties can be achieved by adjusting the monomer ratio in the random copolymer as the initiator. Further, by controlling crystallinity of the initiator itself, the intrinsic properties of polylactic acid are maintained while particularly improving the elongation and increasing the weight average molecular weight. 
     Preferably, a weight average molecular weight (g/mol) of the copolymer is 50,000 to 300,000. As described above, 3HP and lactic acid are first copolymerized, and then lactide is subjected to ring-opening polymerization, thereby preparing the copolymer having the high weight average molecular weight. Preferably, the weight average molecular weight of the copolymer is 60,000 or more, 70,000 or more, 80,000 or more, 90,000 or more, or 100,000 or more. Meanwhile, a method of measuring the weight average molecular weight will be described below. 
     Further, the copolymer according to the present invention has a tensile strength of 20 MPa to 50 MPa. Further, the copolymer according to the present invention has an elongation of 4% to 200%. As compared to a polylactic acid having the same weight average molecular weight, the copolymer according to the present invention has a tensile strength at the similar level, but has an improved elongation, which is attributed to 3HP included in the copolymer, as described above. Meanwhile, methods of measuring the tensile strength and the elongation will be described below. 
     Method of Preparing Copolymer 
     Further, the present invention provides a method of preparing the above-described copolymer, wherein the method comprises the following steps of: 
     1) preparing an oligomer by polycondensation of 3-hydroxypropionic acid and lactic acid; and 
     2) polymerizing the oligomer of the step 1 and a lactide. 
     The step 1 is a step of preparing the above-described random copolymer of the repeating unit of Chemical Formula 1 and the repeating unit of Chemical Formula 2. 
     Preferably, the step 1 is performed in the presence of an acid catalyst or a metal catalyst. Examples of the acid catalyst can include an organic acid, preferably, p-toluenesulfonic acid. Examples of the metal catalyst can include a phosphorus-based catalyst or a tin-based catalyst. 
     Preferably, the amount of the catalyst used in the step 1 can be 0.01 mol % to 10 mol %, 0.1 mol % to 5 mol %, or 0.2 mol % to 1 mol %, assuming that the total number of moles of 3-hydroxypropionic acid and lactic acid is 100 mol %. 
     Preferably, the step 1 is performed at 100° C. to 150° C. Preferably, the step 1 is performed for 10 hours to 80 hours, and more preferably, for 20 hours to 60 hours. Preferably, the step 2 is performed at 0.01 mbar to 50 mbar. 
     Preferably, the step 2 is performed in the presence of a lactide ring-opening polymerization catalyst. For example, the catalyst can be a catalyst of Chemical Formula 4: 
       MA 1   p A 2   2−p    [Chemical Formula 4]
 
     wherein in Chemical Formula 4: 
     M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti, or Zr; 
     p is an integer of 0 to 2; and 
     A 1  and A 2  are each independently an alkoxy group or a carboxyl group. 
     More specifically, the catalyst of Chemical Formula 4 can be tin(II) 2-ethylhexanoate (Sn(Oct) 2 ). 
     Preferably, the amount of the catalyst used in the step 2 can be 0.01 mol % to 10 mol %, 0.01 mol % to 5 mol %, or 0.03 mol % to 1 mol %, assuming that the total number of moles of oligomer of the step 1 and lactide is 100 mol %. 
     Preferably, the step 2 is performed at 150° C. to 200° C. Preferably, the step 2 is performed for 5 minutes to 10 hours, and more preferably, for 10 minutes to 1 hour. Preferably, the step 2 is performed at 0.5 mbar to 1.5 mbar. 
     On the other hand, the step 2 can be performed by bulk polymerization substantially without using a solvent. In this regard, ‘substantially without using a solvent’ can include a case of using a small amount of a solvent for dissolving the catalyst, for example, up to less than 1 ml of the solvent per 1 kg of the monomer used. When the step 2 is performed by bulk polymerization, it is possible to omit a process of removing the solvent after the polymerization, and thus it is possible to suppress the decomposition or loss of the resin during the process of removing the solvent. 
     Effect of the Invention 
     As descried above, the copolymer according to the present invention is characterized by maintaining intrinsic properties of polylactic acid while particularly having an improved elongation and also having a high weight average molecular weight. 
    
    
     DETAILED DESCRIPTION 
     Hereinafter, exemplary embodiments of the present invention will be described in more detail in the following Examples. However, the following Examples are only for illustrating the exemplary embodiments of the present invention, and the content of the present invention is not limited to the following Examples. 
     Hereinafter, a weight average molecular weight, a tensile strength, and an elongation were measured by the following methods.
         Weight average molecular weight: Measurement was performed by GPC using PC Standards and Agilent 1200 series HPLC system.   Elongation, Tensile strength, and Tensile modulus: Measurement was performed in accordance with ASTM D638. Each copolymer was prepared in the form of pellet, and then processed into a dog-bone specimen, followed by measuring using a universal testing machine (UTM). At this time, the measurement speed was 10 mm/min.   Content of 3HP (wt %) in copolymer: Measurement was performed by NMR analysis of each copolymer.       

     PREPARATION EXAMPLES 1 TO 4 
     In a reactor, 3-Hydroxypropionic acid (3HP), lactic acid (LA), and a catalyst (p-TSA; 0.3 wt % with respect to the total weight of 3HP and LA) were mixed in the amounts as described in Table 1 below, and dried under conditions of 70° C. and 50 mbar for 3 hours. Subsequently, the temperature and the pressure in the reactor were controlled to 130° C. and 20 mbar, and then a polycondensation reaction was allowed to proceed for 24 hours. 
     With respect to each of the prepared random copolymers, the content of 3HP in each copolymer and its weight average molecular weight were measured and shown in Table 1 below. 
     
       
         
           
               
               
               
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                   
                   
                 3HP 
                 3HP 
                 Weight average 
               
               
                   
                 3HP 
                 LA 
                 input 
                 content 
                 molecular weight 
               
               
                   
                 input 
                 input 
                 ratio 
                 (wt %) in 
                 (Mw, g/mol) of 
               
               
                   
                 (g) 
                 (g) 
                 (wt %) 
                 copolymer 
                 random copolymer 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 Preparation 
                 7 
                 3 
                 70 
                 68 
                 16,700 
               
               
                 Example 1 
               
               
                 Preparation 
                 5 
                 5 
                 50 
                 44 
                 15,850 
               
               
                 Example 2 
               
               
                 Preparation 
                 3 
                 7 
                 30 
                 31 
                 27,600 
               
               
                 Example 3 
               
               
                 Preparation 
                 10 
                 0 
                 100 
                 100 
                 2,430 
               
               
                 Example 4 
               
               
                   
               
            
           
         
       
     
     EXAMPLES AND COMPARATIVE EXAMPLES 
     As in Table 2 below, each of the random copolymers prepared in Preparation Examples, lactide, and a catalyst (Tin Octoate, 0.05 mol % with respect to lactide) were put in a reactor, which was controlled to 170° C. and 20 mbar, and a lactide ring-opening polymerization was allowed to proceed for 30 minutes. 
     Meanwhile, in Table 2 below, Comparative Example 1 indicates a copolymer prepared by ring-opening polymerization using lactide alone without using the random copolymer prepared in Preparation Example. 
     
       
         
           
               
               
               
             
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Random copolymer 
                 Lactide 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 Example 1-1 
                 Random copolymer of Preparation 
                 lactide 
               
               
                   
                 Example 1 (10 wt %) 
                 (90 wt %) 
               
               
                 Example 1-2 
                 Random copolymer of Preparation 
                 lactide 
               
               
                   
                 Example 1 (30 wt %) 
                 (70 wt %) 
               
               
                 Example 1-3 
                 Random copolymer of Preparation 
                 lactide 
               
               
                   
                 Example 1 (5 wt %) 
                 (95 wt %) 
               
               
                 Example 2-1 
                 Random copolymer of Preparation 
                 lactide 
               
               
                   
                 Example 2 (10 wt %) 
                 (90 wt %) 
               
               
                 Example 3-1 
                 Random copolymer of Preparation 
                 lactide 
               
               
                   
                 Example 3 (10 wt %) 
                 (90 wt %) 
               
               
                 Example 3-2 
                 Random copolymer of Preparation 
                 lactide 
               
               
                   
                 Example 3 (20 wt %) 
                 (80 wt %) 
               
               
                 Example 4-1 
                 Random copolymer of Preparation 
                 lactide 
               
               
                   
                 Example 3 (30 wt %) 
                 (70 wt %) 
               
               
                 Comparative 
                 None 
                 lactide 
               
               
                 Example 1 
                   
                 (100 wt %) 
               
               
                 Comparative 
                 Random copolymer of Preparation 
                 lactide 
               
               
                 Example 2 
                 Example 4 (10 wt %) 
                 (90 wt %) 
               
               
                   
               
            
           
         
       
     
     EXPERIMENTAL EXAMPLE 
     A weight average molecular weight, a tensile strength, and an elongation were measured for the copolymers prepared in Examples and Comparative Examples, and the results are shown in Table 3 below. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 3 
               
               
                   
                   
               
               
                   
                 3HP content 
                 Weight average 
                 Tensile 
                   
               
               
                   
                 (wt %) in 
                 molecular weight 
                 strength 
                 Elongation 
               
               
                   
                 copolymer 
                 (Mw, g/mol) 
                 (MPa) 
                 (%) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Example 1-1 
                 7.2 
                 164,650 
                 36.80 
                 14.90 
               
               
                 Example 1-2 
                 21.0 
                 80,900 
                 27.7 
                 107 
               
               
                 Example 1-3 
                 3.8 
                 214,500 
                 44.5 
                 3.4 
               
               
                 Example 2-1 
                 5.0 
                 190,370 
                 32.40 
                 5.0 
               
               
                 Example 3-1 
                 2.5 
                 255,000 
                 41.45 
                 4.3 
               
               
                 Example 3-2 
                 7.6 
                 179,200 
                 32.8 
                 66.2 
               
               
                 Example 4-1 
                 9.8 
                 108,360 
                 28.73 
                 152.5 
               
               
                 Comparative 
                 0 
                 239,000 
                 50.13 
                 2.2 
               
               
                 Example 1 
               
            
           
           
               
               
               
               
            
               
                 Comparative 
                 10 
                 31,700 
                 Evaluation of 
               
               
                 Example 2 
                   
                   
                 physical properties 
               
               
                   
                   
                   
                 was impossible due to 
               
               
                   
                   
                   
                 low molecular weight 
               
               
                   
               
            
           
         
       
     
     As shown in Table 2, it was confirmed that the copolymer according to the present invention had the increased elongation, as compared with the copolymer prepared by polymerizing lactide alone (Comparative Example 1). When Example 4 was compared with Comparative Example 2, in which lactic acid was not used in the polymerization, the effect of increasing the molecular weight was observed when lactic acid was copolymerized, indicating improvement of physical properties.