Rotaxane and its manufacturing method, as well as crosslinked polymers, polymer fine particles, and polymer resin components.

Abstract

To provide a rotaxane that can give a crosslinked polymer having excellent mechanical properties when used as a crosslinker and a method for producing the same, a crosslinked polymer including the rotaxane as a crosslinker, a polymer fine particle including the crosslinked polymer, and a polymer resin member produced from the crosslinked polymer.SOLUTION: A rotaxane includes two or more cyclic molecules and an axial molecule penetrating the cyclic molecule. The cyclic molecule includes a reactive functional group-containing group. The axial molecule is represented by the formula (1). In the formula (1), A is a polymer chain. A plurality of A's may be the same or different. X is a linking group. L is a single bond or a linking group. Y is a capping group. m is an integer of 1 or greater.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to rotaxanes and methods for producing the same, as well as crosslinked polymers, polymeric fine particles, and polymeric resin components. [Background technology]

[0002] Conventionally, crosslinked polymers using rotaxanes (polyrotaxanes) as crosslinking agents are known (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2005 / 095493 [Overview of the project] [Problems that the invention aims to solve]

[0004] When the present inventors synthesized a crosslinked polymer using rotaxane as a crosslinking agent with reference to Patent Document 1, it became clear that further improvement of mechanical properties (particularly elongation at break and stress at break) was desirable.

[0005] Therefore, in view of the above circumstances, the present invention aims to provide a rotaxane that yields a crosslinked polymer exhibiting excellent mechanical properties (particularly elongation at break and stress at break) when used as a crosslinking agent, a method for producing the same, a crosslinked polymer using the rotaxane as a crosslinking agent, polymer fine particles made of the crosslinked polymer, and a polymer resin component manufactured using the crosslinked polymer. [Means for solving the problem]

[0006] As a result of diligent research into the above-mentioned problems, the inventors of this invention discovered that the above-mentioned problems can be solved by making the axial molecule of the rotaxane a polymer chain of two or more linked groups, and thus arrived at the present invention. In other words, the inventors have found that the above problem can be solved by the following configuration.

[0007] (1) A rotaxane having two or more cyclic molecules and an axial molecule that penetrates the cyclic molecules, The above cyclic molecule has a reactive functional group-containing group, The axial molecule mentioned above is rotaxane, which is represented by formula (1) described later. (2) The rotaxane according to (1) above, wherein the reactive functional group of the reactive functional group-containing group is at least one selected from the group consisting of a hydroxyl group, an amino group, a (meth)acryloyl group, a (meth)acryloyloxy group, an epoxy group, and a vinyl group. (3) The rotaxane according to (1) or (2) above, wherein the polymer chain is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, poly(meth)acrylate, polyisoprene, and polybutadiene. (4) The rotaxane according to any one of (1) to (3) above, wherein the sealing group is at least one selected from the group consisting of a tert-butyl group, a tert-butylphenyl group, a neopentyl group, an adamantyl group, a 3,5-dimethylphenyl group, and a cyclohexyl group. (5) A rotaxane as described in any of (1) to (4) above, which is a crosslinking agent. (6) A method for producing rotaxane as described in any of (1) to (5) above, A method for producing rotaxane, comprising obtaining the above polymer chain by living radical polymerization. (7) A crosslinked polymer using any of the rotaxanes described in (1) to (5) above as a crosslinking agent. (8) A copolymer of a monomer and a rotaxane described in any of (1) to (5) above, The crosslinked polymer according to (7) above, wherein the ratio of the rotaxane to the monomer is 0.001 to 10 mol%. (9) Polymeric microparticles comprising the crosslinked polymer described in (7) or (8) above. (10) A polymer resin member produced using the crosslinked polymer according to (7) or (8) above. [Effects of the Invention]

[0008] As described below, according to the present invention, there can be provided: a rotaxane that, when used as a crosslinking agent, provides a crosslinked polymer exhibiting excellent mechanical properties (in particular, elongation at break and stress at break); a method for producing the same; a crosslinked polymer using the rotaxane as a crosslinking agent; polymer fine particles composed of the crosslinked polymer; and a polymer resin member produced using the crosslinked polymer. [Brief Description of Drawings]

[0009] [Figure 1] It is a 1H NMR spectrum of 1-1. [Figure 2] It is a 1H NMR spectrum of the precursor (complex formation) of 2-1. [Figure 3] It is a 1H NMR spectrum of 2-1. [Mode for Carrying Out the Invention]

[0010] Hereinafter, the rotaxane of the present invention, the method for producing the same, the crosslinked polymer using the rotaxane as a crosslinking agent, and the polymer resin member produced using the crosslinked polymer will be described. In the present specification, a numerical range represented by using "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit, respectively. In addition, in the present specification, each component may be used alone, or two or more types may be used in combination. Here, when two or more types of each component are used in combination, the amount of the component refers to the total amount unless otherwise specified. In addition, in the present specification, (meth)acryl means acryl or methacryl, (meth)acrylate means acrylate or methacrylate, and (meth)acryloyl means acryloyl or methacryloyl. Also, in the present specification, a "methyl group" is also referred to as "Me". Also, in the present specification, a large elongation at break is also referred to as being excellent in elongation at break, and a large breaking stress is also referred to as being excellent in breaking stress. Also, in the present specification, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and may be linear, branched or cyclic.

[0011] [Specific Rotaxane] The rotaxane of the present invention is a rotaxane (polyrotaxane) having two or more cyclic molecules and an axis molecule penetrating through the cyclic molecules, wherein the cyclic molecule has a reactive functional group-containing group, the axis molecule is a molecule represented by formula (1) described below, which is a rotaxane (hereinafter also referred to as "specific rotaxane").

[0012] [Cyclic Molecule] The cyclic molecule is not particularly limited, and specific examples thereof include α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, crown ether, and derivatives of these. The cyclic molecule may have a substituent. Examples of such a substituent include a hydroxy group, an acetyl group, a propionyl group, a hexanoyl group, a methyl group, an ethyl group, a propyl group, a 2-hydroxypropyl group, a 1,2-dihydroxypropyl group, a cyclohexyl group, a butylcarbamoyl group, a hexylcarbamoyl group, a phenyl group, a polycaprolactone group, an alkoxysilane group, an acryloyl group, a methacryloyl group, a cinnamoyl group, polymer chains (a polycaprolactone group, a polycarbonate group, etc.), and derivatives of these. The cyclic molecule is preferably crown ether or a derivative of crown ether, for the reason that the effect of the present invention is more excellent.

[0013] <Reactive Functional Group-Containing Group> As described above, the cyclic molecule has a reactive functional group-containing group.

[0014] The above-mentioned reactive functional group-containing group is a reactive functional group, or a group containing a reactive functional group, and is represented as -ZP (where Z represents a single bond or a divalent linking group, and P represents a reactive functional group).

[0015] The above-mentioned reactive functional group is not particularly limited as long as it contributes to crosslinking, but for reasons that the effects of the present invention are superior, it is preferable that it be at least one selected from the group consisting of a hydroxyl group, an amino group, a (meth)acryloyl group, a (meth)acryloyloxy group, an epoxy group, and a vinyl group.

[0016] The above-mentioned reactive functional group is preferably a polymerizable unsaturated group because it provides superior effects for the present invention. The polymerizable unsaturated group described above is not particularly limited, but specific examples include vinyl groups, acrylic groups (acryloyl groups), methacrylic groups (methacryloyl groups), acryloyloxy groups, and methacryloyloxy groups. Among these, acryloyloxy groups and methacryloyloxy groups are preferred because they provide superior effects for which the present invention is most effective.

[0017] Specific examples of cases where Z in -ZP above is a divalent linking group include divalent aliphatic hydrocarbon groups (especially alkylene groups), divalent aromatic hydrocarbon groups, divalent heterocyclic groups (especially aromatic heterocyclic groups), -O-, -S-, -SO2-, -N(R)- (R: hydrogen atom or substituent), -CO-, -COO-, -CONR- (R: hydrogen atom or substituent), and groups that are combinations of these.

[0018] <Number of cyclic molecules> The number of cyclic molecules in a specific rotaxane is not particularly limited as long as it is 2 or more, but it is preferable that it be 2 for the sake of superior effects of the present invention. The upper limit of the number of cyclic molecules is not particularly limited, but it is preferable that it be 100 or less, and more preferably 10 or less, for the sake of superior effects of the present invention.

[0019] [Axis molecule] The axial molecule mentioned above is the molecule represented by the following formula (1).

[0020] [ka]

[0021] In formula (1), A represents a polymer chain. Multiple A's may be the same or different. X represents a linking group. L represents a single bond or linking group. Multiple L's may be the same or different. Y represents a encapsulating group. Multiple Y's may be the same or different. m represents an integer of 1 or more. If m is an integer of 2 or more, multiple X's may be the same or different.

[0022] As described above, in formula (1), A represents a polymer chain. The polymer chains described above are not particularly limited, but specific examples include polyalkylene oxides, poly(meth)acrylates, and diene polymers. The polymer chain described above is preferably at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, poly(meth)acrylate, polyisoprene, and polybutadiene, for the reason that the effects of the present invention are superior.

[0023] The number-average molecular weight (Mn) of the polymer chain described above is not particularly limited, but is preferably 300 to 1,000,000, more preferably 400 to 10,000, and even more preferably 500 to 1,000, for reasons that the effects of the present invention are superior. In this specification, molecular weight is a standard polystyrene equivalent value based on measurements obtained by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as the solvent.

[0024] The degree of polymerization of the polymer chain described above is not particularly limited, but for reasons that the effects of the present invention are superior, it is preferably 3 to 10,000, more preferably 4 to 1,000, and even more preferably 5 to 10.

[0025] Multiple instances of A may be the same or different.

[0026] <x> As described above, in equation (1), X represents a linking group. Specific examples of the above linking groups include divalent aliphatic hydrocarbon groups (especially alkylene groups), divalent aromatic hydrocarbon groups, divalent heterocyclic groups (especially aromatic heterocyclic groups), -O-, -S-, -SO2-, -N(R)- (R: hydrogen atom or substituent), -CO-, -COO-, -CONR- (R: hydrogen atom or substituent), and groups that combine these.

[0027] In equation (1), if m is an integer greater than or equal to 2, the multiple X values ​​may be the same or different.

[0028] <l> As described above, in formula (1), L represents a single bond or a linking group. Specific examples of cases where L is a divalent linking group include divalent aliphatic hydrocarbon groups (especially alkylene groups), divalent aromatic hydrocarbon groups, divalent heterocyclic groups (especially aromatic heterocyclic groups), -O-, -S-, -SO2-, -N(R)- (R: hydrogen atom or substituent), -CO-, -COO-, -CONR- (R: hydrogen atom or substituent), and groups that are combinations of these.

[0029] Multiple instances of L may be the same or different.

[0030] <y> As described above, in formula (1), Y represents a sealing group. The above-mentioned sealing group is not particularly limited as long as it is a bulky group that prevents the cyclic molecule from detaching from the axial molecule. However, for reasons in which the effects of the present invention are superior, it is preferably at least one selected from the group consisting of a tert-butyl group, a tert-butylphenyl group, a neopentyl group, an adamantyl group, a 3,5-dimethylphenyl group, and a cyclohexyl group, and more preferably a 3,5-dimethylphenyl group.

[0031] <m> As stated above, in equation (1), m represents an integer greater than or equal to 1. The above value of m is preferably 1 because it provides superior effects for the present invention. The upper limit of m is not particularly limited, but for reasons that the effects of the present invention are superior, it is preferably an integer of 100 or less, more preferably an integer of 10 or less, even more preferably an integer of 5 or less, and particularly preferably an integer of 3 or less.

[0032] [Manufacturing method] There are no particular restrictions on the method for producing specific rotaxanes; examples include methods that combine known methods. The preferred method for producing a specific rotaxane is one in which the polymer chain represented by A in formula (1) is obtained by living polymerization in the synthesis of the axial molecule, because the effects of the present invention are superior with respect to the specific rotaxane obtained. Hereinafter, "the effects of the present invention are superior with respect to the specific rotaxane obtained" will also simply be referred to as "the effects of the present invention are superior." Examples of the above-mentioned living polymerization include living cationic polymerization, living anionic polymerization, and living radical polymerization. Among these, living radical polymerization is preferred because it exhibits superior effects compared to the present invention. Examples of the living radical polymerization described above include atom transfer radical polymerization (ATRP), reversible addition-cleavage chain transfer polymerization (RAFT), and nitroxide-mediated polymerization (NMP). Among these, atom transfer radical polymerization is preferred because it exhibits superior effects compared to the present invention.

[0033] [Crosslinked polymer] The crosslinked polymer of the present invention (hereinafter also referred to as "the polymer of the present invention") is a crosslinked polymer using the above-mentioned specific rotaxane as a crosslinking agent.

[0034] [Preferred Embodiment] The polymer of the present invention is preferably a copolymer of a monomer and a specific rotaxane, for which the effects of the present invention are superior.

[0035] <Monomer> The above monomers are not particularly limited, as long as at least some of them react with the reactive functional groups of the specified polysiloxane described above. The above monomer is preferably a (meth)acrylate because it provides superior effects for the present invention.

[0036] ((meth)acrylate) The above (meth)acrylates are not particularly limited, and specific examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, isononyl (meth)acrylate, isodesinonyl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, isobornyl (meth)acrylate, butoxydiethylene glycol (meth)acrylate Benzyl (meth)acrylate, dicyclohexyl (meth)acrylate, 2-dicyclohexyloxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, nonanediol di(meth)acrylate, 2-morpholinoethyl (meth)acrylate, 9-anthryl (meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trans-1,Examples include 4-cyclohexanediol di(meth)acrylate, dicyclopentenyloxyethyl(meth)acrylate, methoxyethyl(meth)acrylate, 3-methoxybutyl(meth)acrylate, methoxydipropylene glycol(meth)acrylate, methoxytripropylene glycol(meth)acrylate, methoxypolyethylene glycol(meth)acrylate, polyethylene glycol(meth)acrylate, polypropylene glycol(meth)acrylate, polypropylene glycol(meth)acrylate, poly(ethylene glycol-tetramethylene glycol)(meth)acrylate, polypropylene glycol-tetramethylene glycol(meth)acrylate, polyethylene glycol-polypropylene glycol(meth)acrylate, glycidyl(meth)acrylate, etc.

[0037] The above (meth)acrylate is preferably an ester of acrylic acid or methacrylic acid with an alcohol having 1 to 10 carbon atoms, more preferably an ester of acrylic acid or methacrylic acid with an alcohol having 1 to 5 carbon atoms, and even more preferably an ester of acrylic acid or methacrylic acid with an alcohol having 1 to 3 carbon atoms, for reasons that the effects of the present invention are superior.

[0038] While one type of (meth)acrylate may be used or two or more types may be used in combination, it is preferable that the (meth)acrylate includes at least methoxyethyl (meth)acrylate for the reasons that the effects of the present invention are superior.

[0039] (Other monomers) Other monomers besides the (meth)acrylate mentioned above may be used, but the ratio of (meth)acrylate to the total monomers ((meth)acrylate and other monomers) is preferably 90 mol% or more, and more preferably 95 mol% or more, for the sake of superior effects of the present invention. There is no particular upper limit to the ratio of (meth)acrylate to the total monomers, and it is 100 mol%.

[0040] <Specific Rotaxane / Monomer> The ratio of the above-mentioned specific rotaxane to the above-mentioned monomer is preferably 0.001 to 10 mol%, and more preferably 0.01 to 1 mol%, for the reasons that the effects of the present invention are superior.

[0041] [Polymer fine particles] The polymeric microparticles of the present invention are polymeric microparticles made of the polymer of the present invention as described above.

[0042] [Harmonic mean diameter] The harmonic mean diameter of the polymer fine particles of the present invention is not particularly limited, but for reasons that the effects of the present invention are better, it is preferably 2000 nm or less, more preferably 1000 nm or less, and even more preferably 500 nm or less. The lower limit of the above harmonic mean diameter is also not particularly limited, but for reasons that the effects of the present invention are better, it is preferably 10 nm or more, more preferably 50 nm or more, even more preferably 100 nm or more, and particularly preferably 200 nm or more. The above harmonic mean diameter is the harmonic mean diameter in DMF (dimethylformamide) measured by the cumulant method using a particle size analyzer (Malvern Zetasizer Nano S).

[0043] [Degree of swelling] The degree of swelling of the polymer microparticles of the present invention is not particularly limited, but it is preferably 10 or more, more preferably 18 or more, and even more preferably 20 or more, for the reason that the effects of the present invention are superior. The upper limit of the above degree of swelling is not particularly limited, but it is preferably 100 or less, for the reason that the effects of the present invention are superior. The degree of swelling mentioned above is a parameter expressed by the following formula. Swelling degree = (D h (DMF)) 3 / (D h (water)) 3 Here, D h (DMF) represents the harmonic mean diameter in the DMF mentioned above. Also, D h (Water) represents the harmonic mean diameter in water, and its measurement method is the same as the harmonic mean diameter in DMF described above, except that water is used instead of DMF.

[0044] [Application] The polymer fine particles of the present invention are useful as additives in, for example, rubber compositions, adhesive compositions, and paint compositions.

[0045] [Polymer resin components] The polymer resin component of the present invention is a polymer resin component (for example, a film) manufactured using the crosslinked polymer of the present invention described above. [Examples]

[0046] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0047] [Synthesis of rotaxanes] Rotaxane (2-2) was synthesized as follows.

[0048] [Combination of 1-3] pMA(1-3) was synthesized according to Scheme 1 below.

[0049] <1-1 synthesis> First, a two-necked flask containing copper bromide (0.17 g, 1.2 mmol) was purged with Ar, and then methyl acrylate (4.3 mL, 48 mmol), N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDETA) (0.25 mL, 1.2 mmol), and 2-hydroxyethyl 2-bromoisobutyrate (0.70 mL, 4.8 mmol) were added in that order, and the mixture was stirred at 80°C for 3 hours. After cooling to room temperature, the reaction solution was diluted with dichloromethane, and the copper catalyst was removed by alumina column chromatography (dichloromethane). The solution was then concentrated (crude yield 5.3 g). Subsequently, reprecipitation with hexane was performed to obtain a colorless, transparent viscous liquid in a yield of 89% (4.6 g) (1-1). 1 The molecular weight was determined to be approximately 800 by 1H NMR (nuclear magnetic resonance spectroscopy) (Figure 1: 1 H NMR spectrum).

[0050] <Synthesis of 1-2> Next, a two-necked flask containing the obtained 1-1 (2.4 g, 3.0 mmol) was purged with Ar, and 1-1 was dissolved in dehydrated dichloromethane (30 mL). 3,5-dimethylphenyl isocyanate (0.63 mL, 4.5 mmol) and dibutyltin dilaurate (DBTDL) (0.18 mL, 0.30 mmol) were added in that order, followed by stirring at room temperature for 23 hours. The reaction solution was concentrated, methanol was added thereto, reprecipitation was performed with hexane, and the white solid was removed by suction filtration. Thereafter, the white solid was completely removed by repeated filtration, whereby a colorless and transparent viscous liquid was obtained in a yield of 83% (2.4 g) (1-2).

[0051] <Synthesis of 1-3> A two-necked flask containing the obtained 1-2 (2.4 g, 2.5 mmol) and sodium azide (0.79 g, 12 mmol) was purged with Ar, N,N-dimethylformamide (dry DMF) (30 mL) was added thereto to dissolve the contents, followed by stirring at room temperature for 24 hours. A large amount of water was added to the reaction solution, extraction was performed with dichloromethane, the organic layer was dried over magnesium sulfate, and the filtrate after filtration was concentrated. Thereafter, reprecipitation was performed with hexane, whereby a colorless and transparent viscous liquid was obtained in a yield of 95% (2.2 g) (1-3).

[0052]

Chemical Formula

[0053] [Synthesis of 2-2] Next, 2-2 was synthesized according to Scheme 2 below.

[0054] <Synthesis of 2-1> First, dichloromethane (3.0 mL) was added to an eggplant flask containing an axial component (a component that becomes a group represented by formula (X1) described below) (240 mg, 0.35 mmol) and a cyclic molecule synthesized as described below (636 mg, 1.0 mmol), and ultrasonic irradiation was performed (complex formation) (Figure 2: 1 (H NMR spectrum). To this, pMA(1-3) (1.2 mg, 1.3 mmol) and [Cu(CH3CN)4]PF6 (239 mg, 0.64 mmol), dissolved in dichloromethane (3.0 mL), were added and stirred at 40°C for 40 hours. The reaction solution was reprecipitated with diethyl ether, the insoluble portion (including copper catalyst) and the soluble portion were separated, the soluble portion was concentrated (0.32 g), and the 1 From the 1H NMR spectrum, it was determined that the mixture consisted of axial components and cyclic molecules. A 10% aqueous ammonium chloride solution and ethyl acetate were added, the mixture was stirred for 30 minutes, followed by liquid-liquid separation. The organic layer was dried and concentrated to obtain a colorless viscous liquid. Subsequently, the viscous liquid was recovered by two preparative GPC methods and vacuum-dried to obtain 390 mg (30% yield) of a transparent, pale yellow solid (2-1) (Figure 3). 1 (H NMR spectrum).

[0055] (Synthesis of cyclic molecules) To a solution of hydroxymethyldibenzo-24-crown-8-ether (1.9 g) in methylene chloride (45 mL), 2-isocyanate ethyl methacrylate (1.4 mL) and dibutyltin dilaurate (0.2 mL) were added at 0°C, and the mixture was stirred at room temperature for 48 hours. The resulting mixture was concentrated to 10 mL and added to hexane to obtain a precipitate. The precipitate was dissolved in an ethyl acetate / hexane mixture (2 / 3) and analyzed using a silica column. 2.5 g of the target cyclic molecule was obtained.

[0056] <Composition of 2-2> Next, a two-necked flask containing 2-1 (114 mg, 0.03 mmol) was purged with Ar, and anhydrous tetrahydrofuran (dry THF) (0.3 mL), acetic anhydride (0.14 mL, 1.5 mmol), and triethylamine (TEA) (0.34 mL, 2.4 mmol) were added. The mixture was stirred at 40°C for 2 days. The reaction solution was concentrated, dissolved in ethyl acetate, washed (saturated ammonium chloride aqueous solution, saturated sodium bicarbonate aqueous solution, brine), and the organic layer was dried and concentrated to obtain a brownish viscous liquid. Subsequently, the liquid was purified by preparative GPC and vacuum-dried to obtain a viscous liquid in yield of 87% (100 mg, 0.026 mmol) (2-2). The obtained rotaxane (2-2) is also called "RC".

[0057] [ka]

[0058] RC is a rotaxane having two cyclic molecules (derivatives of crown ethers) and an axial molecule that penetrates the above cyclic molecules, The above cyclic molecule has a group containing a methacryloyl group (reactive functional group), The above-mentioned axial molecule is a rotaxane represented by the above-mentioned formula (1) (wherein formula (1) is 1, both A's are methyl polyacrylate (polymer chain), X is a group represented by the following formula (X1) (wherein formula (X1) is a bonding position) (linking group), both L's are a group represented by the following formula (L1) (wherein formula (L1) is a bonding position with Y, and *2 is a bonding position with A) (linking group), and both Y's are 3,5-dimethylphenyl groups (sealing groups)), and therefore corresponds to the above-mentioned specific rotaxane.

[0059] [ka]

[0060] [ka]

[0061] [Synthesis of polymer microparticles] A mixed solution of monomers and crosslinking agents in the proportions [molar ratios] listed in Table 1 below (water: 36 g, surfactant (sodium dodecylbenzenesulfonate): 0.1 g, hydrophob (hexadecane): 0.46 g, total monomer concentration: 1600 mM) was emulsified by ultrasonic irradiation (375 W, 3 min) using an ultrasonic homogenizer. Then, an initiator (potassium persulfate) (0.1 g) was added to the resulting emulsion, and the polymerization reaction was carried out at 70°C for 4 hours (stirring speed: 200 rpm (rotations per minute)) to obtain each polymer microparticle. Each polymer microparticle is a polymer microparticle consisting of a crosslinked polymer using the crosslinking agent listed in Table 1. D of each polymer microparticle h (Water) and D h (DMF) is shown in Table 1. h (Water) and D h The method for measuring (DMF) is as described above.

[0062] 〔monomer〕 The abbreviations for monomers in Table 1 below are as follows: • EA: Ethyl acrylate MEA: 2-methoxyethyl acrylate • MMA: Methyl methacrylate

[0063] [Crosslinking agent] The abbreviations for the crosslinking agents in Table 1 below are as follows: • RC: Synthesized RC as described above • HDD: 1,6-Hexanediol dimethacrylate (chemical crosslinking agent) • Comparative RC: ASM SM2450P-20 (a rotaxane having multiple cyclic molecules and an axial molecule penetrating the cyclic molecules, wherein the cyclic molecules have a group containing a methacryloyl group (a reactive functional group-containing group), and the axial molecule is a molecule other than the molecule represented by formula (1) above (a molecule represented by YLALY, A: polymer chain, L: single bond or linking group, Y: sealing group, molecular weight: 20,000)).

[0064] [evaluation] A 5cm square film (thickness: approximately 0.4mm) was prepared using a dispersion of each obtained polymer microparticle (5% by mass, 7mL) (centrifugally purified and dialyzed). Four 1cm x 4cm pieces were cut from the obtained film, and a 2mm incision was made in the center of the longitudinal direction using a diamond cutter. In this way, test specimens for tensile testing were prepared. The obtained specimens were subjected to tensile tests using a Tensilon tensile testing machine (load cell: 50N, elongation rate: 10 mm / min, test temperature: 25°C) to evaluate the elongation at break and the stress at break. The results are shown in Table 1. Higher elongation at break and stress at break are preferable.

[0065] [Table 1]

[0066] As can be seen from Table 1, a comparison between Comparative Examples 1-3 and Example 2 (a comparison of embodiments that differ only in the type of crosslinking agent) shows that Example 2, which uses a specific rotaxane as the crosslinking agent, exhibited superior elongation at break and stress at break compared to Comparative Examples 1-3, which use a crosslinking agent other than a specific rotaxane as the crosslinking agent. Similarly, a comparison between Comparative Examples 4-6 and Example 5 (a comparison of embodiments that differ only in the type of crosslinking agent) shows that Example 5, which uses a specific rotaxane as the crosslinking agent, exhibited superior elongation at break and stress at break compared to Comparative Examples 4-6, which use a crosslinking agent other than a specific rotaxane as the crosslinking agent. Compared to Comparative Examples 7-9, which use a crosslinking agent other than a specific rotaxane as the crosslinking agent, Example 8, which uses a specific rotaxane as the crosslinking agent, exhibited superior elongation at break and stress at break. Comparing Examples 1-3 (comparing embodiments that differ only in the molar ratio of the crosslinking agent), Example 2, in which the ratio of the specific rotaxane to the monomer was 0.07-0.17 mol%, showed superior elongation at break and fracture stress. Similarly, comparing Examples 4-6 (comparing embodiments that differ only in the molar ratio of the crosslinking agent), Example 5, in which the ratio of the specific rotaxane to the monomer was 0.07-0.17 mol%, showed superior elongation at break and fracture stress. Similarly, comparing Examples 7-9 (comparing embodiments that differ only in the molar ratio of the crosslinking agent), Example 8, in which the ratio of the specific rotaxane to the monomer was 0.07-0.17 mol%, showed superior elongation at break and fracture stress.< / m> < / y> < / l> < / x>

Claims

1. A polymeric microparticle comprising a crosslinked polymer using a specific rotaxane as a crosslinking agent, The aforementioned specific rotaxane, A rotaxane having two or more cyclic molecules and an axial molecule penetrating the cyclic molecules, The cyclic molecule may have substituents, and is an α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, crown ether, or a derivative thereof, and has a reactive functional group-containing group. The aforementioned axial molecule is a rotaxane, which is represented by the following formula (1): The crosslinked polymer is a copolymer of a monomer and the specified rotaxane. Polymeric fine particles in which the ratio of the specified rotaxane to the monomer is 0.001 to 10 mol%. 【Chemistry 1】 In formula (1), A represents a polymer chain with a degree of polymerization of 3 or higher. Multiple instances of A may be the same or different. X represents a linking group. L represents a single bond or a linking group. Multiple Ls may be the same or different. Y represents a sealing group. Multiple Ys may be the same or different. m represents an integer of 1 or more. If m is an integer greater than or equal to 2, the multiple X values ​​may be the same or different.

2. The polymer fine particles according to claim 1, wherein the ratio of the specific rotaxane to the monomer is 0.01 to 1 mol%.

3. The polymer fine particles according to claim 1 or 2, wherein the reactive functional group of the reactive functional group-containing group is at least one selected from the group consisting of a hydroxyl group, an amino group, a (meth)acryloyl group, a (meth)acryloyloxy group, an epoxy group, and a vinyl group.

4. The polymer fine particles according to any one of claims 1 to 3, wherein the polymer chain is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, poly(meth)acrylate, polyisoprene, and polybutadiene.

5. The polymer fine particles according to any one of claims 1 to 4, wherein the sealing group is at least one selected from the group consisting of a tert-butyl group, a tert-butylphenyl group, a neopentyl group, an adamantyl group, a 3,5-dimethylphenyl group, and a cyclohexyl group.

6. A method for producing polymer fine particles according to any one of claims 1 to 5, A method for producing polymer nanoparticles, wherein the polymer chain is obtained by living radical polymerization.

Images