JP2023124226A - Rotaxane and method for producing the same, and crosslinked polymer, polymer fine particle and polymer resin member - Google Patents

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 The present invention relates to a rotaxane, a method for producing the same, a crosslinked polymer, a polymer fine particle, and a polymer resin member.

Conventionally, a crosslinked polymer using rotaxane (polyrotaxane) as a crosslinking agent is known (for example, Patent Document 1).

WO2005/095493

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 in mechanical properties (particularly elongation at break and stress at break) is desirable.

Therefore, in view of the above circumstances, the present invention provides a rotaxane that provides a crosslinked polymer that exhibits excellent mechanical properties (especially, breaking elongation and breaking stress) when used as a crosslinker, a method for producing the same, and a crosslinker It is an object of the present invention to provide a crosslinked polymer using the above rotaxane as a polymer, polymer microparticles comprising the above crosslinked polymer, and a polymer resin member produced using the above crosslinked polymer.

As a result of intensive studies on the above problems, the present inventors found that the above problems can be solved by using two or more polymer chains bonded via a linking group as the axial molecule of the rotaxane, leading to the present invention. Ta.
That is, the inventors have found that the above problems can be solved by the following configuration.

(1) A rotaxane having two or more cyclic molecules and an axial molecule passing through the cyclic molecules,
The cyclic molecule has a reactive functional group-containing group,
Rotaxane, wherein the axial molecule is a molecule represented by formula (1) described later.
(2) 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; The rotaxane according to (1) above.
(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 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. The rotaxane according to any one of (1) to (3).
(5) The rotaxane according to any one of (1) to (4) above, which is a cross-linking agent.
(6) A method for producing a rotaxane according to any one of (1) to (5) above,
A method for producing rotaxane, wherein the polymer chain is obtained by living radical polymerization.
(7) A crosslinked polymer using the rotaxane according to any one of (1) to (5) above as a crosslinking agent.
(8) A copolymer of a monomer and the rotaxane according to any one 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) Polymer microparticles comprising the crosslinked polymer described in (7) or (8) above.
(10) A polymeric resin member produced using the crosslinked polymer described in (7) or (8) above.

As shown below, according to the present invention, a rotaxane that provides a crosslinked polymer that exhibits excellent mechanical properties (particularly elongation at break and stress at break) when used as a crosslinker, a method for producing the same, and a crosslinker It is possible to provide a crosslinked polymer using the above rotaxane as a material, polymer microparticles made of the above crosslinked polymer, and a polymer resin member produced using the above crosslinked polymer.

¹ H NMR spectrum of 1-1. ¹ H NMR spectrum of the precursor (complexed) of 2-1. ¹ H NMR spectrum of 2-1.

Hereinafter, the rotaxane of the present invention, a method for producing the same, a crosslinked polymer using the rotaxane as a crosslinking agent, and a polymer resin member produced using the above crosslinked polymer will be described.
In this specification, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
Moreover, in this specification, each component may be used individually by 1 type, or may use 2 or more types together. Here, when two or more of each component are used in combination, the amount of that component refers to the total amount unless otherwise specified.
Moreover, in this specification, (meth)acryl means acryl or methacryl, (meth)acrylate means acrylate or methacrylate, and (meth)acryloyl means acryloyl or methacryloyl.
Moreover, in this specification, a "methyl group" is also represented as "Me."
Further, in this specification, a high breaking elongation is also referred to as excellent breaking elongation, and a high breaking stress is also referred to as excellent breaking stress.
In the present specification, the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and may be chain or branched. It may be either continuous or cyclic.

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

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

<Group containing reactive functional group>
As described above, the cyclic molecule has a reactive functional group-containing group.

The reactive functional group-containing group is a reactive functional group or a group containing a reactive functional group, -ZP (where Z represents a single bond or a divalent linking group, P represents a reactive functional group).

The reactive functional group is not particularly limited as long as it contributes to cross-linking, but for the reason that the effect of the present invention is more excellent, hydroxyl group, amino group, (meth)acryloyl group, (meth)acryloyloxy group, epoxy group and It is preferably at least one selected from the group consisting of vinyl groups.

The reactive functional group is preferably a polymerizable unsaturated group for the reason that the effects of the present invention are more excellent.
Although the polymerizable unsaturated group is not particularly limited, specific examples thereof include a vinyl group, an acrylic group (acryloyl group), a methacrylic group (methacryloyl group), an acryloyloxy group, a methacryloyloxy group, and the like. Among them, an acryloyloxy group and a methacryloyloxy group are preferable because the effects of the present invention are more excellent.

Specific examples of the case where Z in -ZP is a divalent linking group include a divalent aliphatic hydrocarbon group (especially an alkylene group), a divalent aromatic hydrocarbon group, a divalent hetero cyclic group (especially aromatic heterocyclic group), -O-, -S-, -SO ₂ -, -N(R)- (R: hydrogen atom or substituent), -CO-, -COO-, -CONR - (R: hydrogen atom or substituent), groups in which these are combined, and the like.

<Number of cyclic molecules>
The number of the cyclic molecules contained in the specific rotaxane is not particularly limited as long as it is two or more, but two is preferable because the effect of the present invention is more excellent. Although the upper limit of the cyclic molecule is not particularly limited, it is preferably 100 or less, more preferably 10 or less, because the effects of the present invention are more excellent.

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

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 a linking group. Multiple L may be the same or different. Y represents a sealing group. Multiple Y's may be the same or different. m represents an integer of 1 or more. When m is an integer of 2 or more, multiple X's may be the same or different.

<A>
As described above, in formula (1), A represents a polymer chain.
Although the polymer chain is not particularly limited, specific examples thereof include polyalkylene oxide, poly(meth)acrylate, diene-based polymer, and the like.
The polymer chain is preferably at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, poly(meth)acrylate, polyisoprene and polybutadiene, because the effects of the present invention are more excellent.

The number average molecular weight (Mn) of the polymer chain is not particularly limited, but is preferably 300 to 1,000,000, more preferably 400 to 10,000, for the reason that the effects of the present invention are more excellent. , 500 to 1,000.
In addition, in this specification, the molecular weight is a standard polystyrene conversion value based on the measured value by gel permeation chromatography (GPC method) using tetrahydrofuran (THF) as a solvent.

The degree of polymerization of the polymer chain is not particularly limited, but is preferably from 3 to 10,000, more preferably from 4 to 1,000, and more preferably from 5 to 10, because the effects of the present invention are more excellent. is more preferred.

Multiple A's may be the same or different.

<X>
As described above, in formula (1), X represents a linking group.
Specific examples of the linking group include a divalent aliphatic hydrocarbon group (especially an alkylene group), a divalent aromatic hydrocarbon group, a divalent heterocyclic group (especially an aromatic heterocyclic group), -O- , -S-, -SO ₂ -, -N(R)- (R: hydrogen atom or substituent), -CO-, -COO-, -CONR- (R: hydrogen atom or substituent), combinations thereof and the like.

When m in formula (1) is an integer of 2 or more, multiple X's may be the same or different.

<L>
As described above, in formula (1), L represents a single bond or a linking group.
Specific examples of when L is a divalent linking group include a divalent aliphatic hydrocarbon group (especially an alkylene group), a divalent aromatic hydrocarbon group, a divalent heterocyclic group (especially an aromatic heterocyclic group), -O-, -S-, -SO ₂ -, -N(R)- (R: hydrogen atom or substituent), -CO-, -COO-, -CONR- (R: hydrogen atom or a substituent), a group obtained by combining these, and the like.

Multiple L may be the same or different.

<Y>
As described above, in formula (1), Y represents a sealing group.
The above-mentioned blocking group is not particularly limited as long as it is a bulky group for preventing the cyclic molecule from detaching from the axial molecule. It is preferably at least one selected from the group consisting of a phenyl group, a neopentyl group, an adamantyl group, a 3,5-dimethylphenyl group and a cyclohexyl group, more preferably a 3,5-dimethylphenyl group.

<m>
As described above, in formula (1), m represents an integer of 1 or more.
The above m is preferably 1 because the effect of the present invention is more excellent.
The upper limit of m is not particularly limited, but for the reason that the effect of the present invention is more excellent, it is preferably an integer of 100 or less, more preferably an integer of 10 or less, and further an integer of 5 or less. An integer of 3 or less is particularly preferred.

〔Production method〕
The method for producing the specific rotaxane is not particularly limited, and examples thereof include a method combining known methods.
The method of producing the specific rotaxane is preferably a method of obtaining the polymer chain represented by A in the formula (1) by living polymerization in the synthesis of the axial molecule, since the specific rotaxane to be obtained has a more excellent effect of the present invention. . In addition, hereinafter, "the effect of the present invention is more excellent with respect to the obtained specific rotaxane" is simply referred to as "the effect of the present invention is more excellent".
Examples of the living polymerization include living cationic polymerization, living anionic polymerization, and living radical polymerization. Among them, living radical polymerization is preferable because the effects of the present invention are more excellent.
Examples of the living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer polymerization (RAFT), nitroxide-mediated polymerization (NMP), and the like. Among them, atom transfer radical polymerization is preferable because the effects of the present invention are more excellent.

[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 specific rotaxane described above as a crosslinker.

[Preferred embodiment]
The polymer of the present invention is preferably a copolymer of a monomer and a specific rotaxane for the reason that the effects of the present invention are more excellent.

<Monomer>
The above monomers are not particularly limited as long as at least a part of the monomers reacts with the reactive functional groups of the specific polysiloxane described above.
The above monomer is preferably (meth)acrylate for the reason that the effect of the present invention is more excellent.

((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, isodecinonyl (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-dicyclohexyl Oxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylates, 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-1,4-cyclohexanediol di (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, 3-methoxybutyl (Meth) acrylate, methoxydipropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, poly (ethylene glycol-) tetramethylene glycol) (meth)acrylate, poly(propylene glycol-tetramethylene glycol) (meth)acrylate, polyethylene glycol-polypropylene glycol (meth)acrylate, glycidyl (meth)acrylate and the like.

The above (meth)acrylate is preferably an ester of acrylic acid or methacrylic acid and an alcohol having 1 to 10 carbon atoms for the reason that the effect of the present invention is more excellent, and acrylic acid or methacrylic acid and 1 to 5 carbon atoms. is more preferably an ester with an alcohol of , more preferably an ester of acrylic acid or methacrylic acid with an alcohol having 1 to 3 carbon atoms.

The (meth)acrylate may be used singly or in combination of two or more, but the (meth)acrylate contains at least methoxyethyl (meth)acrylate for the reason that the effects of the present invention are more excellent. is preferred.

(other monomers)
Monomers other than the above (meth)acrylates may be used, but the ratio of (meth)acrylates to all monomers ((meth)acrylates and other monomers) is 90 mol for the reason that the effects of the present invention are more excellent. % or more, more preferably 95 mol % or more. The upper limit of the ratio of (meth)acrylate to all monomers is not particularly limited, and is 100 mol %.

<Specific rotaxane/monomer>
The ratio of the specific rotaxane described above to the monomer described above is preferably 0.001 to 10 mol %, more preferably 0.01 to 1 mol %, for the reason that the effects of the present invention are more excellent.

[Polymer particles]
The polymer microparticles of the present invention are polymer microparticles made of the above-described polymer of the present invention.

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

[Swelling degree]
The degree of swelling of the polymer microparticles of the present invention is not particularly limited, but is preferably 10 or more, more preferably 18 or more, and even more preferably 20 or more because the effect of the present invention is more excellent. . Although the upper limit of the degree of swelling is not particularly limited, it is preferably 100 or less because the effects of the present invention are more excellent.
The degree of swelling is a parameter represented by the following formula.
Degree of swelling = (D _h (DMF)) ³ /(D _h (water)) ³
Here, D _h (DMF) represents the above-described harmonic mean diameter in DMF. D _h (water) represents the harmonic mean diameter in water, and the measurement method is the same as the harmonic mean diameter in DMF described above, except that water is used instead of DMF.

[Use]
The polymer microparticles of the present invention are useful, for example, as additives in rubber compositions, adhesive compositions, coating compositions, and the like.

[Polymer resin member]
The polymer resin member of the present invention is a polymer resin member (eg, film) produced using the above-described crosslinked polymer of the present invention.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these.

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

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

<Synthesis of 1-1>
First, a two-necked flask containing copper bromide (0.17 g, 1.2 mmol) was substituted with Ar, and 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 stirred at 80° C. for 3 hours. After cooling to room temperature and diluting the reaction solution with dichloromethane, the copper catalyst was removed by alumina column chromatography (dichloromethane), and the solution was concentrated (crude yield: 5.3 g). Thereafter, reprecipitation was performed with hexane to obtain a colorless and transparent viscous liquid with a yield of 89% (4.6 g) (1-1). A molecular weight of about 800 was determined by ¹ H NMR (nuclear magnetic resonance) (Fig. 1: ¹ H NMR spectrum).

<Synthesis of 1-2>
Next, the two-necked flask containing the obtained 1-1 (2.4 g, 3.0 mmol) was purged with Ar, dissolved in dehydrated dichloromethane (30 mL), and 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, and the mixture was stirred at room temperature for 23 hours. The reaction solution was concentrated, methanol was added, reprecipitation was performed with hexane, and a white solid was removed by suction filtration. After that, the white solid was completely removed by multiple filtrations to obtain a colorless transparent viscous liquid with a yield of 83% (2.4 g) (1-2).

<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 substituted with Ar, and N,N-dimethylformamide (dry DMF) was added thereto. (30 mL) was added and dissolved, and the mixture was stirred at room temperature for 24 hours. A large amount of water was added to the reaction solution, the mixture was extracted with dichloromethane, the organic layer was dried over magnesium sulfate, and the filtrate was concentrated. Thereafter, reprecipitation was performed with hexane to obtain a colorless and transparent viscous liquid with a yield of 95% (2.2 g) (1-3).

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

<Synthesis of 2-1>
First, in an eggplant flask containing an axial component (a component that becomes a group represented by formula (X1) described later) (240 mg, 0.35 mmol) and a cyclic molecule (636 mg, 1.0 mmol) synthesized as described below, dichloromethane was added. (3.0 mL) was added and ultrasonic irradiation was performed (complex formation) (Fig. 2: ¹ H NMR spectrum). pMA(1-3) (1.2 mg, 1.3 mmol) and [Cu(CH ₃ CN) ₄ ]PF ₆ (239 mg, 0.64 mmol) dissolved in dichloromethane (3.0 mL) were added thereto. and 40° C. for 40 hours. The ^reaction solution was reprecipitated with diethyl ether, the insoluble portion (including the copper catalyst) was separated from the soluble portion, and the soluble portion was concentrated (0.32 g). determined to be A 10% aqueous solution of ammonium chloride and ethyl acetate were added, the mixture was stirred for 30 minutes, and then liquid separation was performed. The organic layer was dried and concentrated to obtain a colorless viscous liquid. After that, the viscous liquid was collected by two preparative GPC methods and vacuum dried to obtain 390 mg (yield 30%) of a transparent pale yellow solid (2-1) (Fig. 3: ¹ H NMR spectrum).

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

<Synthesis of 2-2>
Next, a two-necked flask containing 2-1 (114 mg, 0.03 mmol) was replaced with Ar, and dehydrated tetrahydrofuran (dry THF) (0.3 mL) and acetic anhydride (0.14 mL, 1.5 mmol) were added. , triethylamine (TEA) (0.34 mL, 2.4 mmol) was added, and 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), the organic layer was dried and concentrated to obtain a brown viscous liquid. After that, it was purified by a preparative GPC method and vacuum-dried to obtain a viscous liquid with a yield of 87% (100 mg, 0.026 mmol) (2-2). The obtained rotaxane (2-2) is also referred to as “RC”.

RC is a rotaxane having two cyclic molecules (crown ether derivatives) and an axial molecule passing through the cyclic molecules,
The cyclic molecule has a group (reactive functional group-containing group) containing a methacryloyl group (reactive functional group),
The axial molecule is a molecule represented by the above formula (1) (wherein m is 1, two A are both polymethyl acrylate (polymer chain), and X is the following A group represented by formula (X1) (in formula (X1), * represents a bonding position) (linking group), and both of the two Ls are groups represented by the following formula (L1) (formula (L1 ), *1 represents the bonding position with Y, *2 represents the bonding position with A) (linking group), and both Y are 3,5-dimethylphenyl groups (blocking groups) ), it corresponds to the above-mentioned specific rotaxane.

[Synthesis of polymer particles]
A mixed solution of a monomer and a cross-linking agent in the ratio [molar ratio] shown in Table 1 below (water: 36 g, surfactant (sodium dodecylbenzenesulfonate): 0.1 g, hydrophobe (hexadecane): 0.46 g, total Monomer concentration: 1600 mM) was emulsified by ultrasonic irradiation (375 W, 3 minutes) with an ultrasonic homogenizer, and then an initiator (potassium persulfate) (0.1 g) was added to the resulting emulsion and heated to 70°C. for 4 hours (stirring speed: 200 rpm (rotations per minute)) to obtain each polymer microparticle. .
Table 1 shows D _h (water) and D _h (DMF) of each polymer fine particle. The methods for measuring D _h (water) and D _h (DMF) are as described above.

〔monomer〕
The abbreviations of the monomers in Table 1 below are as follows.
・EA: Ethyl acrylate ・MEA: 2-methoxyethyl acrylate ・MMA: Methyl methacrylate

[Crosslinking agent]
The abbreviations of the cross-linking agents in Table 1 below are as follows.
RC: RC synthesized as described above
・HDD: 1,6-hexanediol dimethacrylate (chemical cross-linking agent)
-Comparative RC: SM2450P-20 manufactured by ASM (a rotaxane having a plurality of cyclic molecules and an axial molecule penetrating the cyclic molecule, the cyclic molecule containing a methacryloyl group (reactive functional group-containing group ), and the axial molecule is a molecule other than the molecule represented by the above formula (1) (a molecule represented by YLALY, A: polymer chain, L: single bond or Linking group, Y: sealing group, molecular weight: 20,000) rotaxane)

[evaluation]
A 5 cm square film (thickness: about 0.4 mm) was prepared using the obtained dispersion (5% by mass, 7 mL) of each polymer microparticle (purified by centrifugation and dialyzed). Four films of 1 cm×4 cm were cut out from the obtained film, and a 2 mm cut was made in the center in the longitudinal direction using a diamond cutter. Thus, a test piece for a tensile test was produced.
The obtained test piece was subjected to a tensile test (load cell: 50 N, elongation speed: 10 mm/min, test temperature: 25° C.) using a Tensilon tensile tester to evaluate breaking elongation and breaking stress. Table 1 shows the results. It is preferable that both elongation at break and stress at break are large.

As can be seen from Table 1, from the comparison between Comparative Examples 1 to 3 and Example 2 (comparison of the embodiments in which only the type of cross-linking agent is different), it was found that polymer fine particles using a cross-linking agent other than the specific rotaxane as the cross-linking agent Compared with certain Comparative Examples 1 to 3, Example 2, which is a polymer fine particle using a specific rotaxane as a cross-linking agent, exhibited excellent elongation at break and breaking stress. Similarly, from the comparison between Comparative Examples 4 to 6 and Example 5 (comparison between embodiments in which only the type of cross-linking agent is different), Comparative Example 4, which is a polymer fine particle using a cross-linking agent other than the specific rotaxane as a cross-linking agent 6, Example 5, which is a polymer fine particle using a specific rotaxane as a cross-linking agent, exhibited excellent elongation at break and breaking stress. Compared to Comparative Examples 7 to 9, which are polymer fine particles using a cross-linking agent other than the specific rotaxane as a cross-linking agent, Example 8, which is a polymer fine particle using a specific rotaxane as a cross-linking agent, has excellent elongation at break and indicated the breaking stress.
From the comparison of Examples 1 to 3 (comparison of aspects in which only the molar ratio of the cross-linking agent is different), Example 2, in which the ratio of the specific rotaxane to the monomer is 0.07 to 0.17 mol%, is more excellent rupture Elongation and breaking stress are given. Similarly, from the comparison of Examples 4 to 6 (comparison of embodiments that differ only in the molar ratio of the cross-linking agent), Example 5, in which the ratio of the specific rotaxane to the monomer is 0.07 to 0.17 mol%, is more It exhibited excellent elongation at break and stress at break. Similarly, from the comparison of Examples 7 to 9 (comparison of aspects in which only the molar ratio of the cross-linking agent is different), Example 8 in which the ratio of the specific rotaxane to the monomer is 0.07 to 0.17 mol% is more It exhibited excellent elongation at break and stress at break.

Claims (10)

A rotaxane having two or more cyclic molecules and an axial molecule penetrating the cyclic molecules,
the cyclic molecule has a reactive functional group-containing group,
Rotaxane, wherein the axial molecule is a molecule represented by the following formula (1).

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 a linking group. Multiple L may be the same or different. Y represents a sealing group. Multiple Y's may be the same or different. m represents an integer of 1 or more. When m is an integer of 2 or more, multiple X's may be the same or different. 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. The rotaxane of claim 1. 3. The rotaxane according to claim 1 or 2, wherein the polymer chain is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, poly(meth)acrylate, polyisoprene and polybutadiene. Claims 1-, 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. 4. The rotaxane according to any one of 3. The rotaxane according to any one of claims 1 to 4, which is a cross-linking agent. A method for producing a rotaxane according to any one of claims 1 to 5,
A method for producing rotaxane, wherein the polymer chain is obtained by living radical polymerization. A crosslinked polymer using the rotaxane according to any one of claims 1 to 5 as a crosslinking agent. A copolymer of a monomer and the rotaxane according to any one of claims 1 to 5,
The crosslinked polymer according to claim 7, wherein the ratio of said rotaxane to said monomer is 0.001 to 10 mol%. Polymer fine particles comprising the crosslinked polymer according to claim 7 or 8. A polymer resin member produced using the crosslinked polymer according to claim 7 or 8.