Polymer compound

Abstract

To provide a polymer compound having viscoelasticity.SOLUTION: A polymer compound having a polydimethylsiloxane structure as a main component, wherein a number-average molecular weight is 200000 or more, and a storage modulus (G ') is larger than a loss modulus (G ") at a temperature of 25 °C., a shear strain of 1%, and an angular frequency of 0. 01rad·s - 1 or more and 100rad·s - 1 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to polymeric compounds. [Background technology]

[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). A polymer gel with high elasticity and self-healing properties has been reported, which is formed solely by the physical entanglement of ultra-high molecular weight (UHMW) polymers (Non-Patent Document 2). Solvent-free ultrasoft and ultraelastic polymer melts and networks using bottle-brush polymers have been reported (Non-Patent Document 3). [Prior art documents] [Non-patent literature]

[0003] [Non-Patent Document 1] J. Huang, Y. Xu, S. Qi, J. Zhou, W. Shi, T. Zhao, M. Liu, Nat.Commun. 2021, 12, 3610 [Non-patent document 2] Yuji Kamiyama, Ryota Tamate, Takashi Hiroi, Sadaki Samitsu, Kenta Fujii, Takeshi Ueki, Sci. Adv. 8, eadd0226 (2022) [Non-patent document 3] William FM Daniel, Joanna Burdynska, Mohammad Vatankhah-Varnoosfaderani, Krzysztof Matyjaszewski, Jarosraw Paturej, Michael Rubinstein, Andrey V. Dobrynin & Sergei S. Sheiko, Nature Materials, volume 15, pages 183-189 (2016) Summary of the Invention [Problem to be solved by the invention]

[0004] However, non-crosslinked polymers that are relatively small in molecular weight and soluble in solvents become viscous (liquid-like properties, indicated by loss elasticity) and have relatively low elasticity (solid-like properties, indicated by storage elasticity). In other words, it has been difficult to impart properties that maintain a good balance between viscosity and elasticity like rubber, while also having relatively high solid-like properties (in other words, flexible but resistant to plastic deformation). Furthermore, in the low frequency range, i.e., when moving slowly or at high temperatures, the viscous properties of the material generally become relatively greater than the elastic properties, and there was a demand for a material that exhibited stable viscoelastic properties, especially elasticity, even in the low frequency range. Furthermore, in order to impart elasticity, a chemical crosslinking structure is generally introduced into the system. However, this method cannot accommodate large deformations and results in breakage, rupture, or loss of solubility in organic solvents. Therefore, a process such as crosslinking after forming the uncrosslinked material into the desired shape is required.

[0005] The present disclosure has been made in view of the above circumstances, and an object of one aspect of the present disclosure is to provide a polymer compound having suitable viscoelasticity. [Means for solving the problem]

[0006] The present disclosure includes the following: [1] A polymer compound having a polydimethylsiloxane structure as a main component, The number average molecular weight is 200,000 or more, Temperature: 25°C, shear strain: 1%, measurement angular frequency: 0.01 rad·s -1 More than 100rad·s -1 A polymer compound in which the storage modulus (G') is greater than the loss modulus (G") over the entire range below. [2] Temperature: 25°C, shear strain: 1%, measurement angular frequency: 0.01 rad·s -1 More than 100rad·s -1 The polymer compound according to [1], which has a storage modulus (G') of 100,000 Pa or less over the entire range below. [3] Temperature: 25°C, shear strain: 1%, measurement angular frequency: 0.01 rad·s -1 More than 100rad·s -1 The polymer compound according to [1] or [2], wherein the ratio of G" / G' (Tan δ) is 0.2 or more in the entire range below. [4] The polymer compound according to any one of [1] to [3], which is soluble in an organic solvent. [5] The polymer compound according to any one of [1] to [4], which has a C═C structure. [6] the polymer compound has a cyclic portion that is a cyclic structure, The polymer compound according to any one of [1] to [5], wherein the cyclic portion contains the polydimethylsiloxane structure. [7] The polymer compound according to [6], wherein the number average molecular weight of the cyclic portion is 40,000 or more. [8] Contains three or more structural units represented by the following formula (II) or (II'): The number average molecular weight is 180,000 or more, A polymer compound in which the number average molecular weight of the cyclic portion contained in the structural unit is 40,000 or more. [ka] [ka] In formulas (II) and (II'), R 2 represents a tetravalent hydrocarbon group, and two L 2 each independently represents a divalent linker group, and Q 2 is R 2 and two L 2 and a polymer chain having a polydimethylsiloxane structure forming the cyclic portion. [9] an intramolecular ring-opening metathesis polymerization step of forming a cyclic macromonomer (CM) having a cyclic moiety by intramolecular ring-opening metathesis polymerization of a linear macromonomer (LM) having a polydimethylsiloxane structure and two cyclic olefin structures;

[0023] The method for producing a polymer compound according to any one of [1] to [8], comprising: an intermolecular / intramolecular ring-opening metathesis polymerization step of forming the polymer compound by intramolecular ring-opening metathesis polymerization after intermolecular ring-opening metathesis polymerization of the cyclic macromonomer (CM) with another linear macromonomer (LM).

[10] A vibration suppressing member for countering micro-vibrations, which uses the polymer compound described in [1].

[11] [1] A liquid nitrogen insulation material or a low-temperature storage container for liquid nitrogen, using the polymer compound described in [1].

[12] A sealing material for a low-temperature storage container or a low-temperature storage container, which uses the polymer compound according to [1]. [Effects of the Invention]

[0007] It is possible to provide a polymer compound having suitable viscoelasticity. [Brief explanation of the drawings]

[0008] [Figure 1] 1 shows master curves of G′ and G″ of 5C43 obtained in Example 1. [Figure 2] 1 shows master curves of G′ and G″ of 4C50 obtained in Example 10. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure is not limited to the following examples.

[0010] <Polymer compounds> The polymer compound according to the present disclosure has suitable viscoelasticity. The polymer compound according to the present disclosure has a polydimethylsiloxane structure as a main component. In one embodiment of the polymer compound according to the present disclosure, the number average molecular weight is 180,000 or more. In one embodiment of the polymer compound according to the present disclosure, the number average molecular weight is 190,000 or more. In one embodiment of the polymer compound according to the present disclosure, the number average molecular weight is 200,000 or more. The polymer compound according to the present disclosure was subjected to a test at a temperature of 25°C, a shear strain of 1%, and a measurement angular frequency of 0.01 rad·s -1 More than 100rad·s -1 In the entire range below, the storage modulus (G') is greater than the loss modulus (G").

[0011] One embodiment of the polymer compound according to the present disclosure preferably has solvent solubility while maintaining stable viscoelastic properties, i.e., a balance between viscosity and elasticity, from low frequency regions to high frequency regions, in other words, from high temperature regions to low temperature regions. Furthermore, one embodiment of the polymer compound according to the present disclosure having the above physical properties can provide a material that also has good moldability. One aspect of the present disclosure is a polymer compound that has stable viscoelasticity from a low frequency region to a high frequency region.

[0012] In the present disclosure, the term "main component" means that the ratio of [number average molecular weight of polydimethylsiloxane structure] / [number average molecular weight of polymer compound] is greater than 0.5. The polymer compound according to the present disclosure preferably has a molecular weight of 0.6 or more, more preferably 0.7 or more, and even more preferably 0.8 or more, expressed as [number average molecular weight of polydimethylsiloxane structure] / [number average molecular weight of polymer compound]. The number-average molecular weight of the polydimethylsiloxane structure is preferably 40,000 or more, more preferably 41,000 or more, even more preferably 42,000 to 100,000, and particularly preferably 43,000 to 80,000. A number-average molecular weight of the polydimethylsiloxane structure equal to or greater than the lower limit described above is preferred in that the unique viscoelastic behavior characteristic of the present invention is more strongly exhibited. A number-average molecular weight of the polydimethylsiloxane structure equal to or less than the upper limit described above is preferred in that industrial production is easier. In one embodiment of the polymer compound according to the present disclosure, the number average molecular weight is preferably 200,000 or more and 3,000,000 or less, more preferably 200,000 or more and 2,000,000 or less, and even more preferably 200,000 or more and 1,500,000 or less.

[0013] Although the mechanism by which this effect occurs is unclear, this property tends to appear when the ring size exceeds four times the so-called entanglement molecular weight (Me). The entanglement molecular weight of polydimethylsiloxane homopolymer has been reported to be 10,000 to 12,000, so this range is preferred. It is presumed that within this range, a pseudo-bridged structure is formed due to the interaction of the ring moieties. In one embodiment of the polymer compound according to the present disclosure, the number average molecular weight is preferably 180,000 or more and 3,000,000 or less, more preferably 190,000 or more and 2,000,000 or less, and even more preferably 190,000 or more and 1,500,000 or less. It is preferable that the number average molecular weight of the polymer compound is equal to or greater than the above lower limit in that the unique viscoelastic behavior that is a feature of the present invention is more strongly exhibited, and it is preferable that the number average molecular weight of the polymer compound is equal to or less than the above upper limit in that industrial production is easier. In this specification, unless otherwise specified, the number average molecular weight refers to a value calculated as an absolute number average molecular weight by SEC (size exclusion chromatography)-MALS (multi-angle light scattering) method.

[0014] The storage modulus (G') and loss modulus (G") can be measured using a shear-type dynamic viscoelasticity measurement system (a so-called rheometer) capable of oscillation measurement or a dynamic mechanical analyzer (a so-called DMA). The properties of the present disclosure are shown by angular frequency dispersion measurement of the elastic modulus. In the examples, an Anton Paar shear-type modular compact rheometer, MCR-702e, was used.

[0015] The polymer compound according to the present disclosure was subjected to a test at a temperature of 25°C, a shear strain of 1%, and a measurement angular frequency of 0.01 rad·s -1 More than 100rad·s -1 In the entire range below, the storage modulus (G') is preferably 100 Pa or more and 100,000 Pa or less, more preferably 100 Pa or more and 50,000 Pa or less, and even more preferably 100 Pa or more and 30,000 Pa or less. The polymer compound according to the present disclosure was subjected to a test at a temperature of 25°C, a shear strain of 1%, and a measurement angular frequency of 0.01 rad·s -1 More than 100rad·s -1 In the entire range below, the loss modulus (G") is preferably 100 Pa or more and 100,000 Pa or less, more preferably 100 Pa or more and 50,000 Pa or less, and even more preferably 100 Pa or more and 30,000 Pa or less.

[0016] The polymer compound according to the present disclosure was subjected to a test at a temperature of 25°C, a shear strain of 1%, and a measurement angular frequency of 0.01 rad·s -1 More than 100rad·s -1 In the entire range below, the ratio of G" / G' (Tan δ) is preferably 0.1 or more and 0.5 or less, more preferably 0.2 or more and 0.4 or less, and even more preferably 0.3 or more and 0.4 or less.

[0017] The polymer compound according to the present disclosure is preferably soluble in organic solvents at 25°C. In the present disclosure, "soluble in an organic solvent" means that 1 mg or more of a polymer compound dissolves in 100 mL of an organic solvent at 25° C. Solubility is determined by visually confirming that the solution is transparent.

[0018] Examples of organic solvents capable of dissolving polymer compounds include alcohols (methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol, diacetone alcohol); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone, diacetone alcohol); esters (methyl acetate, ethyl acetate, butyl acetate, n-propyl acetate, isopropyl acetate, methyl formate, propylene glycol monomethyl ether acetate (PGMEA)); aliphatic hydrocarbons (hexane, cyclohexane); halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride); aromatic hydrocarbons (benzene, toluene, xylene); amides (dimethylformamide, dimethylacetamide, n-methylpyrrolidone); ethers (diethyl ether, dioxane, tetrahydrofuran); ether alcohols (1-methoxy-2-propanol); and carbonates (dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate). Among these, ketones are preferred, and methyl ethyl ketone is more preferred. The amount of organic solvent capable of dissolving the polymer compound is preferably 1 mL to 100 mL, more preferably 3 mL to 90 mL, and even more preferably 5 mL to 80 mL, per 1 mg of the polymer compound.

[0019] The polymeric compounds according to the present disclosure are preferably polycyclic polymers having multiple cyclic moieties comprising the polymer chain.

[0020] The cyclic portion of a polycyclic polymer is a portion that forms a single closed ring. In one embodiment of the polymer compound according to the present disclosure, the number of cyclic portions in one molecule of the polycyclic polymer can be, for example, 2 or more. The number of cyclic portions in one molecule of the polycyclic polymer is preferably 2 or more and 100 or less, more preferably 3 or more and 100 or less, more preferably 4 or more and 100 or less, and even more preferably 5 or more and 50 or less. The average number of cyclic portions per molecule of the polycyclic polymer may be within these numerical ranges. In one embodiment of the polymer compound according to the present disclosure, the number of cyclic moieties per molecule of the polycyclic polymer is preferably from 4 to 100, more preferably from 5 to 50. The average number of cyclic moieties per molecule of the polycyclic polymer may be within these numerical ranges. It is preferable that the number of cyclic moieties per molecule of the polycyclic polymer is equal to or greater than the above lower limit, since the unique viscoelastic behavior of the present invention is easily exhibited.It is preferable that the number of cyclic moieties per molecule of the polycyclic polymer is equal to or less than the above upper limit, since industrial production is easier. Although the mechanism by which this effect is exhibited is not yet clear, such properties appear when the average number of rings per molecule exceeds 3, and therefore this range is preferred. It is presumed that within this range, a pseudo-bridged structure is formed due to the interaction of the ring moieties.

[0021] The cyclic portion preferably includes a polydimethylsiloxane structure. The number average molecular weight of the cyclic portion is preferably 40,000 or more, more preferably 43,000 or more, even more preferably 43,000 or more and 80,000 or less, and particularly preferably 43,000 or more and 70,000 or less.

[0022] A polycyclic polymer having two or more cyclic moieties can have two or more structural units having one cyclic moiety. Two or more structural units having one cyclic moiety may be connected in series. The following formulas (II) and (II') show examples of structural units having one cyclic moiety. In formulas (II) and (II'), R 2 represents a tetravalent hydrocarbon group, and two L 2 each independently represents a divalent linker group, and Q 2 is R 2 and two 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 polycyclic polymer.

[0023] [ka]

[0024] [ka]

[0025] R 2 may be an alkanediyl group having 2 or more and 20 or less carbon atoms, or an alkenediyl group having 2 or more and 20 or less carbon atoms.

[0026] R 2 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'), two R 3 each independently represents an alkanediyl group having 1 to 10 carbon atoms, and two R 3 may be the same or different. * represents a bond. 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 polycyclic polymer.

[0027] [ka]

[0028] R 2 Examples are represented by the following formulae (200a), (200b), (200c), and (200d): In formulae (200a) to (200d), two Xs each independently represent -CH2-, -CH2CH2-, -O-, -S-, or -NR a -(R arepresents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and * represents a bond. The structures of formulas (200a) to (200d) may be either a cis or trans isomer at the double bond. The two rings may each have a substituent. The substituent may be a carboxy group or an alkyl group having 1 to 5 carbon atoms. Of these, those represented by the following formulas (20a), (20b), (20c), and (20d) are preferred. In formulas (20a) to (20d), * is the same as above. The structures of formulas (20a) to (20d) may be either a cis or trans isomer at the double bond. R 2 may be a group represented by the following formula (200'a), (200'b), (200'c), or (200'd). X and * in formulas (200'a) to (200'd) are the same as above. The groups of formulas (200'a) to (200'd) can contribute to improving the stability of the polycyclic polymer. R 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) has the same meaning as above. The groups of formulas (20'a) to (20'd) can contribute to improving the stability of the polycyclic polymer.

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] Two L's 2may be the same or different, and Q represents a terminal group having a carbon-carbon double bond for forming a cyclic moiety by an olefin metathesis reaction. 2 In that case, L 2 L can be a divalent group arbitrarily selected from those that can be industrially used as a linker group for introducing a terminal group. 2 may be, for example, a group represented by the following formula (11), (12), or (13). In formula (11), p and q each independently represent an integer of 1 or more and 5 or less. In formula (12), r represents an integer of 0 or more and 5 or 1 or more and 5 or less. The group of formula (11) or (12) usually has R on the carbonyl group side. 2 and combine.

[0034] [ka]

[0035] Q 2 contains a polysiloxane chain. 2 may contain, in addition to the polysiloxane chain, for example, an acrylic polymer chain or a polyoxyalkylene chain.

[0036] Q containing polysiloxane chains 2 An example of this is represented by the following formula (30): In formula (30), multiple R 4 each independently 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. n is preferably 500 to 3,000, more preferably 600 to 2,000, and even more preferably 650 to 1,500. 4 may be the same or different. 4 may be a linear, branched or cyclic, saturated or unsaturated aliphatic group, or an aromatic group. 4 R may each independently be an alkyl group having 1 to 5 or 1 to 3 carbon atoms, a vinyl group, or a phenyl group. 4Specific examples include methyl, ethyl, and propyl groups.

[0037] [ka]

[0038] 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. Examples of the acrylic polymer chain are represented by the following formula (31) or (32). In formula (31), multiple R 7 each independently represents a hydrogen atom or a methyl group, and multiple R 8 each independently represents a hydrocarbon group which may have a substituent, or a hydrogen atom; R 9 represents a divalent organic group, and n 1 and n 2 Each independently represents a positive integer. 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. 2 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 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 2 to 6 carbon atoms. 8 From the viewpoint of stability during production, R may be a saturated hydrocarbon group (e.g., an alkyl group). 8 Specific examples are stearyl, lauryl, isobornyl, n-octyl, 2-ethylhexyl, n-hexyl, cyclohexyl, n-butyl, and ethyl groups.

[0039] [ka]

[0040] R in equation (31) 9 R may 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 each independently represents an alkylene group, and R 11 represents an alkylene group. 10 R may be, for example, a propane-2,2-diyl group (-C(CH3)2-). 11 may be an alkylene group having 2 to 10 carbon atoms (for example, an ethane-1,2-diyl group).

[0041] [ka]

[0042] Q containing polyoxyalkylene chains 2 Examples of the formula (33) or (34) are shown below. In the formula (33), multiple R 12 each independently represents an alkylene group, and R 13 represents a divalent organic group, and n 1 and n 2 Each independently represents a positive integer. In formula (34), R 12 is the same as above, and n represents a positive integer. 12 R 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.

[0043] [ka]

[0044] R in equation (33) 13may be, for example, a divalent group represented by the following formula (330) or (331). In formula (330), two R 14 Each independently represents an alkylene group having 1 to 5 carbon atoms (for example, a methylene group). 15 R represents a divalent aliphatic hydrocarbon group having 2 to 10 carbon atoms. 15 may be an alkylene group having 2 to 10 carbon atoms.

[0045] [ka]

[0046] The polycyclic polymer having a tetravalent group represented by formula (200a), (200b), (200c) or (200d) can be obtained, for example, by polymerizing a compound represented by the following formula (IIa). The compound of formula (IIa) is a compound represented by formula (I) 2 and L 2 and a cycloolefin structure bonded to both ends of the molecular chain. The group represented by formula (200a), (200b), (200c), or (200d) is a structure derived from two cycloolefin structures within the same molecule. Usually, the group of formula (200a) is mainly produced by the reaction of two cycloolefin structures. When each chemical formula described in this specification contains a structure corresponding to the group represented by formula (200a), that structure is described as a representative example and can be replaced with a structure corresponding to the group represented by formula (200b), (200c), or (200d). The tetravalent group represented by formula (200'a), (200'b), (200'c), or (200'd) can be a group formed by hydrogenation to the group represented by formula (200a), (200b), (200c), or (200d), respectively.

[0047] [ka]

[0048] X, L 2 and Q 2Examples of the above are the same as those described above.

[0049] The polycyclic 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 2 and norbornenyl groups bonded to both ends of the molecular chain. The group represented by formula (20a), (20b), (20c), or (20d) is a structure 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.

[0050] [ka]

[0051] L 2 and Q 2 Examples of the above are the same as those described above.

[0052] <Method of manufacturing polymer compounds> An example of a method for producing a polymer compound is shown below. The polycyclic polymer represented by the following formula (IIIa) can be obtained, for example, by polymerizing a compound represented by the following formula (IIa) (hereinafter also referred to as a linear macromonomer (LM)).

[0053] [ka]

[0054] In the formula, X, L 2 and Q 2 Examples of the groups are the same as those described above. m is a number of 2 or more. The phenyl group at the end of the main chain is a group derived from a Grubbs catalyst, and the hydrogen atom on the phenyl group may be substituted with a substituent. In formula (IIIa), L relative to the ring containing X 2 The bonding position of is any carbon atom in the ethylene group, as in the above formulae (200a), (200b), (200c), and (200d). m is preferably 2 or more and 100 or less, more preferably 4 or more and 100 or less, and even more preferably 5 or more and 50 or less. The method for producing a polycyclic polymer includes (i) an intramolecular ring-opening metathesis polymerization step of forming a cyclic macromonomer (CM) having a cyclic portion by intramolecular ring-opening metathesis polymerization of the linear macromonomer (LM), and (ii) an intermolecular / intramolecular metathesis polymerization step of forming the polymer compound by intermolecular metathesis polymerization of the cyclic macromonomer (CM) with another linear macromonomer (LM). The steps (i) and (ii) may be carried out one step at a time, or a multi-step reaction may be carried out in one pot.

[0055] In step (i), an intramolecular ring-opening metathesis polymerization process proceeds in which a linear macromonomer (LM) undergoes intramolecular ring-opening metathesis polymerization to form a cyclic macromonomer (CM) having a cyclic moiety. First, the linear macromonomer (LM) (IIa) reacts with the Grubbs catalyst to form the synthetic intermediate (IIb), which then undergoes intramolecular ring-opening metathesis polymerization to produce the cyclic macromonomer (CM) (IIc), which has a cyclic moiety. In the formula, [M] is a metal-containing group derived from the Grubbs catalyst, which forms a complex with the carbene at the end of the main chain.

[0056] [ka]

[0057] Next, in step (ii), the cyclic macromonomer (CM) (IIc) undergoes intermolecular metathesis polymerization with another linear macromonomer (LM) (IIa) to be converted into a synthetic intermediate (IId) represented by chemical formula (IId).

[0058] [ka]

[0059] Subsequently, the synthetic intermediate (IId) undergoes intramolecular ring-opening metathesis polymerization to produce a dimer (IIe) having two cyclic moieties.

[0060] [ka]

[0061] A polycyclic polymer precursor (IIf) having m cyclic moieties is produced by intermolecular metathesis polymerization and intramolecular ring-opening metathesis polymerization of the dimer (IIe) with another linear macromonomer (LM) (IIa).

[0062] [ka]

[0063] The polycyclic polymer precursor (IIf) is reacted with ethyl vinyl ether to complete the polymerization reaction, thereby obtaining the desired polycyclic polymer (IIIa).

[0064] [ka]

[0065] The method may further include a hydrogenation step (iii) of hydrogenating the resulting polycyclic polymer.

[0066] [ka]

[0067] Specific examples of the polycyclic polymer represented by formula (IIIa) include the polycyclic polymer represented by the following formula (IIIa-1).

[0068] [ka]

[0069] In formula (IIIa-1), R 4 , m, and n are the same as above. 1a represents an alkylene group having 1 to 5 carbon atoms or an alkyleneoxy group having 1 to 5 carbon atoms, and L 2a represents an alkylene group having 1 to 5 carbon atoms.

[0070] Specific examples of the polycyclic polymer represented by formula (IIIa-1) include the polycyclic polymer represented by the following formula (IIIa-1-1):

[0071] [ka]

[0072] In formula (IIIa-1-1), m and n are the same as defined above.

[0073] <Applications of polymer compounds> The polymer compounds according to the present disclosure are useful, for example, as various damping materials. Examples of damping materials include vibration suppression members, sound-insulating materials, and seismic isolation rubber. The present disclosure can provide a viscoelastic body with an ultra-low hardness, having an elastic modulus of 10,000 Pa or less, without the addition of plasticizers, thereby providing vibration isolation and damping for extremely lightweight objects. For example, the polymer compounds according to the present disclosure can be used as vibration-proofing members or vibration-damping materials for the vibrating parts of audio equipment, hard disk pickups, moving and vibrating parts of mechanical watches, moving parts of electron microscopes, moving and vibrating parts of IC manufacturing equipment, and medical devices that use minute needles, etc. The polymer compound according to the present disclosure is useful as a viscoelastic material that can be used in cryogenic environments. The cryogenic environment is, for example, preferably −60° C. or lower, more preferably −80° C. or lower, and even more preferably −100° C. or lower. Examples of the viscoelastic material include seals, gaskets, hoses, and heat insulating materials (e.g., foam heat insulating materials, non-foam heat insulating materials) used in superconducting cables, magnetic resonance imaging devices, low-temperature storage devices for regenerative medicine, etc., low-temperature storage devices for fresh foods, etc., and railway feeders, etc.

[0074] The molded article may be a molded article of a polymer composition containing a polymer compound according to the present disclosure and other components. Examples of the other components include fillers, rubbers different from the polymer compound according to the present disclosure, plasticizers, colorants, crystallization inhibitors, and stabilizers. In the polymer composition, the ratio of the total amount of the other components to 100 parts by mass of the polymer compound according to the present disclosure may be, for example, 0.1 parts by mass, 1 part by mass, or 10 parts by mass or more, or may be 1000 parts by mass or less, or 100 parts by mass or less. [Example]

[0075] The present disclosure is not limited to the following examples. In the following description, the following abbreviations are used for number average molecular weights. M n,MALS : Number average molecular weight by SEC-MALS method M n,ring : Number average molecular weight of linear macromonomers by SEC-MALS method

[0076] < 1 H (400 MHz) NMR spectrum measurement 1 H (400 MHz) NMR spectra were measured at 25 °C on a JEOL JNM-ECS 400 instrument using CDCl3 as the solvent.

[0077] <Molecular weight (M n,MALS , and M n,ring ) Measurement The absolute number average molecular weight (M n,MALS), and the number average molecular weight (M n,ring ) was analyzed by SEC with multi-angle light scattering detection (SEC-MALS-Visco) in CHCl3 eluent (flow rate 1.0 mL min -1 ) and 40°C. The number average molecular weight of the cyclic portion was determined by the number average molecular weight (M n,ring The measurements were performed using a Jasco high-performance liquid chromatography system (PU-4180 HPLC pump, AS-4550 autosampler, CO-4060 column oven) equipped with a Shodex K-800D guard column (8.0 mm × 100 mm; 10 μm particle size), two Shodex columns (K-806L and K-804L; linear, 8.0 mm × 100 mm; 10 μm particle size), a DAWN 8 multi-angle laser light scattering detector (Wyatt Technology), a Viscostar viscosity detector (Wyatt Technology), and a RI-501 refractive index detector (Shodex).

[0078] <Method for purifying polymer compounds> Preparative SEC was performed using a JAIGEL HR-P guard column (8 mm × 40 mm, manufactured by Japan Analytical Industry Co., Ltd. (hereinafter also referred to as JAI)) and a JAIGEL-2HR column (linear, 20.0 mm × 600 mm, exclusion limit 5.0 × 10 3 , manufactured by JAI), JAIGEL-2.5HR column (linear, 20.0 mm × 600 mm, exclusion limit 2.0 × 10 4 , manufactured by JAI), and a JAIGEL-3HR column (linear, 20.0 mm × 600 mm, exclusion limit 7.0 × 10 4 The eluent was CHCl3 (flow rate 10.0 mL min−1) using a LaboACE LC-7080 liquid chromatography system (JAI) equipped with a JAI LC-7080. -1 ) and 25°C.

[0079] <Method for producing evaluation films (films of polymer compounds)> The polymer compounds of each example were dissolved in n-hexane in a vial. The solution in the vial was stirred at 40°C for 24 hours and then slowly cast onto a removable stainless steel plate attached to the rheometer. The solution in the petri dish was left to stand at 22°C to 25°C for 24 hours to distill off the solvent. Then, a film of the polymer compound (thickness: approximately 0.5 mm) was formed by heating at 50°C under vacuum for 24 hours.

[0080] 1. Synthesis of polycyclic polymers Example 1: Polycyclic polymer 5C43 Example 1-1: Preparation of linear macromonomer Polydimethylsiloxane with norbornenyl groups at both ends (NB-PDMS 43k -NB) In a three-neck flask, HOR-PDMS 43k -ROH (polydimethylsiloxane with hydroxypropyl groups at both ends, M n,MALS (41,300, 25.0 g, 0.605 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 dissolved in CHCl (99 mL). The solution in the three-neck flask was stirred at room temperature under an argon atmosphere for 3 days. CHCl was evaporated under reduced pressure, and the residue was dissolved in n-hexane. The NB-PDMS was washed four times with methanol. 43k -NB viscous body (23.2g, M n,MALS = 43,400 (CHCl3), where n is the NB-PDMS 43k -The degree of polymerization of the polysiloxane constituting NB was approximately 586.

[0081] [ka]

[0082] Example 1-2: Preparation of polycyclic polymers by ring-opening metathesis polymerization Under an argon atmosphere, the NB-PDMS prepared in Example 1-1 was placed in a three-neck flask. 43k -NB (5.00 g, 0.196 mmol) was dissolved in CHCl (1.96 L) to form a reaction solution. Subsequently, G3 (Grubbs third generation catalyst, 57.8 mg, 0.0654 mmol) dissolved in a small amount of CHCl was quickly added to the reaction solution to initiate polymerization. After stirring at room temperature for 2 hours, 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 evaporated from the reaction solution, and the residue was washed with acetone, followed by a separation wash with n-hexane and methanol. The catalyst residue was removed from the washed product by preparative SEC using chloroform as a solvent, yielding an elastomer of the polycyclic polymer 5C43 (4.99 g, M) with an average of five ring units. n,MALS = 217,500 (CHCl3), M n,SEC =73,500(THF), M n,ring =43,400), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 586. Below, per ring part 1 H-NMR is described. 1 H-NMR(400MHz,CDCl3):(ppm)5.50-5.10(br,2H,internal double bond of oligo(norbornene)backbone),4.15-3.85(br,4H,-SiCH2CH2CH2OCO-),3.30-1.80(br,14H,alkenyl of oligo(norbornene)backbone),1.78-1.58(m,4H,-SiCH2CH2CH2CH2O-),0.56-0.47(m,4H,-SiCH2CH2CH2CH2O-),0.20- -0.03(m,6×n H,-Si(CH3)2-).

[0083] [ka]

[0084] Example 2: Polycyclic polymer 6C50 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 50k -NB(M n,MALS = 49,700, a multicyclic polymer 6C50 (M n,MALS = 287,800 (CHCl3), M n,ring = 49,700), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 672.

[0085] Example 3: Polycyclic polymer 11C64 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 64k -NB(M n,MALS = 64,200, a multicyclic polymer 11C64 (M n,MALS = 681,400 (CHCl3), M n,ring =64,200), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 868.

[0086] Example 4: Polycyclic polymer 15C58 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 58k -NB(M n,MALS = 57,900, a multicyclic polymer 15C58 (M n,MALS = 864,400 (CHCl3), M n,ring = 57,900), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 782.

[0087] Example 5: Polycyclic polymer 16C73 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 73k -NB(M n,MALS= 72,600, a multicyclic polymer 16C73 (M n,MALS = 1,128,000 (CHCl3), M n,ring = 72,600), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 981.

[0088] Example 6: Polycyclic polymer 26C50 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 50k -NB(M n,MALS = 49,700, a multicyclic polymer 26C50 (M n,MALS = 1,311,000 (CHCl3), M n,ring = 49,700), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 672.

[0089] Example 7: Polycyclic polymer 28C73 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 73k -NB(M n,MALS = 72,600, a multicyclic polymer 28C73 (M n,MALS = 2,064,000 (CHCl3), M n,ring = 72,600), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 981.

[0090] Example 8: Polycyclic polymer 31C64 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 64k -NB(M n,MALS = 64,200, a multicyclic polymer 31C64 (M n,MALS = 1,987,000 (CHCl3), M n,ring=64,200), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 868.

[0091] Example 9: Polycyclic polymer 49C58 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 58k -NB(M n,MALS = 57,900, a multicyclic polymer 49C58 (M n,MALS = 2,833,000 (CHCl3), M n,ring = 57,900), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 782.

[0092] Comparative Example 1: Linear polymer L318 High molecular weight components were separated from hydroxy-terminated PDMS (Sigma-Aldrich, product number 482005) using preparative SEC, and linear polymer L318 (M n,MALS = 318,200 (CHCl3)).

[0093] The polycyclic polymers obtained in each example were subjected to various measurements, and the results are shown in Table 1.

[0094] [Table 1]

[0095] 2. Viscoelasticity of polycyclic polymers The dynamic viscoelasticity of the polycyclic polymers of Examples 1 to 9 was measured using an MCR-702e rheometer (manufactured by Anton Paar) equipped with P-PTD220 and H-PTD220 Peltier temperature controllers. The measurement tool consisted of parallel circular plates with a diameter of 25 mm, with the sample sandwiched between them to form a polymer film. The measurement was performed at 25°C, a shear strain of 1%, and an angular frequency (ω) of 0.01 rad·s -1 More than 100rad·s -1The angular frequency dispersion of the elastic modulus was measured in the following range. For Example 1 (5C43), in order to obtain the elastic modulus in a wider frequency range, the angular frequency (ω) was set to 0.00063 rad·s at the same temperature of 25°C and a shear strain of 1%. -1 More than 398rad·s -1 The viscoelasticity of the film was measured in the following ranges:

[0096] FIG. 1 shows the master curves of G' and G'' of 5C43 obtained in Example 1. It was found that the polycyclic polymers 5C43 and 6C50 satisfy the relationship G'>G'' over a wide frequency range and exhibit favorable dynamic viscoelasticity compared to the linear polymer L318.

[0097] 3.Verification of solubility in organic solvents 3-1. Evaluation of solubility in methyl ethyl ketone The polycyclic polymers of Examples 1 to 9 were evaluated for solubility in methyl ethyl ketone. The test was carried out as follows. First, 18 g of methyl ethyl ketone was placed in a round-bottom flask and gently stirred using a magnetic stirrer at 25° C. To this, 2.0 g of the polycyclic polymer of each example was added all at once, and the state inside the flask during dissolution was observed. The solubility was evaluated using the following criteria immediately after dissolution, 2 hours later, on the second, third and fourth days. Evaluation criteria: After gentle stirring at 25° C. using a magnetic stirrer, the solubility was evaluated visually according to the following evaluation criteria. The results are shown in Table 2. <Evaluation criteria> A: The methyl ethyl ketone solution was a transparent, homogeneous solution at all times. B: The solution was cloudy at some point. C: Insoluble matter precipitated at some point. D: Not completely dissolved at any time during dissolution.

[0098] [Table 2]

[0099] As shown in Table 2, the polycyclic polymers of Examples 1 to 9 exhibited stable viscoelasticity from low to high frequency ranges while maintaining solubility in organic solvents. On the other hand, the linear polymer of Comparative Example 1 had G'≧G" in the high frequency region around 100 rad / s, but in the low frequency region, G">G', that is, the loss elasticity property (viscosity) was relatively greater than the storage elasticity property (elasticity), and the effects of the present disclosure could not be exhibited.

[0100] Comparative Example 2: Polycyclic polymer 2C50 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 50k -NB(M n,MALS = 49,700), a multicyclic polymer 2C50 (M n,MALS = 89,500 (CHCl3), M n,ring = 49,700), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 672.

[0101] Comparative Example 3: Polycyclic polymer 3C50 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 50k -NB(M n,MALS = 49,700, a multicyclic polymer 3C50 (M n,MALS = 139,000 (CHCl3), M n,ring = 49,700), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 672.

[0102] Example 10: Polycyclic polymer 4C50 NB-PDMS as polydimethylsiloxane with norbornenyl groups at both ends 50k -NB(M n,MALS= 49,700, a multicyclic polymer 4C50 (M n,MALS = 192,000 (CHCl3), M n,ring = 49,700), where n is the degree of polymerization of the polysiloxane that constitutes the cyclic portion of the polycyclic polymer, and is approximately 672.

[0103] The polycyclic polymers obtained in each example were subjected to various measurements, and the results are shown in Table 3.

[0104] [Table 3]

[0105] [Table 4]

[0106] FIG. 2 shows the master curves of G' and G'' of 4C50 obtained in Example 10. Compared with 2C50 and 3C50, which have fewer rings, 4C50 satisfies G'>G'' over a wide frequency range and is found to exhibit favorable dynamic viscoelasticity.

[0107] As shown in Table 4, the polycyclic polymer of Example 10 maintained its solubility in organic solvents and exhibited stable viscoelasticity from low to high frequency regions. On the other hand, the polycyclic polymers of Comparative Examples 2 and 3 had G'≦G" in the low frequency region. In other words, in the low frequency region, the loss elasticity (viscosity) was relatively greater than the storage elasticity (elasticity), and the effects of the present disclosure could not be achieved.

Claims

1. A polymer compound having a polydimethylsiloxane structure as a main component, The number average molecular weight is 200,000 or more, Temperature 25°C, shear strain 1%, measurement angular frequency 0.01 rad・s －１ More than 100rad・s －１ A polymer compound in which the storage modulus (G') is greater than the loss modulus (G") over the entire range below.

2. Temperature 25°C, shear strain 1%, measurement angular frequency 0.01 rad・s －１ More than 100rad・s －１ 2. The polymer compound according to claim 1, wherein the storage modulus (G') is 100,000 Pa or less over the entire range of:

3. Temperature 25°C, shear strain 1%, measurement angular frequency 0.01 rad・s －１ More than 100rad・s －１ 2. The polymer compound according to claim 1, wherein the ratio of G″ / G′ (Tan δ) is 0.2 or more in the entire range below.

4. The polymer compound according to claim 1 , which is soluble in an organic solvent.

5. The polymer compound according to claim 1 , having a C═C structure.

6. the polymer compound has a cyclic portion that is a cyclic structure, The polymer compound according to claim 1 , wherein the cyclic portion comprises the polydimethylsiloxane structure.

7. The polymer compound according to claim 6 , wherein the number average molecular weight of the cyclic portion is 40,000 or more.

8. Contains three or more structural units represented by the following formula (II) or (II'): The number average molecular weight is 180,000 or more, A polymer compound in which the number average molecular weight of the cyclic portion contained in the structural unit is 40,000 or more. 【Chemistry 1】 【Chemistry 2】 In formulas (II) and (II′), R ２ represents a tetravalent hydrocarbon group, and two L ２ each independently represents a divalent linker group; Q ２ is R ２ and two L ２ and a polymer chain having a polydimethylsiloxane structure forming the cyclic portion.

9. an intramolecular ring-opening metathesis polymerization step of forming a cyclic macromonomer (CM) having a cyclic moiety by intramolecular ring-opening metathesis polymerization of a linear macromonomer (LM) having a polydimethylsiloxane structure and two cyclic olefin structures; and a step of forming the polymer compound by intermolecular / intramolecular ring-opening metathesis polymerization after intermolecular ring-opening metathesis polymerization of the cyclic macromonomer (CM) with another linear macromonomer (LM).

10. A vibration suppressing member for suppressing micro-vibrations, which uses the polymer compound according to claim 1.

11. A liquid nitrogen heat insulating material or a liquid nitrogen low-temperature storage container, which uses the polymer compound according to claim 1.

12. A sealing material for a low-temperature storage container or a low-temperature storage container, which uses the polymer compound according to claim 1.

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