polymer

Abstract

To provide a zwitterionic polymer with new characteristics, and applications based on the characteristics.SOLUTION: The polymer comprises a polymer unit represented by general formula (1) in the figure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to polymers, etc. [Background technology]

[0002] Several examples of the synthesis of zwitterionic polymers incorporating zwitterionic groups such as sulfobetaine and phosphobetaine have been reported. Zwitterionic polymers possess excellent biocompatibility, anti-fouling properties, low friction, and oil repellency. Currently, their excellent biocompatibility and low friction are attracting particular attention, and they are mainly being applied to biomaterials such as artificial hip joints and artificial hearts.

[0003] Examples of zwitterionic polymers that have been reported include polymers that can be used for non-specific protein adsorption treatment, polymers that can be used for analysis of ion-specific hydration states, polymers that can be used as anti-fouling materials, and polymers that are insoluble in water but salt-sensitive in salt-containing solutions (Non-Patent Documents 1-3, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2005-97510 [Non-patent literature]

[0005] [Non-Patent Document 1] Langmuir 2001, 17, 2841-2850 [Non-Patent Document 2] Langmuir 2019, 35, 1413-1420 [Non-Patent Document 3] Langmuir 2020, 36, 9015-9024 [Overview of the project] [Problems that the invention aims to solve]

[0006] The present invention aims to provide zwitterionic polymers with new properties and uses based on such properties. [Means for Solving the Problems]

[0007] As a result of intensive research in view of the above problems, the present inventor has found that the general formula (1):

[0008] [Chemical formula]

[0009] [In the formula: R , , , , ,

[0013] , ,

[0012] and R 2 One of them independently represents a divalent hydrocarbon group in each occurrence, and R 1 and R 2 The other independently represents a group represented by the general formula (2a), the general formula (2b1), or the general formula (2b2) in each occurrence:

[0010] [Chemical formula]

[0011] (In the formula: R 31 and R 32 represent the same or different divalent hydrocarbon groups, and R 33 represents a monovalent hydrocarbon group. m represents an integer of 1 to 5.) represents a group (provided that at least one of R 1 or R 2 represents a group represented by the general formula (2a).). n represents an integer of 1 or more.] It has been found that a polymer containing a polymer unit represented by has oil repellency, hydrophilicity, adhesiveness, etc. Based on this finding, the present inventor has further conducted research and completed the present invention. That is, the present invention includes the following aspects.

[0012] Item 1. General formula (1):

[0013] [Chemical formula]

[0014] [In the formula: R 1 and R 2 One of them independently exhibits a divalent hydrocarbon group in each appearance, R 1 and R 2 The other of these is independent in each occurrence of general formula (2a), general formula (2b1), or general formula (2b2):

[0015] [ka]

[0016] (In the formula: R 31 and R 32 These represent the same or different divalent hydrocarbon groups. 33 (where m represents a monovalent hydrocarbon group, and m represents an integer from 1 to 5.) The group represented by (wherein at least one R) 1 or R 2 This represents the base represented by the general formula (2a). n represents an integer greater than or equal to 1. A polymer containing polymer units represented by [the symbol].

[0017] Section 2. The aforementioned R 1 is a divalent hydrocarbon group, and the R 2 The polymer according to item 1, wherein the group is represented by general formula (2a), general formula (2b), or general formula (2b2).

[0018] Section 3. The aforementioned R 1 is a divalent hydrocarbon group containing an aromatic ring, and the R 31 and R 32 is an alkylene group, and the R 33 The polymer according to item 2, wherein the alkyl group is an alkyl group.

[0019] Section 4. The polymer according to any one of items 1 to 3, wherein the ratio (x / n) of the number of groups represented by the general formula (2a) in the polymer unit to n is 0.6 or more.

[0020] Section 5. The polymer according to any one of items 1 to 4, wherein the ratio (x / n) of the number of groups represented by the general formula (2a) in the polymer unit to n is 0.6 to 0.9.

[0021] Section 6. The polymer according to any one of items 1 to 4, wherein the ratio (x / n) of the number of groups represented by the general formula (2a) in the polymer unit to n is 0.9 or more.

[0022] Section 7. The polymer according to any one of items 1 to 6, wherein the ratio (x / n) of the number of groups represented by the general formula (2a) in the polymer unit to n is less than 1.

[0023] Section 8. The polymer according to any one of items 1 to 7, wherein the weight-average molecular weight of the polymer unit is 5000 or more.

[0024] Section 9. A composition containing the polymer described in any of items 1 to 8.

[0025] Section 10. The composition according to item 9, which is an oil repellent, an antifouling agent, a hydrophilic agent, or an adhesive.

[0026] Section 11. A composition for coating purposes, as described in item 9 or 10.

[0027] Section 12. An article containing a polymer as described in any of items 1 to 8.

[0028] Section 13. General formula (1):

[0029] [ka]

[0030] [In the formula: R 1 and R 2 One of them independently exhibits a divalent hydrocarbon group in each appearance, R 1 and R 2 The other side, independently in each occurrence, is given by the general formula (2b1):

[0031] [ka]

[0032] (In the formula: R 31 and R 32 R represents the same or different divalent hydrocarbon group. 33 (This indicates a monovalent hydrocarbon group.) This indicates a base represented by . n represents an integer greater than or equal to 1. The process involves reacting a polymer containing polymer units represented by a sultone in a solvent. A method for producing the polymer described in any of items 1 to 8.

[0033] Section 14. The method according to item 13, wherein the solvent is a fluoroalcohol. [Effects of the Invention]

[0034] According to the present invention, it is possible to provide a zwitterionic polymer with novel properties, and applications based on these properties. [Brief explanation of the drawing]

[0035] [Figure 1] The 1H NMR spectra of PMDAT and PDSBT (CF3COOD, 400 MHz) are shown. [Figure 2] This shows the molecular weight distribution of PMDAT. The two lines represent the results of each run. [Figure 3-1]The TG curves for PMDAT and PDSBT before neutralization are shown. The PMDAT curve is from Run 1. [Figure 3-2] The TG curves for PMDAT and PDSBT after neutralization are shown. The PMDAT curve is from Run 1. [Figure 4-1] The DSC curves for PMDAT and PDSBT before neutralization are shown. The PMDAT curve is the result from Run 1. [Figure 4-2] The DSC curves for PMDAT and PDSBT after neutralization are shown. The PMDAT curve is from Run 1. [Figure 5] This chart shows the turbidity of PMDAT at varying salt concentrations. From left to right, the lines represent the measurement results at salt concentrations of 0.5M, 0.8M, and 1.0M. [Figure 6] This shows the turbidity of PDSBT (sulfobetaine introduction rate 98%) in a 1 M NaCl aqueous solution. [Figure 7] Images of the contact angles of PMDAT and PDSBT with respect to water are shown. [Figure 8] Images showing the contact angles of PMDAT and PDSBT with respect to hexadecane in water are shown. [Modes for carrying out the invention]

[0036] In this specification, the terms “contains” and “includes” include the concepts of “contains,” “includes,” “substantially consist of,” and “consist solely of.”

[0037] 1. Polymer In one embodiment, the present invention is based on the general formula (1):

[0038] [ka]

[0039] This invention relates to a polymer (sometimes referred to as "the polymer of the present invention" in this specification) comprising a polymer unit represented by (sometimes referred to as "the polymer unit of the present invention" in this specification). This is described below.

[0040] In general formula (1), R 1 and R 2 One of them independently exhibits a divalent hydrocarbon group in each appearance, R 1 and R 2 The other of these is independent in each occurrence of general formula (2a), general formula (2b1), or general formula (2b2):

[0041] [ka]

[0042] The group represented by (wherein at least one R) 1 or R 2 This represents the group represented by general formula (2a).

[0043] In other words, the polymer of the present invention is R 1 is a divalent hydrocarbon group, and R 2 When is a group represented by general formula (2a), general formula (2b1), or general formula (2b2), and R 1 is a group represented by general formula (2a), general formula (2b1), or general formula (2b2), and R 2 This includes the case where is a divalent hydrocarbon group. The polymer units of the present invention are the units represented by general formula (1A1) and the units represented by general formula (1A2) (or the units in which N is NH):

[0044] [ka]

[0045] The units consist of, or are represented by the general formula (1B1), and the units represented by the general formula (1B2) (or units in which N is NH):

[0046] [ka]

[0047] It consists of.

[0048] In the polymer of the present invention, from the viewpoint of oil repellency, hydrophilicity, adhesion, etc., R 1 is a divalent hydrocarbon group, and R 2 It is preferable that the group is represented by general formula (2a), general formula (2b1), or general formula (2b2).

[0049] R 1 or R 2 The divalent hydrocarbon group represented by is not particularly limited and includes, for example, alkylene groups, arylene groups, and groups formed by any combination thereof.

[0050] R 1 or R 2 The alkylene group represented by includes linear, branched, and cyclic groups. The number of carbon atoms in the alkylene group is not particularly limited, for example, 1 to 12, preferably 2 to 10, and more preferably 3 to 8. Specific examples of the alkylene group include methylene, ethylene, ethylidene, trimethylene, propylene, propyridene, tetramethylene, ethylethylene, butane-2-ylidene, 1,2-dimethylethylene, pentamethylene, and pentane-2,3-diyl.

[0051] R 1 or R 2 The arylene group represented by is not particularly limited, but preferably has 6 to 12 carbon atoms, more preferably 6 to 10, and even more preferably 6 to 8 carbon atoms. The arylene group may be monocyclic or polycyclic (e.g., bicyclic, tricyclic, etc.), but is preferably monocyclic. Specific examples of the arylene group include phenylene, naphthylene, and biphenylene groups, with phenylene being preferred.

[0052] In the polymer of the present invention, R is preferred from the viewpoint of oil repellency, hydrophilicity, adhesion, etc. 1 and R 2 One of them (preferably) is a divalent hydrocarbon group containing an aromatic ring, more preferably R 1 and R 2 One of them (preferably) is a divalent hydrocarbon group containing an aromatic ring, and more preferably R 1 and R 2 One of them (preferably) is a divalent hydrocarbon group containing a phenylene group, and particularly preferably R 1 and R 2 One of them (preferably) is a phenylene group.

[0053] In general formula (2a), general formula (2b1), and general formula (2b2), R 31 and R 32 These represent the same or different divalent hydrocarbon groups.

[0054] R 31 and R 32 The divalent hydrocarbon group represented by is not particularly limited and includes, for example, alkylene groups, arylene groups, and groups formed by any combination thereof.

[0055] R 31 and R 32 The alkylene group represented by includes linear, branched, and cyclic (preferably linear or branched, more preferably linear) groups. The number of carbon atoms in the alkylene group is not particularly limited, for example, 1 to 12, preferably 1 to 6, more preferably 1 to 4, and most preferably 2. Specific examples of the alkylene group are the same as those described above.

[0056] R 31 and R 32The arylene group represented by is not particularly limited, but preferably has 6 to 12 carbon atoms, more preferably 6 to 10, and even more preferably 6 to 8 carbon atoms. The arylene group may be monocyclic or polycyclic (e.g., bicyclic, tricyclic, etc.), but is preferably monocyclic. Specific examples of the arylene group are the same as those described above.

[0057] In the polymer of the present invention, R is preferred from the viewpoint of oil repellency, hydrophilicity, adhesion, etc. 31 and R 32 is an alkylene group, more preferably R 31 and R 32 is a linear alkylene group, and is particularly preferably R 31 and R 32 These are alkylene groups with 1 to 4 carbon atoms.

[0058] In general formula (2a), general formula (2b1), and general formula (2b2), R 33 This indicates a monovalent hydrocarbon group.

[0059] R 33 The hydrocarbon group represented by is not particularly limited and includes, for example, alkyl groups, aryl groups, and groups formed by any combination of these (e.g., aralkyl groups, alkylaryl groups, alkylaralkyl groups).

[0060] R 33 The alkyl group represented by includes linear, branched, or cyclic (preferably linear or branched, more preferably linear). The number of carbon atoms in the alkyl group is not particularly limited, for example, 1 to 12, preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 2, and most preferably 1. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, neopentyl group, n-hexyl group, 3-methylpentyl group, and the like.

[0061] R 33The aryl group represented by is not particularly limited, but preferably has 6 to 12 carbon atoms, more preferably 6 to 10, and even more preferably 6 to 8 carbon atoms. The aryl group may be monocyclic or polycyclic (e.g., bicyclic, tricyclic, etc.), but is preferably monocyclic. Specific examples of the aryl group include phenyl, naphthyl, and biphenyl groups.

[0062] In the polymer of the present invention, R is preferred from the viewpoint of oil repellency, hydrophilicity, adhesion, etc. 33 is an alkyl group, more preferably R 33 is a linear alkyl group, and is particularly preferably R 33 These are alkyl groups with 1 to 4 carbon atoms.

[0063] In general formulas (2a), (2b1), and (2b2), m represents an integer from 1 to 5.

[0064] In the polymer of the present invention, from the viewpoint of oil repellency, hydrophilicity, adhesion, etc., m is preferably 2 to 4, and particularly preferably 3.

[0065] In the polymer of the present invention, from the viewpoint of oil repellency, hydrophilicity, adhesion, etc., R 1 and R 2 One of them is independently a divalent hydrocarbon group in each appearance, R 1 and R 2 The other is independently in each occurrence a base represented by general formula (2a) or general formula (2b1) (where at least one R 1 or R 2 The group is represented by general formula (2a). ) is preferred.

[0066] In the polymer of the present invention, the water solubility of the polymer itself (particularly from the viewpoint of water solubility at high salt concentrations, R 1 and R 2 One of them is independently a divalent hydrocarbon group in each appearance, R 1 and R 2On the other hand, each occurrence is independently a group represented by general formula (2a) or general formula (2b2) (however, at least one R 1 or R 2 is a group represented by general formula (2a).) It is preferable.

[0067] In general formula (1), n represents an integer of 1 or more. n is, for example, 10 or more, preferably 20 to 400, more preferably 32 to 200.

[0068] In the polymer of the present invention, at least one R 1 or R 2 is a group represented by general formula (2a).

[0069] In the polymer of the present invention, from the viewpoints of oil repellency, hydrophilicity, adhesiveness, etc., the ratio (x / n) of the number (x) of groups represented by general formula (2a) in the polymer units of the present invention to n is particularly preferably 0.6 or more. Among this range, it is more preferably 0.65 or more.

[0070] In the polymer of the present invention, from the viewpoints of oil repellency, adhesiveness, etc. (particularly adhesiveness), the ratio (x / n) of the number (x) of groups represented by general formula (2a) in the polymer units of the present invention to n is particularly preferably 0.6 to 0.9. Among this range, it is more preferably 0.65 to 0.9, further preferably 0.65 to 0.87, and even more preferably 0.65 to 0.85.

[0071] In the polymer of the present invention, from the viewpoints of oil repellency, hydrophilicity, etc., the ratio (x / n) of the number (x) of groups represented by general formula (2a) in the polymer units of the present invention to n is particularly preferably 0.9 or more. Among this range, it is more preferably 0.93 or more, further preferably 0.95 or more, and even more preferably 0.97 or more.

[0072] In one aspect of the polymer of the present invention, the ratio (x / n) of the number (x) of the groups represented by the general formula (2a) in the polymer unit of the present invention to n can be less than 1 (or 0.999 or less, 0.995 or less, or 0.99 or less).

[0073] x / n (sulfobetaine introduction rate) can be calculated from the integration ratio of the peaks of the H NMR spectrum according to the method described in Test Example 1. 1 It can be calculated from the integration ratio of the peaks of the H NMR spectrum.

[0074] The weight average molecular weight of the polymer unit of the present invention is not particularly limited as long as it can exhibit oil repellency, hydrophilicity, adhesiveness, etc., but can be, for example, 5000 or more. The weight average molecular weight is preferably 10000 or more, more preferably 15000 or more, still more preferably 20000 or more. The upper limit of the weight average molecular weight is, for example, 1000000, preferably 500000, more preferably 200000, still more preferably 100000, and even more preferably 50000.

[0075] The number average molecular weight of the polymer unit of the present invention is not particularly limited as long as it can exhibit oil repellency, hydrophilicity, adhesiveness, etc., but can be, for example, 3000 or more. The number average molecular weight is preferably 5000 or more, more preferably 8000 or more, still more preferably 10000 or more. The upper limit of the number average molecular weight is, for example, 1000000, preferably 500000, more preferably 200000, still more preferably 100000, and even more preferably 50000.

[0076] In the present specification, the weight average molecular weight and the number average molecular weight can be calculated based on the GPC measurement results according to the method described in Test Example 1.

[0077] The ratio (M w / M n ) of the number average molecular weight (M w ) to the weight average molecular weight (M n ) of the polymer unit of the present invention is, for example, 1.0 to 3.0, preferably 1.0 to 2.0.

[0078] The polymer of the present invention may consist solely of the polymer units of the present invention, or it may contain other polymer units. From the viewpoint of oil repellency, hydrophilicity, adhesion, etc., it is necessary that the proportion of the polymer units of the present invention be above a certain level. For example, the content of the polymer units of the present invention is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, particularly preferably 99% by mass or more, and especially preferably 100% by mass, based on 100% by mass of the polymer of the present invention.

[0079] The weight-average molecular weight of the polymer of the present invention is not particularly limited as long as it exhibits oil repellency, hydrophilicity, adhesiveness, etc., but can be, for example, 5000 or more. The weight-average molecular weight is preferably 10000 or more, more preferably 15000 or more, and even more preferably 20000 or more. The upper limit of the weight-average molecular weight is, for example, 1000000, preferably 500000, more preferably 200000, even more preferably 100000, and even more preferably 50000.

[0080] The number-average molecular weight of the polymer of the present invention is not particularly limited as long as it exhibits oil repellency, hydrophilicity, adhesiveness, etc., but can be, for example, 3000 or more. The number-average molecular weight is preferably 5000 or more, more preferably 8000 or more, and even more preferably 10000 or more. The upper limit of the number-average molecular weight is, for example, 1,000,000, preferably 500,000, more preferably 200,000, even more preferably 100,000, and even more preferably 50,000.

[0081] The 5% weight loss temperature of the polymer of the present invention can be, for example, 180 to 300°C. The glass transition temperature of the polymer of the present invention can be, for example, 18 to 103°C. The melting point of the polymer of the present invention can be, for example, 110 to 120°C. These parameters can be calculated based on TG measurement results and DSC measurement results according to the method described in Test Example 2.

[0082] 2. Method for producing polymers In one embodiment, the present invention is based on the general formula (1):

[0083] [ka]

[0084] The present invention relates to a method for producing the polymer of the present invention (sometimes referred to as the "production method of the present invention" in this specification), which includes reacting a polymer (sometimes referred to as the "precursor polymer" in this specification) containing polymer units represented by a sultone in a solvent. This is described below.

[0085] The precursor polymer is R 1 and R 2 One of them independently exhibits a divalent hydrocarbon group in each appearance, R 1 and R 2 The other is the same as the definition of the polymer of the present invention, except that each occurrence independently represents a group represented by general formula (2b1).

[0086] As the precursor polymer, a commercially available one can be used, or one synthesized according to a known method (for example, according to or similar to the method in Test Example 1) can be used.

[0087] Sultones are cyclic sulfonic acid esters of hydroxysulfonic acids. Typically, sultones are represented by general formula (3):

[0088] [ka]

[0089] [In the formula: p represents an integer between 1 and 5 (preferably m is an integer between 2 and 4, and especially preferably 3).] It is a compound represented by [formula].

[0090] From the viewpoint of yield and ease of synthesis, the amount of sultone used is usually preferably 0.1 to 30 moles, and more preferably 0.3 to 15 moles, per mole of precursor polymer. By changing the amount of sultone used, the polymer of the present invention with the desired x / n (sulfobetaine introduction rate) can be obtained.

[0091] This reaction is carried out in a solvent (reaction solvent). The solvent is not particularly limited, but using a fluoroalcohol allows for a particularly simple and efficient acquisition of the polymer of the present invention. Preferably, the fluoroalcohol is a partially fluorinated alcohol, and among these, 2,2,2-trifluoroethanol (TFE) is particularly preferred.

[0092] The reaction can be carried out under heating, room temperature, or cooling conditions, and is typically carried out at 0-80°C. A reaction temperature of 0-10°C is particularly preferred. The reaction time is not particularly limited and is typically 30 minutes to 60 hours.

[0093] The reaction can be tracked using conventional methods such as chromatography. After the reaction is complete, the solvent is removed by distillation, and the product can be isolated and purified using conventional methods such as chromatography and reprecipitation. The structure of the product can also be determined by elemental analysis, MS (ESI-MS) analysis, IR analysis, etc. 1 H-NMR, 13 The product can be identified by 13C-NMR or the like. Furthermore, if necessary, a base such as sodium bicarbonate can be added to the product of the above reaction to neutralize the amino group in the product.

[0094] 3.Applications The polymer of the present invention possesses oil repellency (particularly oil repellency in water), hydrophilicity, adhesiveness, and other properties. Therefore, the polymer of the present invention can be suitably used as an oil repellent, antifouling agent, hydrophilic agent, adhesive, and the like. Furthermore, in order to exhibit the above effects, the polymer of the present invention can also be suitably used as a coating agent.

[0095] In one embodiment, the present invention relates to a composition (hereinafter referred to as "the composition of the present invention") containing the polymer of the present invention.

[0096] The composition of the present invention may be an oil repellent, an antifouling agent, a hydrophilic agent, or an adhesive. Furthermore, the composition of the present invention may be used for coatings.

[0097] The composition of the present invention may consist solely of the polymer of the present invention, or it may contain the polymer of the present invention and other components. Other components may include those commonly used for various applications. The content of the polymer of the present invention in the total components of the composition of the present invention, excluding the solvent, may be, for example, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more.

[0098] In one embodiment, the present invention relates to an article comprising the polymer of the present invention.

[0099] There are no particular restrictions on the type of article. Furthermore, there are no particular restrictions on the shape of the article.

[0100] In one embodiment, the polymer of the present invention has excellent water solubility (particularly in high-salt water), so articles of the present invention can be used as plastic products in which microplastic formation in the sea is suppressed.

[0101] Since the polymer of the present invention has properties such as oil repellency, hydrophilicity, and adhesiveness, articles of the present invention (particularly articles having a coating layer containing the polymer of the present invention on their surface) can be used in a variety of applications as articles exhibiting these properties. For example, by utilizing its oil repellency, it can be used as an oil-water separation material. [Examples]

[0102] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples.

[0103] Test Example 1. Synthesis of Sulfobetaine Polyester (Poly(diethyl sulfobetaine terephthalate); PDSBT) <1.1. Synthesis of Polyester (Poly(N-methyl-N,N-diethylamino terephthalate); PMDAT)>

[0104] [ka]

[0105] [Table 1]

[0106] PMDAT, a polyester, was synthesized according to Scheme 1 and Table 1. Terephthaloyl chloride (TPC) was dissolved in N-methyl-2-pyrrolidone (NMP) under an Ar atmosphere, and pyridine was added. Further, a solution of 2,2'-Methyliminodiethanol (MDEA) in NMP was added, and the mixture was stirred for 24 hours. After stirring, an excess amount of methanol was added. The precipitate was collected by suction filtration, and a white solid was obtained by vacuum drying at 50 °C.

[0107] <1. 2. 1 Identification of PMDAT by 1H NMR measurement > 1 PMDAT was identified by 1H NMR measurement. PMDAT was dissolved in trifluoroacetic acid-d at a concentration of 10 mg / mL as the solvent. Sodium 3-(trimethylsilyl) propionate-2,2,3,3-d4 was used as the reference substance, and measurements were performed with 64 cumulative counts.

[0108] <1.3. GPS measurement of PMDAT> The molecular weight of PMDAT was determined by GPC measurement. PMDAT was dissolved in 2,2,2-trifluoroethanol (TFE) at a concentration of 5 mg / mL. After filtering through a 0.45 μm PTFE membrane, 20 μL of the solution was injected into the GPC. The measurement conditions were a flow rate of 1.0 mL / min, a temperature of 40 °C, and radioisotope detection. Two PSS PFG analytical columns, 100 Å and 1000 Å, were connected in series and used as columns. A molecular weight calibration curve was prepared using Poly(methyl methacrylate).

[0109] <1.4. Synthesis of PDSBT>

[0110] [ka]

[0111] [Table 2]

[0112] PDSBT, a sulfobetaine polyester, was synthesized according to Scheme 2 and Table 2. PDSBT was dissolved in TFE under an Ar atmosphere. A TFE solution of 1,3-propanesultone was then added, and the mixture was stirred for 48 hours. After stirring, the reaction solution was added dropwise to 300 mL of acetone. The precipitate was collected by centrifugation, and a yellow solid was obtained by vacuum drying at 50 °C.

[0113] <1. 5. 1 Identification of PDSBT by 1H NMR measurement > 1 PDSBT was identified by 1H NMR measurement. PDSBT was dissolved in trifluoroacetic acid-d at a concentration of 10 mg / mL as the solvent. Sodium 3-(trimethylsilyl)propionate-2,2,3,3-d4 was used as the reference material, and measurements were performed with 64 cumulative counts.

[0114] <1.6. Neutralization of PDSBT>

[0115]

Table 3

[0116] The amino groups of PDSBT were neutralized according to Table 3. PDSBT was dissolved in ultrapure water, and an aqueous solution of NaHCO3 was slowly added. The precipitate was collected by centrifugation and washed with ultrapure water. A yellow solid was obtained by freeze-drying.

[0117] <Results> < 1 1H NMR measurement results Figure 1 shows the 1H NMR spectra of PMDAT and PDSBT. In PDSBT, the sulfobetaine introduction rates of PDSBT for Run1-6 were calculated to be 20, 56, 68, 83, 95, and 98% respectively from the integration ratios of the d and h peaks. Hereinafter, PDSB 1 T, PDSB 20 T, PDSB 56 T, PDSB 68 T, PDSB 83 T, PDSB 95 T, PDSB 98 T is denoted. Calculation formula: Sulfobetaine introduction rate (%) = ((integration value of peak h / 2) / (integration value of peak d / 4)) × 100

[0118] <GPC measurement results of PMDAT> Figure 2 and Table 4 show the results of the GPC measurement of PMDAT for Run1 and Run2.

[0119]

Table 4

[0120] Test Example 2. Thermal properties of PDSBT before and after neutralization. PDSBT before and after neutralization was added to an aluminum pan, and the decomposition temperature was measured by differential thermogravimetric analysis (TG / DTA measurement). The measurement conditions are shown in Table 5.

[0121] [Table 5]

[0122] Furthermore, PDSBT was added to an aluminum pan, sealed using a sample sealer, and the glass transition temperature or melting point of PDSBT was measured by differential scanning calorimetry (DSC measurement). The measurement conditions are shown in Table 6.

[0123] [Table 6]

[0124] The TG measurement results for PMDAT and PDSBT are shown in Figures 3-1 and 3-2, and the DSC measurement results are shown in Figures 4-1 and 4-2. Furthermore, the 5% weight loss temperature (T) obtained from these results is shown. d ), and glass transition temperature (T g ), melting point (T m The results are summarized in Table 7.

[0125] [Table 7]

[0126] Test Example 3. Water solubility of PMDAT and PDSBT PMDAT or PDSBT 6 mg was added to 2 mL of ultrapure water, and changes in solubility with temperature and salt concentration were evaluated.

[0127] Table 8 summarizes the water solubility of PMDAT and PDSBT when their salt concentrations are varied.

[0128] [Table 8]

[0129] Temperature-responsive behavior was observed when PMDAT and PDSBT were dissolved in a 1 M NaCl aqueous solution before neutralization. The turbidity measurement results for PMDAT at varying salt concentrations are shown in Figure 5 and Table 9, and the turbidity measurement results for PDSBT with a sulfobetaine introduction rate of 98% in a 1 M NaCl aqueous solution are shown in Figure 6.

[0130] [Table 9]

[0131] Test Example 4. Contact Angle of PMDAT and PDSBT Neutralized PMDAT or PDSBT was dissolved at a concentration of 3 wt% using TFE as the solvent. The silicon wafer used as the substrate was washed twice for 5 minutes each with Methanol, ultrapure water, and Acetone in that order, and then treated with ozone. 40 μL of the sample solution was spread onto the silicon wafer and the surface was coated with a spin coater. The spin coater was rotated at 2000 rpm for 1 minute. The contact angle of the sample thin film in air was measured using ultrapure water. The droplet size was 2 μL.

[0132] Figure 7 shows images of the contact angles of PMDAT and PDSBT with respect to water, and Table 10 shows the average contact angles. Excellent hydrophilicity was observed in PDSBT, which has a high sulfobetaine introduction rate.

[0133] [Table 10]

[0134] Test Example 5. Oil repellency of PMDAT and PDSBT in water A sample thin film was formed in the same manner as in Test Example 4, and the contact angle of the sample thin film with respect to hexadecane in water was measured. The droplet size was 2 μL.

[0135] Figure 8 shows images of the contact angles of PMDAT and PDSBT with respect to hexadecane in water, and Table 11 shows the average contact angles. In Table 12, "-" indicates that no hexadecane oil droplets adhered (i.e., the oil repellency in water was high enough that no oil droplets adhered), as shown in Figure 8. Excellent oil repellency in water was observed in PDSBT, which has a high sulfobetaine introduction rate.

[0136] [Table 11]

[0137] Test Example 6. Adhesion properties of PMDAT and PDSBT Test Example 6-1. Tensile Shear Test Neutralized PMDAT or PDSBT was placed on one end of a 1 cm x 3 cm PET film and heated to 130 °C. Another PET film was placed over it, overlapping by 1 cm, and pressurized at 1 MPa for 1 minute. Afterwards, it was cooled to room temperature and stretched at a speed of 50 mm / min at a 180° angle to the adhesive surface.

[0138] Test Example 6-2. Peel Test Neutralized PMDAT or PDSBT was placed on one end of a 3 cm x 3 cm PET film and heated to 130 °C. A 1 cm x 3 cm PET film was placed over it, overlapping by 1 cm, and pressurized at 1 MPa for 1 minute. Afterwards, it was cooled to room temperature and stretched at a speed of 50 mm / min at a 90° angle to the adhesive surface.

[0139] The results of the tensile shear test are shown in Table 12, and the results of the peel test are shown in Table 13.

[0140] [Table 12]

[0141] [Table 13]

Claims

1. General formula (1): 【Chemistry 1】 [In the formula: R 1 and R 2 One of them independently exhibits a divalent hydrocarbon group in each appearance, R 1 and R 2 The other, in each occurrence, is independently given by general formula (2a), general formula (2b1), or general formula (2b2): 【Chemistry 2】 (In the formula: R 31 and R 32 These represent the same or different divalent hydrocarbon groups. 33 (where m represents a monovalent hydrocarbon group, and m represents an integer from 1 to 5.) represents a group (however, at least one R 1 or R 2 represents a group represented by the general formula (2a).). n represents an integer of 1 or more.] It consists of polymer units represented by, The ratio (x / n) of the number of groups (x) represented by the general formula (2a) in the polymer unit to n is 0.6 or more and 0.99 or less. polymer.

2. The aforementioned R 1 is a divalent hydrocarbon group, and the R 2 The polymer according to claim 1, wherein the group is represented by general formula (2a), general formula (2b1), or general formula (2b2).

3. The aforementioned R 1 is a divalent hydrocarbon group containing an aromatic ring, and the R 31 and R 32 is an alkylene group, and the R 33 The polymer according to claim 2, wherein is an alkyl group.

4. The polymer according to claim 1, wherein the ratio (x / n) of the number of groups represented by the general formula (2a) in the polymer unit to n is 0.65 or more and 0.99 or less.

5. The polymer according to claim 1, wherein the ratio (x / n) of the number of groups represented by the general formula (2a) in the polymer unit to n is 0.83 or more and 0.99 or less.

6. The polymer according to claim 1, wherein the ratio (x / n) of the number of groups represented by the general formula (2a) in the polymer unit to n is 0.9 or more and 0.99 or less.

7. The polymer according to claim 1, wherein the ratio (x / n) of the number of groups represented by the general formula (2a) in the polymer unit to n is 0.65 or more and 0.95 or less.

8. The polymer according to claim 1, wherein the weight-average molecular weight of the polymer unit is 5000 or more.

9. A composition containing the polymer described in any one of claims 1 to 8.

10. The composition according to claim 9, which is an oil repellent, an antifouling agent, a hydrophilic agent, or an adhesive.

11. The composition according to claim 9, which is for coating purposes.

12. An article comprising the polymer according to any one of claims 1 to 8.

13. General formula (1): 【Transformation 3】 [In the formula: R 1 and R 2 One of them independently exhibits a divalent hydrocarbon group in each appearance, R 1 and R 2 The other side, independently in each occurrence, is given by the general formula (2b1): 【Chemistry 4】 (In the formula: R 31 and R 32 R represents the same or different divalent hydrocarbon group. 33 (This indicates a monovalent hydrocarbon group.) This indicates a base represented by . n is an integer greater than or equal to 1. The process involves reacting a polymer, consisting of polymer units represented by [the specified formula], with a sultone in a solvent. A method for producing the polymer according to any one of claims 1 to 8.

14. The method according to claim 13, wherein the solvent is a fluoroalcohol.

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