Polymer material, damping material, method for producing polymer material, and cyclic polymer

Abstract

Disclosed is a polymer material that comprises: a cyclic polymer which has one or more annular parts; and a crosslinked polymer which has a plurality of linear parts, and in which the plurality of linear parts are bonded to each other at crosslinking points so as to form a crosslinked body. At least some of the cyclic polymers in the polymer material each have an annular part that is penetrated by a linear part of the crosslinked polymer. The ratio of the amount of the cyclic polymer to the amount of the crosslinked polymer may be 15% by mass or more.

Description

Polymer material, damping material, method for producing polymer material, and cyclic polymer

[0001] The present disclosure relates to polymeric materials, damping materials, methods of making polymeric materials, and cyclic polymers.

[0002] In recent years, polymer gels in which linear polymers are filled into crosslinked polymers have been reported as vibration-damping materials (Non-Patent Document 1).

[0003] J. Huang, Y. Xu, S. Qi, J. Zhou, W. Shi, T. Zhao, M. Liu, Nat.Commun. 2021, 12, 3610

[0004] One aspect of the present disclosure relates to novel polymeric materials that contain additive modifying components and exhibit reduced bleed-out properties.

[0005] The present disclosure includes the following: [1] A polymer material comprising: a cyclic polymer having one or more cyclic segments; and a crosslinked polymer having a plurality of linear chain segments, the plurality of linear chain segments being bonded to each other at crosslinking points to form a crosslinked body, wherein at least a portion of the cyclic polymer in the polymer material has the cyclic segment pierced by the linear chain segment of the crosslinked polymer, and the ratio of the amount of the cyclic polymer to the amount of the crosslinked polymer is 15% by mass or more. [2] The polymer material according to [1], wherein the trapping rate of the cyclic polymer is 50% by mass or more, as calculated by the following formula: Trap rate (mass%) = {(W0 - W1) / W0} × 100, where W0 is the mass of the cyclic polymer in the polymer material, and W1 is the mass of a portion of the cyclic polymer in the polymer material that dissolves in a solvent at 25°C in which the cyclic polymer is soluble, when the polymer material is immersed in the solvent for 48 hours to 120 hours. [3] The polymer material according to [1] or [2], wherein the cyclic polymer has a number average molecular weight of 3,000 or more per cyclic portion in the cyclic polymer as determined by SEC-MALS. [4] The polymer material according to any one of [1] to [3], wherein the linear portion of the crosslinked polymer comprises a polymer chain corresponding to a linear polymer having a number average molecular weight of 1,500 or more as determined by SEC-MALS. [5] The polymer material according to any one of [1] to [4], wherein the cyclic portion and the linear portion comprise a polysiloxane chain. [6] The polymer material according to any one of [1] to [5], wherein the polymer material exhibits a tan δ of 0.08 or more at an angular frequency of 100 rad / s and a temperature of 25°C. [7] A polymer material comprising: a cyclic polymer having one or more cyclic segments; and a crosslinked polymer having a plurality of linear segments, the linear segments being bonded to each other at crosslinking points to form a crosslinked body, wherein at least a portion of the cyclic polymers in the polymer material have the cyclic segments pierced by the linear segments of the crosslinked polymer, and at least one of the cyclic segments or the linear segments comprises an acrylic polymer chain or a polyoxyalkylene chain. [8] The polymer material according to [7], wherein the cyclic segments and the linear segments comprise acrylic polymer chains.[9] The polymer material according to [7], wherein the cyclic portion and the linear portion comprise polyoxyalkylene chains.

[10] A damping material comprising the polymer material according to any one of [1] to [9].

[11] A method for producing a polymer material, comprising: preparing a mixture containing monomer components including a cyclic polymer having one or more cyclic portions and a monomer having an ethylenically unsaturated group; and polymerizing the monomer components in the mixture to form a crosslinked polymer having a plurality of linear portions, the plurality of linear portions being bonded to each other at crosslinking points to form a crosslinked body.

[12] The method according to

[11] , wherein at least one of the cyclic portion or the linear portion comprises an acrylic polymer chain, a polyoxyalkylene chain, or a polysiloxane chain.

[13] The method according to

[11] , wherein the cyclic portion and the linear portion comprise an acrylic polymer chain.

[14] The polymer material according to

[11] , wherein the cyclic portion and the linear portion comprise a polyoxyalkylene chain.

[15] The method according to

[11] , wherein the cyclic portion and the linear portion comprise a polysiloxane chain.

[16] A compound represented by the following formula (II) or (II'): R ２ represents a tetravalent hydrocarbon group; L ２ represents a divalent linker group, and Q ２ contains an acrylic polymer chain and R ２ and L ２

[17] A cyclic polymer, which represents a polymer chain forming a cyclic portion together with the following formula (II) or (II'): R ２ represents a tetravalent hydrocarbon group; L ２ represents a divalent linker group, and Q ２ contains a polyoxyalkylene chain and R ２ and L ２

[18] R represents a polymer chain forming a cyclic portion together with ２ is represented by the following formula (20a), (20b), (20c), (20d), (20′a), (20′b), (20′c) or (20′d):

[18] The cyclic polymer according to

[16] or

[17] , wherein R is a tetravalent hydrocarbon group represented by the formula:

[0006] A novel polymer material with little bleed-out can be provided while containing additive components for property modification. According to one aspect of the present disclosure, a polymer material with high tan δ over a wide temperature range and little bleed-out can be provided. Polymer materials with high tan δ are thought to have excellent vibration-damping properties and are useful, for example, as damping materials. According to another aspect of the present disclosure, a polymer material with little bleed-out can be provided while containing additive components that increase breaking elongation.

[0007] FIG. 1 is a schematic diagram showing an example of the structure of a polymer material; FIG. 2 is a schematic diagram showing an example of the structure of a polymer material; FIG. 3 is a schematic diagram showing an example of a method for producing a polymer material; FIG. 4 is a master curve of G' and G'' of a polymer material; FIG. 5 is a master curve of tan δ of a polymer material (Example); FIG. 6 is a master curve of tan δ of a polymer material (Comparative Example);

[0008] The present invention is not limited to the following examples.

[0009] The polymer material according to the present disclosure includes a cyclic polymer having one or more cyclic segments and a crosslinked polymer. FIG. 1 is a schematic diagram showing an example of the structure of a polymer material including a cyclic polymer having one cyclic segment. FIG. 2 is a schematic diagram showing an example of the structure of a polymer material including a cyclic polymer having three cyclic segments. The crosslinked polymer 20 has multiple linear segments 21, and the multiple linear segments 21 are bonded to each other at crosslinking points 25 to form a crosslinked structure. The linear segments 21 of the crosslinked polymer 20 pierce the cyclic segments of at least some of the cyclic polymers 10 in the polymer material, thereby forming a rotaxane structure. When the cyclic polymer 10 has multiple cyclic segments, one or more of the cyclic segments may be pierced by the linear segments 21.

[0010] The cyclic polymer 10 forming the rotaxane structure is less likely to bleed out because it is trapped between the two crosslinking points 25 of the crosslinked polymer 20. In addition, the cyclic polymer 10 can move to some extent between the crosslinking points 25, which can contribute to improving the viscoelastic properties and flexibility (e.g., breaking elongation), etc.

[0011] In the polymer material, the ratio of the amount of cyclic polymer to the amount of crosslinked polymer may be 15% by mass or more. A higher cyclic polymer content tends to result in a higher tan δ of the polymer material. The ratio of the amount of cyclic polymer to the amount of crosslinked polymer may be 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more. The ratio of the amount of cyclic polymer to the amount of crosslinked polymer may be 100% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, or 70% by mass or less. The ratio of the amount of cyclic polymer to the amount of crosslinked polymer may be 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, 40% by mass or more, 45% by mass or more, 50% by mass or more, 55% by mass or more, or 60% by mass or more, but 100% by mass or less.

[0012] In a polymer material, even if the ratio of the amount of cyclic polymer to the amount of crosslinked polymer is less than 15% by mass, the introduction of the cyclic polymer can increase the breaking elongation of the polymer material. From this perspective, the ratio of the amount of cyclic polymer to the amount of crosslinked polymer may be 0.5% by mass or more, 1% by mass or more, or 2% by mass or more, or may be 100% by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less. The ratio of the amount of cyclic polymer to the amount of crosslinked polymer may be 0.5% by mass or more, 1% by mass or more, or 2% by mass or more, and may be 100% by mass or less.

[0013] When the proportion of the cyclic polymer in the polymer material that forms a rotaxane structure and is trapped by the crosslinked polymer (trapping rate) is high, bleed-out tends to be suppressed. For example, the trapping rate of the cyclic polymer calculated by the following formula may be 50% by mass or more: Trap rate (mass%) = {(W0 - W1) / W0} × 100

[0014] W0 is the mass of the cyclic polymer in the polymer material, and W1 is the mass of the portion of the cyclic polymer in the polymer material that dissolves in the solvent when the polymer material is immersed in a solvent at 25°C in which the cyclic polymer dissolves for 48 hours to 120 hours. The trapping rate may be 60% by mass or more, 70% by mass or more, or 80% by mass or more. The upper limit of the trapping rate is 100% by mass, in which case no component that dissolves in the solvent is detected. The trapping rate when the polymer material is immersed in a solvent at 25°C in which the cyclic polymer dissolves for 48 hours or 120 hours may be within the above range.

[0015] The type and amount of solvent used to measure the trapping rate are selected so that an amount of cyclic polymer equivalent to the total amount of cyclic polymer in the polymer material can be dissolved. For example, when the cyclic polymer has a polysiloxane chain or an acrylic polymer chain, toluene can be used as the solvent. When the cyclic polymer has a polyoxyalkylene chain, methanol can be used as the solvent. For example, a film of the polymer material having a thickness of about 0.5 to 1.5 mm can be immersed in the solvent.

[0016] The trapping rate can be evaluated at the operating temperature by changing the temperature of the solvent used to measure the trapping rate to a temperature that simulates the operating environment of the polymer material.In addition, by changing the temperature of the solvent used to measure the trapping rate to a higher temperature, an accelerated test can be performed.

[0017] A larger molecular weight of the cyclic portion of a cyclic polymer tends to increase the trapping rate. Therefore, the number average molecular weight of the cyclic polymer may be 3,000 or more, 5,000 or more, 10,000 or more, 15,000 or more, 20,000 or more, 25,000 or more, or 30,000 or more per cyclic portion in the cyclic polymer. The number average molecular weight of the cyclic polymer may be 100,000 or less per cyclic portion in the cyclic polymer. The number average molecular weight of the cyclic polymer may be 3,000 or more, 5,000 or more, 10,000 or more, 15,000 or more, 20,000 or more, 25,000 or more, or 30,000 or more per cyclic portion in the cyclic polymer, and may be 100,000 or less. Unless otherwise specified, the number average molecular weight in this specification refers to a value measured by SEC (size exclusion chromatography)-MALS (multi-angle light scattering) method.

[0018] The cyclic portion of a cyclic polymer is a portion that forms a single closed ring. The number of cyclic portions per molecule of the cyclic polymer can be, for example, 1 to 50. The number of cyclic portions per molecule of the cyclic polymer may be 1 or more, or 2 or more, or may be 50 or less, 45 or less, 35 or less, 30 or less, 25 or less, 20 or less, 15 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, 5 or less, 4 or less, or 3 or less. The average number of cyclic portions per molecule of the cyclic polymer contained in the polymer material may be within these numerical ranges.

[0019] A cyclic polymer having one cyclic group (monocyclic polymer) is represented, for example, by the following formula (I): １ represents a divalent hydrocarbon group, and L １ represents a divalent linker group, and Q １ is R １ and L １ The figure shows a polymer chain that forms a ring with two L in the same molecule. １ may be the same or different.

[0020]

[0021] R １ may be an alkanediyl group having 2 to 15 carbon atoms or an alkenediyl group having 2 to 15 carbon atoms.１ may be a residue of two terminal groups bonded by an olefin metathesis reaction, examples of which are represented by the following formula (10) or (10'): In formulas (10) and (10'), R ３ represents an alkanediyl group having 1 to 10 carbon atoms, and two R ３ may be the same or different. The group of formula (10') may be a group formed by a hydrogenation reaction of the group of formula (10), and can contribute to improving the stability of the polymer material.

[0022]

[0023] L １ Q is a terminal group having a carbon-carbon double bond for forming a cyclic moiety by olefin metathesis reaction. １ In that case, L １ L can be any group selected from those that are industrially available as linker groups for introducing terminal groups. １ may be a group represented by the following formula (11), (12), or (13), for example. In formula (11), p and q each independently represent an integer of 1 to 5. In formula (12), r represents an integer of 0 to 5 or 1 to 5. The group of formula (11) or (12) usually has R on the carbonyl group side. １ (or R described below) ２ ) and combines with

[0024]

[0025] Q １ may include, for example, a polysiloxane chain, an acrylic polymer chain, or a polyoxyalkylene chain.

[0026] Q containing polysiloxane chains １ An example of the formula (30) is shown below. In formula (30), R ４ represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a fluorine atom, or an alkoxy group having 1 to 5 carbon atoms which may be substituted with a fluorine atom, and n represents a positive integer. ４ may be the same or different. ４R may be a linear, branched or cyclic saturated or unsaturated aliphatic group, or an aromatic group. ４ may be an alkyl group having 1 to 5 or 1 to 3 carbon atoms, a vinyl group, or a phenyl group.

[0027]

[0028] The acrylic polymer chain is a polymer chain formed by polymerization of one or more monomers having an acryloyl group or a methacryloyl group. The monomer constituting the acrylic polymer chain may be a (meth)acrylic acid alkyl ester. １ Examples of the formula (31) or (32) are shown below. In formula (31), R ７ represents a hydrogen atom or a methyl group, and R ８ represents a hydrocarbon group which may have a substituent, or a hydrogen atom; R ９ represents a divalent organic group, n １ and n ２ In formula (32), R ７ represents a hydrogen atom or a methyl group, and R ８ represents an alkyl group which may have a substituent, or a hydrogen atom, and n represents a positive integer. １ Multiple R's in ７ and R ８ may be the same or different. ８ When R is a hydrocarbon group which may have a substituent, the hydrocarbon group may have 1 to 18, 1 to 12, 1 to 8, or 2 to 6 carbon atoms. ８ R may be a saturated hydrocarbon group (e.g., an alkyl group) from the viewpoint of stability during production. ８ Specific examples include stearyl, lauryl, isobornyl, n-octyl, 2-ethylhexyl, n-hexyl, cyclohexyl, n-butyl, and ethyl groups.

[0029]

[0030] R in formula (31) ９may be the residue derived from any bifunctional initiator for atom transfer radical polymerization (ATRP) to form acrylic polymer chains. For example, R ９ may be a divalent group represented by the following formula (310): １０ and R １１ R each independently represents an alkylene group. １０ is, for example, a propane-2,2-diyl group (—C(CH ３ ) ２ -) may also be used. １１ may be an alkylene group having 2 to 10 carbon atoms (for example, an ethane-1,2-diyl group).

[0031]

[0032] Q containing a polyoxyalkylene chain １ Examples of the formula (33) or (34) are shown below. In formula (33), R １２ represents an alkylene group, and R １３ represents a divalent organic group, n １ and n ２ R in formula (33) or (34) each independently represents a positive integer. １２ may be an ethane-1,2-diyl group, a propane-1,2-diyl group, a butane-1,2-diyl group, or a butane-1,4-diyl group. １２ When is a propane-1,2-diyl group, either the 1-position or the 2-position may be bonded to the oxygen atom.

[0033]

[0034] R in formula (33) １３ may be, for example, a divalent group represented by the following formula (330) or (331). In formula (330), R １４ represents an alkylene group having 1 to 5 carbon atoms (for example, a methylene group). １５ represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0035]

[0036] A cyclic polymer having two or more cyclic portions (polycyclic polymer) can have two or more structural units having one cyclic portion. Two or more structural units having one cyclic portion may be continuously bonded in series. The following formulas (II) and (II') show examples of structural units having one cyclic portion. In formulas (II) and (II'), R ２ represents a tetravalent hydrocarbon group, L ２ represents a divalent linker group, and Q ２ is R ２ and L ２ The structural unit of formula (II′) may be a group formed by a hydrogenation reaction of the double bond in the structural unit of formula (II), and can contribute to improving the stability of the polymer material.

[0037]

[0038] R ２ may be an alkanediyl group having 2 to 20 carbon atoms or an alkenediyl group having 2 to 20 carbon atoms. ２ Examples of R are represented by the following formulae (20a), (20b), (20c), and (20d). In formulae (20a) to (20d), * indicates a bond. The structure of formula (20) may be either a cis or trans isomer at the double bond. ２ may be a group represented by the following formula (20'a), (20'b), (20'c), or (20'd). * in formulas (20'a) to (20'd) also represents a bond. The groups of formulas (20'a) to (20'd) can contribute to improving the stability of the polymer material.

[0039]

[0040] The cyclic polymer having a tetravalent group represented by formula (20a), (20b), (20c), or (20d) can be obtained, for example, by polymerizing a compound represented by formula (IIA) below. The compound of formula (IIA) is a compound represented by formula (I) ２ and L ２and norbornenyl groups bonded to both ends of the molecular chain. The group represented by formula (20a), (20b), (20c), or (20d) is a structural unit derived from two norbornenyl groups in the same molecule. Usually, the reaction of two norbornenyl groups mainly produces the group of formula (20a). When each chemical formula described in this specification contains a structure corresponding to the group represented by formula (20a), that structure is described as a representative example and can be replaced with a structure corresponding to the group represented by formula (20b), (20c), or (20d). The tetravalent group represented by formula (20'a), (20'b), (20'c), or (20'd) can be a group formed by hydrogenation to the group represented by formula (20a), (20b), (20c), or (20d), respectively.

[0041] L ２ and Q ２ Examples of the groups are L in formula (I), respectively. １ and Q １ This is similar to the example above. ２ may contain a polysiloxane chain, an acrylic polymer chain, or a polyoxyalkylene chain. ２ may comprise a polysiloxane chain or an acrylic polymer chain, and the cyclic polymer may comprise two or more cyclic moieties.

[0042] In the crosslinked polymer, the linear portion can be a linear polymer chain. The crosslinking points may be located at both ends of each linear portion. Three or more linear portion ends may be bonded to one crosslinking point. The crosslinked polymer may be a crosslinked product of polysiloxane (silicone) in which the linear portion is a polysiloxane chain and the crosslinking point is a silicon atom. In this case, the crosslinked polymer may contain a partial structure having a polysiloxane chain as the linear portion 21, for example, as represented by the following formula (35). In formula (35), R ５ represents a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms which may be substituted with a fluorine atom, or an alkoxy group having 1 to 5 carbon atoms which may be substituted with a fluorine atom; L ２１represents another linear chain portion (polysiloxane chain), n represents a positive integer, x and y each independently represent an integer of 0 to 3, and at least one of x and y is 2 or 3. ２１ , R ５ and R ６ may be the same or different. ２１ The dashed line connecting to L ２１ indicates that R can be attached to other similar substructures. ５ R may be a linear, branched or cyclic, saturated or unsaturated aliphatic group, or an aromatic group. ５ may be an alkyl group having 1 to 5 or 1 to 3 carbon atoms, a vinyl group, or a phenyl group.

[0043]

[0044] The linear portion containing the polysiloxane chain may be bonded to a crosslinking point, which is a carbon atom adjacent to a carbonyl group derived from an acryloyl group or a methacryloyl group. In this case, the crosslinked polymer may contain, for example, a partial structure represented by the following formula (36): ５ is R in formula (35) ５ is defined in the same way as R ７ represents a hydrogen atom or a methyl group, and R １６ represents an alkylene group having 1 to 10 carbon atoms (for example, propane-1,3-diyl group), n represents a positive integer, and * represents a bond.

[0045]

[0046] The crosslinked polymer may have a linear chain portion containing an acrylic polymer chain and a crosslinking point which is a carbon atom derived from an ethylenically unsaturated group. For example, the crosslinking point may be a carbon atom adjacent to a carbonyl group derived from an acryloyl group or a methacryloyl group, and may be a vinyloxy group (—O—CH═CH ２ ) or an allyl group (—CH ２ -CH=CH ２) may be a carbon atom derived from the carbon atom at the 2-position of the acrylic polymer chain. Examples of the acrylic polymer chain constituting the linear chain portion are the same as the examples of the acrylic polymer chain constituting the cyclic polymer. A crosslinked polymer having a linear chain portion containing an acrylic polymer chain may contain, for example, a partial structure represented by the following formula (37). R in formula (37) ７ and R ８ is R in formula (31) ７ and R ８ where n represents a positive integer and * represents a bond.

[0047] The crosslinked polymer may have a linear portion containing a polyoxyalkylene chain and a crosslinking point which is a carbon atom adjacent to a carbonyl group derived from an acryloyl group or a methacryloyl group, or a carbon atom derived from the carbon atom at the second position of a vinyloxy group. The crosslinked polymer having a linear portion containing a polyoxyalkylene chain may contain, for example, a partial structure represented by the following formula (38) or (39). R in formulas (38) and (39) １２ is R in formula (33) １２ where n represents a positive integer and * represents a bond.

[0048]

[0049] Both the cyclic portion of the cyclic polymer and the linear portion of the crosslinked polymer may contain a polysiloxane chain. Both the cyclic portion of the cyclic polymer and the linear portion of the crosslinked polymer may contain an acrylic polymer chain. Both the cyclic portion of the cyclic polymer and the linear portion of the crosslinked polymer may contain a polyoxyalkylene chain. When the cyclic portion and the linear portion contain similar structures, bleeding out can be particularly effectively suppressed.

[0050] The linear portion of the crosslinked polymer may include a polymer chain corresponding to a linear polymer having a number average molecular weight of 1500 or more. For example, if the crosslinked polymer is formed by a method including forming a crosslinked body from a linear polymer having a reactive group, the linear portion can be said to include a polymer chain corresponding to the linear polymer. In other words, the crosslinked polymer may be a crosslinked body formed by reacting a linear polymer having a number average molecular weight of 1500 or more and two reactive groups with a crosslinking agent. The number average molecular weight of the linear polymer corresponding to the linear portion of the crosslinked polymer may be 2000 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, 7000 or more, 8000 or more, 9000 or more, or 10000 or more, or may be 100,000 or less.

[0051] FIG. 3 is a schematic diagram illustrating an example of a method for producing a polymer material. The method illustrated in FIG. 3 involves forming a crosslinked product having a linear portion including a polymer chain derived from the linear polymer 20A by reacting the reactive groups of the linear polymer 20A with the crosslinker 20B in a mixture 30 containing a cyclic polymer 10, a linear polymer 20A having two reactive groups, and a crosslinker 20B. For example, the linear polymer may be a polydialkylsiloxane having silanol groups at both ends, and the crosslinker may be a tetraalkoxysilane. The cyclic polymer can be produced according to methods known to those skilled in the art. The mixture 30 is introduced into a mold having a predetermined shape, and a polymer material is formed in the mold, thereby obtaining molded polymer material bodies having various shapes.

[0052] The polymer material can also be produced by a method including: preparing a mixture containing a cyclic polymer having one or more cyclic segments and a monomer having two or more ethylenically unsaturated groups; and polymerizing the monomer components in the mixture to form a crosslinked polymer having multiple linear segments, the multiple linear segments being linked to each other at crosslinking points to form a crosslinked body. The crosslinked polymer may include a linear segment derived from a partial structure of the monomer having two or more ethylenically unsaturated groups and a linear segment including a polymer chain formed by polymerization of the monomer components. The monomer components may further include a monofunctional monomer. The monomer components may include a monomer having an acryloyl group or a methacryloyl group. When the monomer components include a monomer having an acryloyl group or a methacryloyl group, a linear segment including an acrylic polymer chain can be formed by polymerization of the monomer.

[0053] The polymerization of the monomer components can be promoted by irradiating the mixture with ultraviolet light, an electron beam, or the like, or by heating the mixture. The mixture may contain a photopolymerization initiator or a thermal polymerization initiator.

[0054] The monomer component may contain a monofunctional monomer represented by the following formula (41) and a polyfunctional monomer having two or more (meth)acryloyl groups. ７ and R ８ is R in formula (31). ７ and R ８ The monomer of formula (41) is polymerized to form a linear portion containing an acrylic polymer chain. The polyfunctional monomer may be a compound having two or more (meth)acryloyl groups, a compound having two or more vinyloxy groups, or a combination thereof.

[0055]

[0056] The monomer component may contain a polyfunctional monomer represented by the following formula (36A): R ５ , R ７ and R １６ is R in formula (36). ５ , R ７ and R１６ In this case, polymerization of the monomer components forms a crosslinked polymer having linear portions that include polysiloxane chains.

[0057]

[0058] The monomer component may contain a polyfunctional monomer represented by the following formula (38A) or (39A): R in formula (38A) ７ and R １２ is R in formula (38). ７ and R １２ R in formula (39A) is defined as ７ and R １２ is R in formula (39). １２ In this case, the polymerization of the monomer components forms a crosslinked polymer having a linear portion containing a polyoxyalkylene chain.

[0059]

[0060] While typical elastomer materials often exhibit a decrease in tan δ at low temperatures below their glass transition temperature, polymer materials containing many rotaxane structures based on cyclic polymers can exhibit high tan δ over a wide temperature range, including low temperatures. For example, a polymer material may exhibit a tan δ of 0.08 or greater at an angular frequency of 100 rad / s and a temperature of 25°C. A high tan δ at an angular frequency of 100 rad / s means that a high tan δ is maintained even at low temperatures. The tan δ of the polymer material at an angular frequency of 100 rad / s and a temperature of 25°C may be 0.09 or greater, 0.10 or greater, 0.11 or greater, 0.12 or greater, 0.13 or greater, 0.14 or greater, or 0.15 or greater, or may be 0.30 or less, 0.29 or less, 0.28 or less, 0.27 or less, 0.26 or less, 0.25 or less, 0.24 or less, 0.23 or less, or 0.22 or less. Tan δ at an angular frequency of 100 rad / s and a temperature of 25°C can be determined from a master curve at a reference temperature of 25°C obtained by dynamic viscoelasticity measurement. In this case, "angular frequency" means the "converted angular frequency" in the master curve. Polymer materials containing 15% by mass or more of cyclic polymers tend to exhibit tan δ in these ranges.

[0061] Molded articles containing the polymer materials exemplified above are useful, for example, as various damping materials. The damping material may be, for example, a vibration suppression member, a sound-insulating material, or a seismic isolation rubber. Because polymer materials are unlikely to elute components when in contact with a highly soluble medium, they are also useful as sealing materials for sealing against fluids such as liquids and gases, or for covering and protecting components from fluids. The sealing material may be a molded article such as an oil seal, a packing, an O-ring, or a gasket. The polymer material, or a mixture for forming the polymer material, may be used as a filler for forming the sealing material.

[0062] The molded article may be a molded article of a polymer composition containing a polymer material and other components. Examples of the other components include a filler, a rubber different from the polymer material, a plasticizer, a colorant, and a stabilizer. In the polymer composition, the ratio of the total amount of the other components to 100 parts by mass of the polymer material may be, for example, 0.1 parts by mass, 1 part by mass, or 10 parts by mass or more, or may be 1,000 parts by mass or less, or 100 parts by mass or less.

[0063] The present invention is not limited to the following examples. In the following description, the following abbreviations are used for number average molecular weights: M ｎ，ＮＭＲ : １ Number average molecular weight by H NMR spectrum M ｎ，ＭＡＬＳ : Number average molecular weight by SEC-MALS method M ｎ，ＳＥＣ : Number average molecular weight (standard polystyrene equivalent) determined by size exclusion chromatography (SEC)

[0064] <Study 1: Polymer material having polysiloxane chain> 1. Synthesis of cyclic polymer 1-1. Polycyclic polymer Polydimethylsiloxane having norbornenyl groups at both ends (NB-PDMS ２６ｋ -NB) In a three-neck flask, HOR-PDMS ２６k -ROH (polydimethylsiloxane having hydroxypropyl groups at both ends, M ｎ，ＮＭＲ =25300(CDCl ３), 25.0 g, 0.988 mmol), exo-NB-COOH (546 mg, 3.95 mmol), 4-dimethylaminopyridine (DMAP, 724 mg, 5.93 mmol), and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC.HCl, 1.14 g, 5.93 mol) were added to CH ２ Cl ２ (99 mL). The solution in the three-neck flask was stirred at room temperature under an argon atmosphere for 3 days. ２ Cl ２ The solvent was distilled off under reduced pressure, and the residue was dissolved in n-hexane. ２６ｋ -NB viscous body (23.2 g, M ｎ，ＮＭＲ =25500(CDCl ３ ), M ｎ，ＭＡＬＳ =22300(CHCl ３ ), M ｎ,ＳＥＣ = 26,800 (THF)).

[0065]

[0066] 6c-PDMS ２６ｋ Under an argon atmosphere, NB-PDMS was ２６ｋ -NB (5.00 g, 0.196 mmol) was dissolved in CH ２ Cl ２ (1.96 L) to form a reaction solution. ２ Cl ２ G3 (Grubbs third generation catalyst, 57.8 mg, 0.0654 mmol) dissolved in 1000 ml of ... ２６ｋ Viscous body (4.99g, M ｎ，ＭＡＬＳ =145300(CHCl ３ ), M ｎ，ＳＥＣ= 87,800 (THF)).

[0067]

[0068] 5c—PDMS ４３ｋ HOR-PDMS is a polydimethylsiloxane having hydroxypropyl groups at both ends. ４1k -ROH (M ｎ，ＭＡＬＳ = 41300) and 6c-PDMS ２６ｋ The polycyclic polymer 5c-PDMS having an average of five ring moieties was synthesized by the same procedure as in the synthesis of ４３ｋ (M ｎ，ＭＡＬＳ =217500(CHCl ３ ), M ｎ，ＳＥＣ = 73,500 (THF)).

[0069] 1-2. Monocyclic polymer Polydimethylsiloxane with vinyl groups at both ends (VN-PDMS １４ｋ -VN) In a three-neck flask, HOR-PDMS １５k -ROH (polydimethylsiloxane having hydroxypropyl groups at both ends, M ｎ，ＮＭＲ =15300(CDCl ３ ), 1.00 g, 0.0654 mmol), 4-pentenoic acid (26.2 mg, 0.261 mmol), DMAP (47.9 mg, 0.392 mmol), and EDC.HCl (75.2 mg, 0.392 mmol) were added to CH ２ Cl ２ (6.5 mL) and the solution was stirred at room temperature for 3 days. ２ Cl ２ The solvent was distilled off under reduced pressure, and the residue was dissolved in n-hexane. After washing with methanol four times, VN-PDMS was obtained as a viscous material. １４ｋ -VN (852 mg, M ｎ，ＮＭＲ =14000(CDCl ３ ), M ｎ，ＭＡＬＳ =11700(CHCl ３ ), M ｎ，ＳＥＣ = 14700 (THF)).

[0070]

[0071] 1c-PDMS １４ｋUnder an argon atmosphere, VN-PDMS was １４ｋ -VN (250 mg, 0.0179 mmol) was dissolved in CH ２ Cl ２ (180 mL) to form a reaction solution. ２ Cl ２ HG2 (Hoveyda-Grubbs second generation catalyst, VN-PDMS) dissolved in １４ｋ 0.7 equivalents (7.8 mg, 0.013 mmol) of HG2 was quickly added to HG2-VN. The reaction was initiated by heating to reflux at 45°C. 24 hours and 48 hours after the start of the reaction, 0.7 equivalents of HG2 were added. 72 hours after the start of the reaction, an excess amount of ethyl vinyl ether relative to HG2 was added, and the reaction solution was stirred for 1 hour to terminate the reaction. The solvent was distilled off from the reaction solution, and the reaction solution was subjected to separation and washing with n-hexane and methanol. The catalyst residue was removed from the washed product by preparative SEC using chloroform as a solvent, yielding the monocyclic polymer 1c-PDMS as a viscous material. １４ｋ (180 mg, number of rings: 1, M ｎ，ＭＡＬＳ =30400(CHCl ３ ), M ｎ，ＳＥＣ = 12800 (THF))).

[0072]

[0073] 1c-PDMS ２８ｋ , 1c-PDMS ３７ｋ HOR-PDMS is a polydimethylsiloxane having hydroxypropyl groups at both ends. ２６k -ROH (M ｎ，ＮＭＲ =25300(CDCl ３ )) or HOR-PDMS ４１k -ROH (M ｎ，ＭＡＬＳ =41300(CHCl ３ )) and 1c-PDMS １４ｋ The monocyclic polymer 1c-PDMS was synthesized by the same procedure as in the synthesis of ２８ｋ (M ｎ，ＭＡＬＳ =16600(CHCl ３ ), M ｎ，ＳＥＣ = 21700 (THF)), and 1c-PDMS ３７ｋ (Mｎ，ＭＡＬＳ =37300(CHCl ３ ), M ｎ,ＳＥＣ = 27700 (THF)).

[0074] 2. Verification of trapping rate 2-1. Preparation of evaluation membranes (polymer material membranes) #1, #2 (1c-PDMS / silicone crosslinked body) Polydimethylsiloxane (HO-PDMS) with silanol groups at both ends １３ｋ -OH, M ｎ，ＭＡＬＳ = 13000) 1.0 g and 1c-PDMS as a cyclic polymer １４ｋ or 1c-PDMS ２８ｋ (100 mg) was dissolved in n-hexane in a vial. After shaking the solution in the vial at room temperature for 24 hours, an n-hexane solution of tetraethoxysilane (TEOS, crosslinking agent) (0.13 mL, n-hexane / TEOS = 9 / 1 (v / v)) and an n-hexane solution of tin(II) 2-ethylhexanoate (0.020 mL, concentration 250 g / L) were added. The solution was shaken for an additional 20 minutes and then poured into a 35 mm diameter petri dish. The solvent was distilled off from the solution in the petri dish by leaving it to stand at 22-25°C for 24 hours. Thereafter, 1c-PDMS was obtained by heating under vacuum at 50°C for 5 days. １４ｋ or 1c-PDMS ２８ｋ Films (thickness: about 1 mm) of silicone compositions (polymer materials) #1 and #2 containing a crosslinked silicone were formed.

[0075] #3 (linear-PDMS １４ｋ / Silicone crosslinked body) Cyclic polymer is linear polydimethylsiloxane (linear-PDMS １４ｋ , M ｎ，ＮＭＲ = 14000, 100 mg), and a film of silicone composition #3 was formed in the same manner as #1 and #2.

[0076] #4 (Example 1, 6c-PDMS ２６ｋ / Silicone crosslinked product) 6c-PDMS as a cyclic polymer ２６ｋ Using the resulting mixture (100 mg), a film of silicone composition (polymer material) #4 was formed in the same manner as in #1 and #2.

[0077] 2-2. Trapping Rate The membranes of the silicone compositions #1 to #4 were immersed in toluene (250 mL) at 25°C for approximately 120 hours. The toluene was distilled off from the toluene solution containing the components eluted from the membrane, and the mass W of the residue (soluble fraction) was Ａ The soluble fraction was analyzed by SEC, and the mass W of the cyclic polymer or linear polydimethylsiloxane in the eluted component was determined by peak decomposition analysis of the obtained chromatogram. ｍｃ－ＰＤＭＳ , and the mass of the sol derived from the silicone crosslinked body (W ｓｏｌ The ratio of these to the amount of tin (II) 2-ethylhexanoate W ｃａｔ From this, the mass W1 of the cyclic polymer or linear polydimethylsiloxane contained in the eluted fraction was calculated using the following formula: W1 = (W Ａ -W ｃａｔ ) × W ｍｃ－ＰＤＭＳ / (W ｓｏｌ +W ｍｃ－ＰＤＭＳ )

[0078] The trapping rate was calculated from the mass W1 of the cyclic polymer or linear polydimethylsiloxane contained in the eluted fraction and the amount of cyclic polymer charged W0 using the following formula: Trap rate (mass%) = {(W0 - W1) / W0} x 100

[0079] As shown in Table 1, the trapping rate for the membrane containing 40% by mass of cyclic polymer was 100% by mass, suggesting that the majority of the cyclic polymer formed a rotaxane structure threaded by the silicone crosslinked polymer as the axial polymer. The trapping rate for linear polydimethylsiloxane was low, suggesting that linear polymers tend to bleed out from the membrane. A comparison of #1 and #2 also revealed a tendency for the trapping rate to increase as the molecular weight of the cyclic portion increased.

[0080]

[0081] 3. Viscoelasticity of polymer materials Example 2-1 (1c-PDMS ３７ｋ / Silicone crosslinked body) HO-PDMS １３ｋ -OH (850 mg) and 1c-PDMS ３７ｋ Using the resulting mixture (510 mg), a film of the silicone composition (polymer material) of Example 2-1 was formed in the same manner as in #1 and #2.

[0082] Example 2-2 (5c-PDMS ４３ｋ / Silicone crosslinked body) HO-PDMS １３ｋ -OH (850 mg) and 5c-PDMS ４３ｋ Using the resulting mixture (510 mg), a film of the silicone composition (polymer material) of Example 2-2 was formed in the same manner as in #1 and #2.

[0083] Comparative Example 2-1 (crosslinked silicone) HO-PDMS １３ｋ Using —OH (850 mg), a film of the silicone composition (crosslinked silicone) of Example 2-1 was formed in the same manner as in #1 and #2.

[0084] Comparative Example 2-2 (linear-PDMS ４１ｋ / Silicone crosslinked body) HO-PDMS １３ｋ —OH (850 mg) and linear polydimethylsiloxane (linear-PDMS ４１ｋ , M ｎ，ＭＡＬＳ Using the silicone composition (=41300, 510 mg), a film of the silicone composition of Comparative Example 2-2 was formed in the same manner as in #1 and #2.

[0085] Comparative Example 2-3 (crosslinked silicone) HO-PDMS １３ｋ -OH (850 mg) and 6c-PDMS ２６ｋ Using the resulting mixture (85 mg), a film of the silicone composition (polymer material) of Comparative Example 2-3 was formed in the same manner as in #1 and #2.

[0086] Dynamic Viscoelasticity The dynamic viscoelasticity of films of the silicone compositions of Examples 2-1 and 2-2, and Comparative Examples 2-1, 2-2, and 2-3 was measured using a rheometer (MCR-702e, Anton Paar) equipped with a Peltier-type temperature control device. A frequency sweep measurement was performed using parallel plates with a diameter of 12 mm as the measurement jig. In the frequency sweep measurement, the viscoelasticity of the film was measured at each temperature in 10°C increments from -5°C to 55°C over an angular frequency (ω) range of 0.1 to 100 rad / s. From the measurement results, a master curve was created with a reference temperature of 25°C and a reduced angular frequency of 0.03 to 300 rad / s. The reduced angular frequency refers to the angular frequency on the horizontal axis of the master curve.

[0087] FIG. 4 shows the master curves of G' and G'', and FIG. 5 shows the master curve of tan δ. The values ​​of tan δ at angular frequencies of 0.1 rad / s, 1 rad / s, 10 rad / s, and 100 rad / s, read from the master curve in FIG. 5, are shown in Table 2. Table 2 also shows the blend ratios (mass %) of the materials used to form each film. Cyclic polymer 1c-PDMS ３７ｋ or 5c-PDMS ４３ｋ Films of the silicone compositions (polymer materials) of the examples containing the crosslinked silicone alone exhibited high tan δ over a wide frequency range, compared to Comparative Example 2-1. Considering this together with the trapping rate verification results in Table 1, it was suggested that silicone compositions (polymer materials) containing rotaxane structures formed by a high proportion of cyclic polymers not only exhibit low bleed-out, but also have excellent properties as damping materials. The tan δ value can also be increased by using a linear polymer rather than a cyclic polymer, as in Comparative Example 2-2. However, in this case, as confirmed by the verification results in Table 1, the trapping rate is low and bleed-out is likely to occur.

[0088]

[0089] <Study 2: Polymer materials having acrylic polymer chains> 1. Synthesis of cyclic polymers Both-end brominated poly(n-butyl acrylate) (Br-PBA-Br) n-butyl acrylate (BA), ethylene bis(2-bromoisobutyrate) (EBBiB), CuBr, CuBr ２ The reaction solution containing N,N,N',N'',N''-pentamethyldiethylenetriamine (PMDEA) and a mixed solvent of anisole and DMF was stirred at 70°C for 8 hours to allow the polymerization reaction of BA to proceed, with both ends of EBBiB as reaction initiation points. The initial concentration of BA in the reaction solution was 4.0 mmol / L. The molar ratio of the amounts of the compounds charged was [BA] / [EBBiB] / [CuBr] / [CuBr ２ ] / [PMDETA]=182 / 1.0 / 0.95 / 0.05 / 1.1. １０ｋ Br-PBA (9.08 g, yield 36.3%) was obtained in the same manner.２４ｋ -Br and Br-PBA ６２ｋ The obtained Br-PBA １０ｋ -Br, Br-PBA ２４ｋ -Br and Br-PBA ６２ｋ -Br M ｎ，ＳＥＣ and M ｎ，ＮＭＲ is shown in Table 3.

[0090]

[0091]

[0092] Poly(n-butyl acrylate) having norbornenyl groups at both ends (NB-PBA-NB) Br-PBA １０ｋ The reaction mixture containing Br, exo-NB-COOH, diazabicycloundecene (DBU), and DMF was stirred at room temperature for 168 hours to allow the reaction to proceed. １０ｋ The initial concentration of —Br was 100 g / L. The molar ratio of the amount of each compound charged was [Br-PBA １０ｋ The reaction mixture had a yield of NB-PBA, which was the product of NB-COOH / DBU=1.0 / 4.0 / 4.1. １０ｋ NB-PBA was obtained in the same manner as above. ２４ｋ -NB, and NB-PBA ６２ｋ -NB was obtained. The obtained NB-PBA １０ｋ -NB, NB-PBA ２４ｋ -NB, and NB-PBA ６２ｋ -NB's M ｎ，ＳＥＣ , M ｎ，ＳＥＣ and M ｎ，ＭＡＬＳ is shown in Table 4.

[0093]

[0094]

[0095] 17c-PBA ２４ｋ Under an argon atmosphere, NB-PBA was ２４ｋ -NB to CH ２ Cl ２ The reaction mixture was dissolved in a small amount of CH ２ Cl２ G3 (Grubbs third generation catalyst) dissolved in NB-PBA was quickly added to initiate polymerization. ２４ｋ The initial concentration of NB was 0.23 mmol / L. The molar ratio of the amounts of each compound charged was [NB-PBA ２４ｋ The reaction mixture was stirred at room temperature for 3.5 hours, and an excess of ethyl vinyl ether was added to G3. The reaction mixture was further stirred overnight to terminate the polymerization. The solvent was distilled off from the reaction mixture, and the catalyst residue was removed by preparative SEC using chloroform as a solvent to obtain a polycyclic polymer 17c-PBA having an average of 17 ring moieties. ２４ｋ 17c-PBA was obtained. ２４ｋ of １ In the H NMR spectrum, NB-PBA ２４ｋ -NB's １ The signal attributed to hydrogen of the norbornene group observed in the 1 H NMR spectrum disappeared.

[0096]

[0097] 3c-PBA １０ｋ , 7c-PBA ２４ｋ , 8c-PBA ２４ｋ and 45c-PBA ６２ｋ 17c-PBA ２４ｋ 3c-PBA was synthesized in the same manner as in the synthesis of １０ｋ , 7c-PBA ２４ｋ , 8c-PBA ２４ｋ and 45c-PBA ６２ｋ obtained.

[0098] M of each cyclic polymer ｎ，ＭＡＬＳ , and the average values ​​of the cyclic radicals calculated therefrom are shown in Table 5.

[0099]

[0100] 2. Polymer Material 2-1. Polymer Material Film 1.92 g of n-butyl acrylate (BA), 59.4 mg of ethylene glycol dimethacrylate (EGDM), 19.8 mg of diethoxyacetophenone (DEAP, photopolymerization initiator), and a cyclic polymer were uniformly mixed to obtain a mixed solution for forming a polymer material. Mixed solutions of Examples 3-1 to 3-4 containing cyclic polymers of the types and blending ratios shown in Table 6 were prepared. The blending ratios of the cyclic polymers shown in Table 6 are percentages (mass %) based on the total amount of BA, EGDM, and DEAP. For comparison, a linear polymer, Br-PBA, was used instead of the cyclic polymer. ６２ｋ A mixture of Comparative Example 3-1 containing —Br was also prepared.

[0101] A mold (9 × 6 cm) was prepared, consisting of a silicon spacer approximately 500 μm thick sandwiched between two quartz plates. The prepared mixture was poured into the mold. The mixture in the mold was irradiated with ultraviolet light to polymerize the BA and EGDM. Polymerization resulted in the formation of a film (thickness: approximately 500 μm) of a polymer material containing a crosslinked acrylic polymer and a cyclic polymer.

[0102] 2-2. Trapping Rate A polymer film was immersed in toluene at room temperature for 48 hours. The toluene was distilled off from the toluene solution containing the components eluted from the film, and the mass W of the residue (soluble fraction) was Ａ The soluble fraction was analyzed by SEC, and the peak decomposition analysis of the resulting chromatogram determined the area A attributable to the cyclic polymer or linear polymer in the eluted components. ｍｃ－ＰＢＡ , and the area of ​​the sol derived from the acrylic crosslinked polymer (A ｓｏｌ The mass W1 of the cyclic polymer or linear polymer contained in the eluted fraction was calculated using the following formula: W1 = W Ａ ×A ｍｃ－ＰＢＡ / (A ｓｏｌ +A ｍｃ－ＰＢＡ )

[0103] The trapping rate was calculated from the mass W1 of the cyclic polymer or linear polymer contained in the eluted fraction and the amount W0 of the cyclic polymer or linear polymer charged using the following formula. The results are shown in Table 5. Trap rate (mass%) = {(W0 - W1) / W0} x 100

[0104]

[0105] 2-3. Viscoelasticity Master curves were created by dynamic viscoelasticity measurement using the same method as in Study 1 for the membranes of Example 3-4 and Comparative Example 3-1 before immersion in toluene. Master curves were also created for each membrane after 48 hours of immersion in toluene. Furthermore, a master curve was also created for a membrane (neat) containing only a crosslinked polymer (BA / EDGM polymer) that did not contain a cyclic polymer. A graph showing the relationship between tan δ and angular frequency ω was created from the master curve. Figure 6 is a graph showing the relationship between tan δ and angular frequency ω for the membrane of Example 3-4 and a membrane containing no cyclic polymer. Figure 7 is a graph showing the relationship between tan δ and angular frequency ω for the membrane of Comparative Example 3-1 and a membrane containing no cyclic polymer. As shown in Figure 6, the membrane of Example 3-4 maintained a high tan δ over a wide frequency range, and this high tan δ was maintained even after immersion in toluene. As shown in Figure 7, in the case of the membrane of Comparative Example 3-1, tan δ at low angular frequencies significantly decreased after immersion in toluene.

[0106] <Study 3: Polymer materials having polyoxyethylene chains> 1. Synthesis of cyclic polymer 6c-PEG ８．５ｋ The reaction of polyethylene glycol with exo-NB-COOH produces polyethylene glycol having norbornenyl groups at both ends (NB-PEG). ８．５ｋ NB-PEG was prepared in a three-neck flask under an argon atmosphere. ８．５ｋ -NB (2.00 g, 0.235 mmol) was dissolved in CH ２ Cl ２ (2.35 L) to form a reaction solution. ２ Cl ２G3 (Grubbs third generation catalyst, 69.2 mg, 0.0782 mmol) dissolved in 100 ml of PEG was quickly added to initiate polymerization. After stirring at room temperature for 2 hours and 40 minutes, an excess amount of ethyl vinyl ether relative to G3 was added, and the reaction solution was further stirred overnight to terminate the polymerization. The solvent was distilled off from the reaction solution. The residue was purified by reprecipitation using diethyl ether as a poor solvent, and the resulting product was washed. The catalyst residue was removed from the washed product by preparative SEC using chloroform as a solvent, yielding a cyclic polymer 6c-PEG having an average of six cyclic moieties. ８．５ｋ obtained.

[0107]

[0108] 14c-PEG ８．５ｋ 6c-PEG ８．５ｋ A multicyclic polymer 14c-PEG having an average of 14 cyclic moieties was prepared by the same procedure as in Example 1. ８．５ｋ obtained.

[0109] For each cyclic polymer, the average number of cyclic groups and M ｎ，ＭＡＬＳ is shown in Table 7.

[0110]

[0111] 2. Polymer Material 2-1. Film of Polymer Material for Tensile Test 1.00 g of polyethylene glycol diacrylate (PEGDA, Sigma-Aldrich, Mn=700), 10.0 mg of diethoxyacetophenone (DEAP, photopolymerization initiator), and a cyclic polymer were uniformly mixed to obtain a mixed solution for forming a polymer material. Mixed solutions of Examples 4-1 to 4-4 containing cyclic polymers of the types and blending ratios shown in Table 8 were prepared. The blending ratios of the cyclic polymers shown in Table 8 are percentages (mass %) based on the amount of PEGDA. For comparison, the mixed solution of Comparative Example 4-1, which does not contain a cyclic polymer, and the mixed solution of Comparative Example 4-2, which contains a linear polymer, polyethylene glycol (linear-PEG), instead of a cyclic polymer, were also prepared. ８．３ｋA mixed solution of Comparative Example 4-2 containing PEGDA was also prepared. A mold (15 x 15 cm) was prepared, with a silicon spacer approximately 100 μm thick sandwiched between two quartz plates. The prepared mixed solution was poured into this mold. The mixed solution in the mold was irradiated with 365 nm ultraviolet light for 5 minutes, thereby polymerizing the PEGDA. The polymerization resulted in the formation of a film (thickness: approximately 100 μm) of a polymer material containing an acrylic cross-linked polymer, which is a cross-linked polymer, and a cyclic polymer or a linear polymer.

[0112] 2-2. Tensile Test A tensile test was performed using a dumbbell-shaped test piece cut out from a film of the polymer material. The elastic modulus, elongation at break, and toughness were determined from the stress-strain curve obtained by the tensile test. The results are shown in Table 8.

[0113]

[0114] 2-3. Trapping Rate Using the same procedure as in "2-1. Polymer Material Film for Tensile Test," a polymer material film was formed from a mixed solution containing a cyclic polymer or a linear polymer in the blending ratio shown in Table 9. The weighed polymer material film was immersed in approximately 300 mL of methanol (room temperature) for 48 hours while stirring at 10 rpm. The methanol was replaced twice during the immersion. The total amount of methanol used was approximately 900 mL. The polymer material film was removed, and all the methanol in the methanol solution in which the film had been immersed was distilled off to obtain the mass W of the residue (soluble fraction). Ａ The trapping rate was then calculated using the same procedure as in Study 1. The results are shown in Table 9.

[0115]

[0116] <Study 4: Polymer materials having polyoxypropylene chains> 1. Synthesis of cyclic polymer 9c-PPO １０．１ｋ A polypropylene glycol derivative having a norbornenyl group at the end of the polypropylene glycol chain bonded to a phenylene group (NB-PPO １０．１ｋ NB-PPO was prepared in a three-neck flask under an argon atmosphere. １０．１ｋ -NB (1.50 g, 0.149 mmol) was dissolved in CH ２ Cl２ (1.67 L) to form a reaction solution. ２ Cl ２ G3 (Grubbs third generation catalyst, 0.0167 mmol) dissolved in 1000 ml of ... １０．１ｋ obtained.

[0117]

[0118] Cyclic polymer 9c-PPO １０．１ｋ For ｎ，ＭＡＬＳ is shown in Table 10.

[0119]

[0120] 2-1. Polymer Material Film 1.00 g of polypropylene glycol diacrylate (PPGDA, Sigma-Aldrich, Mn = 800), 10.0 mg of diethoxyacetophenone (DEAP, photopolymerization initiator), and a cyclic polymer were uniformly mixed to obtain a mixture for forming a polymer material. Mixed solutions of Examples 5-1 and 5-2 containing cyclic polymers of the type and blending ratio shown in Table 10 were prepared. The blending ratio of the cyclic polymer shown in Table 10 is the percentage (mass %) based on the amount of PPGDA. For comparison, a mixed solution of Comparative Example 5-1, which did not contain a cyclic polymer, was also prepared. A mold (15 x 15 cm) was prepared, with a silicon spacer approximately 100 μm thick sandwiched between two quartz plates. The prepared mixture was poured into this mold. The mixture in the mold was irradiated with 365 nm ultraviolet light for 5 minutes to polymerize the PPGDA. By the polymerization, a film (thickness: about 100 μm) of a polymer material containing an acrylic cross-linked polymer, which is a cross-linked polymer, and a cyclic polymer was formed.

[0121] 2-2. Tensile Test A tensile test was carried out using dumbbell-shaped test pieces cut out from the films of the polymer materials of Example 5-1 and Comparative Example 5-1. The elastic modulus, elongation at break, and toughness were determined from the stress-strain curves obtained by the tensile test. The results are shown in Table 11.

[0122] 2-3. Trapping Rate For the membranes of the polymer materials of Examples 5-1 and 5-2, the trapping rates were estimated using the same procedure as in Study 3. The results are shown in Table 11.

[0123]

[0124] <Study 5> 1. Cyclic polymer 6c-PDMS from Study 1 ２６ｋ The cyclic polymer 6c-PDMS was synthesized in the same manner as in Example 1. １１．５ｋ , and 15c-PDMS １１．５ｋ The Mn and MALS of each cyclic polymer are shown in Table 12.

[0125]

[0126] 2-1. Polymer Material Film A mixed solution for forming a polymer material was obtained by uniformly mixing 1.00 g of polydimethylsiloxane having methacryloyloxypropyl groups at both ends (MA-PDMS-MA, FM-7111 manufactured by JNC Corporation), 10.0 mg of diethoxyacetophenone (DEAP, photopolymerization initiator), and a cyclic polymer. Mixed solutions of Examples 6-1 to 6-4 containing cyclic polymers of the types and blending ratios shown in Table 13 were prepared. The blending ratios of the cyclic polymers shown in Table 13 are percentages (mass %) based on the amount of MA-PDMS-MA. For comparison, the mixed solution of Comparative Example 6-1, which did not contain a cyclic polymer, and the mixed solution of Comparative Example 6-2, which contained a linear polymer, polydimethylsiloxane (linear-PDMS), instead of a cyclic polymer, were also prepared. １２ｋA mixed solution of Comparative Example 6-2 containing PDMS-MA was also prepared. A mold (15 x 15 cm) was prepared by sandwiching a silicon spacer approximately 100 μm thick between two quartz plates. The prepared mixed solution was poured into this mold. The mixed solution in the mold was irradiated with 365 nm ultraviolet light for 5 minutes to polymerize MA-PDMS-MA. The polymerization resulted in the formation of a film (thickness: approximately 100 μm) of a polymer material containing an acrylic cross-linked polymer, which is a cross-linked polymer, and a cyclic polymer or a linear polymer.

[0127] 2-2. Tensile Test A tensile test was performed using dumbbell-shaped test pieces cut out from the films of the polymer materials of Comparative Examples 6-1 and 6-2 and Examples 6-1 and 6-2. The elastic modulus, elongation at break, and toughness were determined from the stress-strain curves obtained by the tensile test. The results are shown in Table 13.

[0128] 2-3. Trapping Rate For the membranes of the polymer materials of Examples 6-3 and 6-4, the trapping rate was estimated using the same procedure as in Study 3. The results are shown in Table 13.

[0129]

[0130] 10...cyclic polymer, 20...crosslinked polymer, 20A...linear polymer, 20B...crosslinking agent, 21...linear portion, 25...crosslinking point, 30...mixture.

Claims

1. A polymer material comprising: a cyclic polymer having one or more cyclic portions; and a crosslinked polymer having a plurality of linear portions, the linear portions being bonded to each other at crosslinking points to form a crosslinked body, wherein at least a portion of the cyclic polymer in the polymer material has the cyclic portion pierced by the linear portions of the crosslinked polymer, and the ratio of the amount of the cyclic polymer to the amount of the crosslinked polymer is 15 mass% or more.

2. The polymer material according to claim 1, wherein the trapping rate of the cyclic polymer calculated by the following formula is 50 mass% or more: Trap rate (mass%) = {(W0 - W1) / W0} x 100, where W0 is the mass of the cyclic polymer in the polymer material and W1 is the mass of a portion of the cyclic polymer in the polymer material that dissolves in a solvent at 25°C in which the cyclic polymer dissolves when the polymer material is immersed in the solvent for 48 hours or more and 120 hours or less.

3. The polymer material according to claim 1, wherein the cyclic polymer has a number average molecular weight, as determined by SEC-MALS, of 3,000 or more per cyclic portion in the cyclic polymer.

4. The polymeric material of claim 1, wherein the linear portion of the crosslinked polymer comprises polymer chains corresponding to a linear polymer having a number average molecular weight of 1500 or more by SEC-MALS method.

5. The polymeric material of claim 1, wherein said cyclic portions and said linear portions comprise polysiloxane chains.

6. The polymer material according to claim 1, which exhibits a tan δ of 0.08 or more at an angular frequency of 100 rad / s and a temperature of 25°C.

7. A polymer material comprising: a cyclic polymer having one or more cyclic portions; and a crosslinked polymer having a plurality of linear portions, the linear portions being bonded to each other at crosslinking points to form a crosslinked body, wherein at least a portion of the cyclic polymer in the polymer material has the cyclic portion pierced by the linear portion of the crosslinked polymer, and at least one of the cyclic portion or the linear portion comprises an acrylic polymer chain or a polyoxyalkylene chain.

8. The polymeric material of claim 7, wherein said cyclic portions and said linear portions comprise acrylic polymer chains.

9. The polymeric material of claim 7, wherein said cyclic portions and said linear portions comprise polyoxyalkylene chains.

10. A damping material comprising the polymer material according to any one of claims 1 to 9.

11. A method for producing a polymeric material, comprising: providing a mixture containing a monomer component including a cyclic polymer having one or more cyclic portions and a monomer having an ethylenically unsaturated group; and polymerizing the monomer component in the mixture, thereby forming a crosslinked polymer having a plurality of linear portions, the plurality of linear portions being linked to each other at crosslink points to form crosslinks.

12. The method of claim 11, wherein at least one of the cyclic portion or the linear portion comprises an acrylic polymer chain, a polyoxyalkylene chain, or a polysiloxane chain.

13. The method of claim 11, wherein said cyclic portion and said linear portion comprise acrylic polymer chains.

14. The method of claim 11, wherein said cyclic portion and said linear portion comprise polyoxyalkylene chains.

15. The method of claim 11, wherein said cyclic portion and said linear portion comprise polysiloxane chains.

16. A compound represented by the following formula (II) or (II'): R ２ represents a tetravalent hydrocarbon group; L ２ represents a divalent linker group; Q ２ contains an acrylic polymer chain and R ２ and L ２ A cyclic polymer, which refers to a polymer chain that, together with 17. A compound represented by the following formula (II) or (II'): R ２ represents a tetravalent hydrocarbon group; L ２ represents a divalent linker group; Q ２ contains a polyoxyalkylene chain, R ２ and L ２ A cyclic polymer, which refers to a polymer chain that, together with 18. R ２ is represented by the following formula (20a), (20b), (20c), (20d), (20′a), (20′b), (20′c) or (20′d): The cyclic polymer according to claim 16 or 17, wherein the cyclic polymer is a tetravalent hydrocarbon group represented by the following formula: