Heat-resistant polymer

Abstract

To provide a heat-resistant polymer that is a novolac type phenolic resin able to exhibit excellent heat resistance.SOLUTION: This heat-resistant polymer at least includes units based on dihydroxy biphenyl or derivatives thereof, connected via a C1-5 alkylene group and / or a structure represented by a formula (3). In the formula (3), R41 and R42 are, in at least some parts, substituent R04, and the substituent R04 is selected from C1-5 alkyl groups and aryl groups.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a heat-resistant polymer, and more particularly to a heat-resistant polymer belonging to novolac-type phenolic resins. [Background technology]

[0002] Novolac-type phenolic resins obtained by using phenols and aldehydes have been conventionally used as resin raw materials in various fields. For example, they are used as sealants in the manufacture of electronic components, dry resists, wet resists, fiber sizing agents in the manufacture of fiber-reinforced materials, matrix materials for fiber-reinforced materials, various thermosetting resins, cured resins for construction materials, urethane foams, epoxy resin compositions, paints, etc. When used as raw material components for these, higher heat resistance is generally required. For example, Patent Document 1 below discloses that a monohydroxy aromatic aldehyde such as salicylaldehyde can be used to improve the heat resistance of a novolac-type phenolic resin. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2002-107925 A Summary of the Invention [Problem to be solved by the invention]

[0004] However, as mentioned above, novolak-type phenolic resins have a very wide range of applications, and therefore, in addition to replacing aldehydes, other measures to improve heat resistance are required. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a heat-resistant polymer, which is a novolac-type phenolic resin capable of exhibiting excellent heat resistance. [Means for solving the problem]

[0005] That is, the present invention includes the following inventions. [1] Having units connected to each other via an alkylene group having 1 to 5 carbon atoms and / or a structure represented by the following formula (3), The unit includes a first unit represented by the following formula (1) and at least the second unit represented by the following formula (2): [ka] R in the above formula (1) 11 R in the formula (2) 21 R in the formula (2) 31 is at least partially a substituent R 01 and The substituent R 01 is a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and an aryl group, R in the above formula (1) 12 R in the formula (2) 22 R in the formula (2) 32 is at least partially a substituent R 02 and The substituent R 02 is selected from the group consisting of alkyl groups having 1 to 5 carbon atoms and alkoxyalkyl groups having 2 to 10 carbon atoms; R in the above formula (3) 41 R in the formula (3) 42 is at least partially a substituent R 04 and The substituent R 04 is selected from the group consisting of alkyl groups having 1 to 5 carbon atoms and aryl groups. [2] The heat-resistant polymer according to the above [1], wherein, when the number of the first units is n and the number of the second units is m, 0.05≦m / (n+m)≦1 is satisfied. [3] The heat-resistant polymer according to the above [1] or [2], having an average weight molecular weight of 2,500 or more. [4] The heat-resistant polymer according to any one of [1] to [3] above, having a glass transition temperature of 85° C. or higher. Effect of the Invention

[0006] The heat-resistant polymer of the present invention can provide excellent heat resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The present invention will be described below based on specific embodiments. However, the present invention is not limited to these embodiments. These embodiments are merely examples shown for the sake of convenience, and the present invention is not limited to these in any sense. The present invention can be modified in various ways depending on the purpose and application. In addition, all publications, patents, and patent applications cited in this specification are incorporated herein by reference as they are. In addition, in this specification, the description "XX-YY" means "XX or more and YY or less." Furthermore, in the compounds exemplified in this specification, a CAS Registry Number may be written in addition to a part of a compound name that has multiple notations, but since the CAS Registry Number differs depending on the isomeric form, etc., this is only an example of the compound name written in addition, and does not correspond one-to-one to the compound name and the CAS Registry Number.

[0008] [1] Heat-resistant polymer The heat-resistant polymer has units connected to each other via an alkylene group having 1 to 5 carbon atoms and / or a structure represented by the following formula (3): The unit includes a first unit represented by the following formula (1) and at least a second unit of a second unit represented by the following formula (2). [ka] However, R in formula (1) 11 , R in Eq. (2) 21 , R in Eq. (2) 31 is at least partially a substituent R 01 (i.e., R 11 , R 21 and R 31 are each independently at least a part of which is a substituent R 01 ), the substituent R01 is a group selected from the group consisting of alkyl groups having 1 to 5 carbon atoms and aryl groups. In addition, R in formula (1) 12 , R in Eq. (2) 22 , R in Eq. (2) 32 is at least partially a substituent R 02 (i.e., R 12 , R 22 and R 32 are each independently at least a part of which is a substituent R 02 ), the substituent R 02 is selected from the group consisting of alkyl groups having 1 to 5 carbon atoms and alkoxyalkyl groups having 2 to 10 carbon atoms. Furthermore, R in formula (3) 41 R in the formula (3) 42 is at least partially a substituent R 04 and the substituent R 04 is selected from the group consisting of alkyl groups having 1 to 5 carbon atoms and aryl groups.

[0009] The heat-resistant polymer may be obtained by any method, but may be obtained, for example, as a copolymer (novolac resin) in which a phenolic compound (a compound having an aromatic ring and a phenolic hydroxyl group) and an aldehyde compound are used as monomers. That is, the first unit and the second unit are structural units derived from a phenolic compound, and the alkylene group having 1 to 5 carbon atoms is a structural unit derived from an aldehyde compound. A phenolic compound is a compound having a phenolic hydroxy group. That is, the phenolic hydroxy group is a hydroxy group bonded to a carbon atom that constitutes an aromatic ring and has no substituent other than the hydroxy group. An aldehyde compound is a compound having an aldehyde group (-CHO).

[0010] The group connecting the units (hereinafter, simply referred to as a "unit connecting group") is an alkylene group having 1 to 5 carbon atoms and / or a structure represented by formula (3) (R 5 , R in Eq. (8) 4 , R in Eq. (8)5 ). That is, examples of alkylene groups that serve as unit connecting groups include methylene groups, ethylene groups, propylene groups (n-propylene groups, isopropylene groups, etc.), butylene groups (n-butylene groups, 1-methylpropylene groups, 2-methylpropylene groups, 1,1-dimethylethylene groups, 1,2-dimethylethylene groups, etc.), pentylene groups (n-pentylene groups, 1-methylbutylene groups, 2-methylbutylene groups, 1,1-dimethylpropylene groups, 1,2-dimethylpropylene groups, 1,3-dimethylpropylene groups, 1-methyl-2,2-dimethylethylene groups, etc.), etc. These may be used alone or in combination of two or more.

[0011] The compound (monomer) that is the base of the alkylene group that is the unit connecting group may be any compound that can form a unit connecting group that is an alkylene group having 1 to 5 carbon atoms, and the type of the compound is not limited, but as described above, an aldehyde compound may be mentioned. Specifically, an aliphatic aldehyde may be mentioned. In addition, an aliphatic aldehyde generating compound that can generate an aliphatic aldehyde may also be used. Examples of the aliphatic aldehyde include formaldehyde, acetaldehyde, propanal, butanal (n-butanal, 2-methylpropanal, etc.), pentanal (n-pentanal, 2-methylbutanal, 3-methylbutanal, etc.), acrolein, glyoxal, glyoxylic acid, succindialdehyde, malondialdehyde, glutaric dialdehyde, allyl aldehyde, crotonaldehyde, etc. These may be used alone or in combination of two or more. Examples of the aliphatic aldehyde generating compound include hexamethylenetetramine, trioxane, tetraoxane, polyoxymethylene, paraldehyde, metaldehyde, etc. These may be used alone or in combination of two or more.

[0012] On the other hand, the structure represented by formula (3) which is the unit connecting group is R 41 and R 42 At least a part of the substituent R 04 It is. [ka] There are multiple unit connecting groups in one heat-resistant polymer molecule. Therefore, there are multiple R 41 and R 42 There are also multiple R 41 and R 42 At least a part of the substituent R 04 That is, R 41 and R 42 A part of the substituent R 04 In that case, R 41 and R 42 becomes a hydrogen atom. Also, R 41 and R 42 is a substituent R 04 If R 41 and R 42 each independently represents a substituent R 04 That is, in one unit connecting group, R 41 and R 42 Each of the substituents R 04 R may be 41 and R 42 Only one of the substituents R 04 and the other may be a hydrogen atom, R 41 and R 42 may be hydrogen atoms. 41 and R 42 Both are substituents R 04 In the case where R 41 and R 42 Only one of the substituents R 04 In the case where the substituent R 04 may be the same as or different from R 41 and R 42 is a substituent R 04 If R 41 and R 42 is one substituent R 04 may be configured as follows.

[0013] Substituent R 04 is an alkyl group having 1 to 5 carbon atoms and / or an aryl group. Among these, examples of the alkyl group having 1 to 5 carbon atoms include the above-mentioned methyl group, ethyl group, propyl group (n-propyl group, isopropyl group, etc.), butyl group (n-butyl group, 1-methylpropyl group, 2-methylpropyl group, 1,1-dimethylethyl group, 1,2-dimethylethyl group, etc.), pentyl group (n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group, 1-methyl-2,2-dimethylethyl group, etc.), etc. These may be used alone or in combination of two or more kinds.

[0014] The aryl group may be a monocyclic aryl group or a polycyclic aryl group, and these may be used alone or in combination of two or more kinds. Examples of the monocyclic aryl group include a phenyl group, a tolyl group (a p-tolyl group, an o-tolyl group, an m-tolyl group), and a xylyl group (a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, and a 2,6-xylyl group). Examples of polycyclic aryl groups include naphthyl groups (1-naphthyl groups, 2-naphthyl groups, etc.), anthracenyl groups (1-anthracenyl groups, 2-anthracenyl groups, 9-anthracenyl groups, etc.), phenanthrenyl groups, pyrenyl groups, and fluororenyl groups. These may be used alone or in combination of two or more. The number of carbon atoms constituting the aryl group is not limited, but may be 6 to 20.

[0015] The first unit (the unit represented by the above formula (1)) is a phenol or a phenol having a substituent R 01 (In the first unit, R 11 ) is a unit based on a phenol derivative having the substituent R 01 (In the first unit, R 11 ) include alkyl groups and aryl groups having 1 to 5 carbon atoms (however, the first unit and the second unit do not have the same chemical structure). Therefore, R in Equation (1) 11 Examples of R include H (hydrogen atom), an alkyl group having 1 to 5 carbon atoms, and an aryl group. These may be used alone or in combination of two or more. That is, since there are a plurality of first units constituting the heat-resistant polymer, there are a plurality of R 11 There are multiple R 11 may be the same or different from each other.

[0016] Substituent R 01 (In the first unit, R 11 Among these, examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), a butyl group (n-butyl group, isobutyl group, tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, tert-pentyl group, etc.), etc. These may be used alone or in combination of two or more kinds.

[0017] Substituent R 01 (In the first unit, R 11 Examples of the aryl group among these include a phenyl group, a tolyl group (p-tolyl group, o-tolyl group, m-tolyl group), and a xylyl group (2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group). These may be used alone or in combination of two or more. The number of carbon atoms constituting the aryl group is not limited, but may be 6 to 12.

[0018] That is, examples of the compound (monomer) that serves as the base of the first unit include phenol, 2-alkylphenol, 2-arylphenol, etc. These may be used alone or in combination of two or more kinds. Among the above, examples of 2-alkylphenols include 2-methylphenol (o-cresol), 2-ethylphenol, 2-propylphenol, 2-butylphenol, and 2-pentylphenol. These may be used alone or in combination of two or more. Examples of 2-arylphenols include 2-phenylphenol [also known as 1,1'-biphenyl-2-ol], 2-(2-methylphenyl)phenol [also known as 1,1'-biphenyl-2-ol, 2'-methyl], and 1,1'-biphenyl-2-ol, 2',4'-dimethyl. These may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining solubility in a solvent, 2-alkylphenols are preferred, and o-cresol is more preferred. On the other hand, from the viewpoint of better heat resistance, 2-phenylphenol is preferred.

[0019] The second unit (the unit represented by the above formula (2)) is a unit based on dihydroxybiphenyl or a derivative thereof. That is, examples of the compound (monomer) that is the base of the second unit include dihydroxybiphenyl and its derivatives. These may be used alone or in combination of two or more.

[0020] Among the above, the dihydroxybiphenyls include 2,2'-dihydroxybiphenyl, 2,3'-dihydroxybiphenyl, 2,4'-dihydroxybiphenyl, 2,5'-dihydroxybiphenyl, 2,6'-dihydroxybiphenyl, 3,2'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 3,5'-dihydroxybiphenyl, 3,6'-dihydroxybiphenyl, 4,2'-dihydroxybiphenyl, 4,3'-dihydroxybiphenyl, 4 , 4'-dihydroxybiphenyl, 4,5'-dihydroxybiphenyl, 4,6'-dihydroxybiphenyl, 5,2'-dihydroxybiphenyl, 5,3'-dihydroxybiphenyl, 5,4'-dihydroxybiphenyl, 5,5'-dihydroxybiphenyl, 5,6'-dihydroxybiphenyl, 6,2'-dihydroxybiphenyl, 6,3'-dihydroxybiphenyl, 6,4'-dihydroxybiphenyl, 6,5'-dihydroxybiphenyl, 6,6'-dihydroxybiphenyl, etc. These may be used alone or in combination of two or more.

[0021] Dihydroxybiphenyl derivatives include those in which a hydroxy group and a substituent R are each attached to two adjacent carbon atoms of one benzene ring forming a biphenyl structure. 01 (In the second unit, R 21 or R 31 and a compound having a hydroxy group at any of the carbon atoms at positions 2 to 5 of the other benzene ring forming the biphenyl structure (a compound represented by the following formula (4) or (5)). As a derivative of dihydroxybiphenyl, there is a compound having a hydroxy group and a substituent R at each of two adjacent carbon atoms of one benzene ring forming the biphenyl structure. 01 (In the second unit, R 21 ), and two adjacent carbon atoms of the other benzene ring forming the biphenyl structure each have a hydroxy group and a substituent R 01 (In the second unit, R 31 ) (compounds represented by the following formula (6)), and the like.

[0022] [ka]

[0023] Substituent R 01 (In the second unit, R 21 , R 31 ) include alkyl groups and aryl groups having 1 to 5 carbon atoms. These may be used alone or in combination of two or more kinds. In other words, since there are multiple second units constituting the heat-resistant polymer, there are multiple R 21 and R 31 There are multiple R 21 may be the same or different. Similarly, these multiple R 31 may be the same or different from each other.

[0024] Substituent R 01 (In the second unit, R 21 or R 31 Among these, examples of the alkyl group having 1 to 5 carbon atoms include the various groups described above in the description of the first unit. These may be used alone or in combination of two or more kinds. Substituent R 01 (In the second unit, R 21 or R 31 Among these, examples of the aryl group include the various groups described above in the description of the first unit. These may be used alone or in combination of two or more kinds.

[0025] Therefore, examples of the derivatives of dihydroxybiphenyl represented by the above formula (4) or (5) include 4,2'-dihydroxy-2-alkylbiphenyl, 4,2'-dihydroxy-3-alkylbiphenyl, 4,2'-dihydroxy-5-alkylbiphenyl, 4,2'-dihydroxy-6-alkylbiphenyl, 4,3'-dihydroxy-2-alkylbiphenyl, 4,3'-dihydroxy-3-alkylbiphenyl, 4,3'-dihydroxy-5-alkylbiphenyl, 4,3'-dihydroxy-6-alkylbiphenyl, 4,4' 4,4'-dihydroxy-3-alkylbiphenyl, 4,4'-dihydroxy-2-alkylbiphenyl, 4,5'-dihydroxy-2-alkylbiphenyl, 4,5'-dihydroxy-3-alkylbiphenyl, 4,5'-dihydroxy-5-alkylbiphenyl, 4,5'-dihydroxy-6-alkylbiphenyl, 4,6'-dihydroxy-2-alkylbiphenyl, 4,6'-dihydroxy-3-alkylbiphenyl, 4,6'-dihydroxy-5-alkylbiphenyl, 4,6'-dihydroxy-6-alkylbiphenyl, etc. These may be used alone or in combination of two or more.

[0026] Furthermore, examples of the derivatives of dihydroxybiphenyl represented by the above formula (6) include 3,2'-dihydroxy-2,3'-dialkylbiphenyl, 3,2'-dihydroxy-4,3'-dialkylbiphenyl, 3,3'-dihydroxy-2,2'-dialkylbiphenyl, 3,3'-dihydroxy-4,2'-dialkylbiphenyl, 4,2'-dihydroxy-2,3'-dialkylbiphenyl, 4,2'-dihydroxy-3,3'-dialkylbiphenyl, 4,2'-dihydroxy-3,4'-dialkylbiphenyl, 4,2'-dihydroxy-5,5'-dialkylbiphenyl, 4,2'-dihydroxy-6,6'-dialkylbiphenyl, 4,3'-dihydroxy-2,2'-dialkylbiphenyl, 4,3'-dihydroxy-3,4'-dialkylbiphenyl, and 4,3'-dihydroxy-5,5'-dialkylbiphenyl. , 4,3'-dihydroxy-6,6'-dialkylbiphenyl, 4,4'-dihydroxy-2,2'-dialkylbiphenyl, 4,4'-dihydroxy-3,3'-dialkylbiphenyl, 4,4'-dihydroxy-2,5'-dialkylbiphenyl, 4,4'-dihydroxy-2,6'-dialkylbiphenyl, 4,5'-dihydroxy-2,2'-dialkylbiphenyl, 4,5'-dihydroxy-3,3'-dialkylbiphenyl, 4,5'-dihydroxy-5,4'-dialkylbiphenyl, 4,5'-dihydroxy-6,6'-dialkylbiphenyl, 4,6'-dihydroxy-2,2'-dialkylbiphenyl, 4,6'-dihydroxy-3,3'-dialkylbiphenyl, 4,6'-dihydroxy-5,4'-dialkylbiphenyl, 4,6'-dihydroxy-6,5'-dialkylbiphenyl, and the like. These may be used alone or in combination of two or more.

[0027] Among the dihydroxybiphenyl derivatives represented by the above formula (6), the substituent R 01 (In the second unit, R 21 or R 31Examples of compounds having a methyl group as the aryl group include 4,4'-dihydroxy-3,3'-dimethylbiphenyl (CAS RN 612-84-0), 4,3'-dihydroxy-3,4'-dimethylbiphenyl, 3,3'-dihydroxy-2,2'-dimethylbiphenyl, 3,2'-dihydroxy-2,3'-dimethylbiphenyl, 3,3'-dihydroxy-4,2'-dimethylbiphenyl, 3,2'-dihydroxy-4,3'-dimethylbiphenyl, 4,2'-dihydroxy-3,3'-dimethylbiphenyl, etc. These may be used alone or in combination of two or more.

[0028] From the above, an example of a heat-resistant polymer obtained by using the compound serving as the base of the second unit described above as a phenolic compound, without using the compound serving as the base of the first unit described above, is polymer 《1》 represented by the following formula (7). Also, an example of a heat-resistant polymer obtained by using the compound serving as the base of the first unit described above and the compound serving as the base of the second unit described above as a phenolic compound is polymer 《2》 represented by the following formula (8). These may be used alone or in combination of two or more. That is, the heat-resistant polymer may be a resin containing polymer 《1》 and / or polymer 《2》.

[0029] Polymer 1: Unit connecting group R 5 A polymer having second units connected to each other via [ka]

[0030] The abundance ratio of the first units and the second units in this polymer 1 is m / (n+m)=1, where n is the number of the first units and m is the number of the second units. The range of m in the formula (7) is not limited, but can be, for example, 1 to 3,000. In addition, in formula (7), the second unit is a unit connecting group R 5The number of repeating units with m is expressed as m. Since this heat-resistant polymer has a structure having units via unit connecting groups, the number of repeating units is equal to the number of second units, so it can be expressed in this way.

[0031] R in Equation (7) 21 and R 31 As mentioned above, R in formula (7) E1 is usually a hydrogen atom. Furthermore, R in (7) E2 is usually a second unit (a structure in which a hydrogen atom is bonded to the end of the second unit represented by formula (2)). That is, in the raw material resin, the second unit can also form a polymerization end.

[0032] As for the polymer 1, as shown in the examples described later, a unit connecting group R 5 A methylene group can be selected as the unit connecting group R 5 As described above, R in formula (3) is a group represented by the formula (3). 41 and R 42 is one substituent R 04 The substituent R 04 can be selected from an aryl group, a polycyclic aryl group, and a fluororenyl group. The fluororenyl group is a monovalent or divalent group having a fluorene skeleton, and in particular, the fluororenyl group is a divalent substituent in which the 9-position carbon of the fluorene has two bonds, and when the 9-position carbon is incorporated into the main chain of a heat-resistant polymer, the heat-resistant polymer can have a cardo structure and can have excellent heat resistance. Specifically, in the above formula (7), the unit connecting group R 5 is a divalent fluororenyl group, and a polymer in which the 9-position carbon of the fluororenyl group is incorporated into the main chain can be exemplified by the following formula (9). [ka] In addition, in formula (9), "m'" is R E1 and R E2This means that the chemical structure sandwiched between and is a repeating structure. The range of m' is not limited, but can be, for example, 1 to 1,500. The polymer represented by formula (9) can be obtained as a copolymer (novolac resin) using the above-mentioned dihydroxybiphenyl and / or its derivative as the phenolic compound and fluorenone as the aldehyde compound as the monomers.

[0033] Polymer 2: Unit connecting group R 4 and R 5 wherein the number of first units is n and the number of second units is m, and the polymer satisfies 0.05≦m / (n+m)<1. [ka]

[0034] The range of m in formula (8) is not limited, but can be, for example, 1 to 3,000. In addition, in formula (8), the first unit is a unit connecting group R 4 The number of repeating units with the unit connecting group R is expressed as n, and the second unit is 5 The number of repeating structures with the unit is expressed as m. Since the present heat-resistant polymer has a structure having each unit via a unit connecting group, the number of each repeating structure described above coincides with the number of the first unit or the number of the second unit, and therefore it can be expressed in this way.

[0035] R in Equation (8) 11 , R 21 and R 31 is as described above. That is, R 11 , R 21 and R 31 is at least partially a substituent R 01 Therefore, multiple R 11 At least a part of the substituents R 01 If multiple R 21 At least a part of the substituents R 01If multiple R 31 At least a part of the substituents R 01 Furthermore, if R 11 As the substituent R 01 If R 21 and R 31 is the substituent R 01 Similarly, R 21 As the substituent R 01 If R 11 and R 31 is the substituent R 01 Similarly, R 31 As the substituent R 01 If R 11 and R 21 is the substituent R 01 The substituent R 01 The case where R 01 is a hydrogen atom.

[0036] In addition, R in formula (8) 4 and R 5 is as described above as a unit connecting group. Furthermore, R E1 is usually a hydrogen atom. Furthermore, R in (8) E2 is usually a first unit (a structure in which a hydrogen atom is bonded to the end of a first unit represented by formula (1)) or a second unit (a structure in which a hydrogen atom is bonded to the end of a second unit represented by formula (2)). That is, in the raw material resin, the first unit and the second unit can also form a polymerization end.

[0037] In addition, it is convenient to express the polymer 2 as the above formula (8), but formula (8) does not mean that each unit (same in the repeating structure described above) exists as a block. That is, the first unit (same in the repeating structure containing the first unit described above) may exist in a block form or randomly. Of these, it is more preferable that it exists randomly. The term "the first unit is present in a block form" refers to a case where there is a molecular chain region in which it is apparent that the first unit is present in greater numbers than the second unit. That is, for example, there is a case where there is a molecular chain region in which only unit connecting groups and the first unit are present alternately. The term "the first unit is present randomly" refers to a state in which the first unit is present evenly throughout the molecular chain. That is, there is no case where there is a molecular chain region in which it is apparent that the first unit is present in greater numbers than the second unit.

[0038] Similarly, the second unit (the same applies to the repeating structure containing the second unit described above) may be present in a block form or randomly, and among these, it is more preferable that it is present randomly. The second units being present in a block manner refers to the case where there is a molecular chain region where it is apparent that there are more second units than first units. That is, for example, there is a molecular chain region where only unit connecting groups and second units are present alternately. The second units being present randomly refers to a state where the second units are present evenly throughout the molecular chain. That is, there is no molecular chain region where it is apparent that there are more second units than first units.

[0039] The abundance ratio of the first units to the second units in the polymer 2 satisfies 0.05≦m / (n+m)<1, where n is the number of the first units and m is the number of the second units. In this range, it can have better heat resistance than other heat-resistant polymers. The lower limit of m / (n+m) can be 0.10 or more, 0.15 or more, 0.20 or more, or 0.25 or more. On the other hand, the upper limit of m / (n+m) is not limited and can be 0.99, 0.95, 0.90, 0.85, or 0.80. These upper and lower limits can be appropriately combined. Therefore, for example, it can be 0.05 to 0.99, 0.10 to 0.95, 0.15 to 0.90, 0.20 to 0.85, or 0.25 to 0.80.

[0040] In addition, the polymer 《2》 has a unit connecting group R 4 and R 5 As described above, R in formula (3) is a group represented by the formula (3). 41 and R 42 and one substituent R 04 and the substituent R 04 In particular, when the fluororenyl group is a divalent substituent in which the 9-position carbon of fluorene has two bonds, and the 9-position carbon is incorporated into the main chain of a heat-resistant polymer, the heat-resistant polymer can have a cardo structure and can have excellent heat resistance.

[0041] In addition, the hydrogen atoms of the phenolic hydroxyl group in the polymer 1 represented by the above formula (7) may be partially or entirely substituted with a substituent R 02 (R 22 , R 32 The polymer having this substitution can be represented as polymer 3 of the following formula (10). Furthermore, the hydrogen atoms of the phenolic hydroxyl groups in the polymer 2 represented by the above formula (8) may be partially or entirely substituted with substituents R 02 (R 12 , R 22 , R 32The polymer having this substitution can be represented as polymer 4 of the following formula (11). That is, the present heat-resistant polymer can include one or more polymers selected from the group consisting of polymer <<1>>, polymer <<2>>, polymer <<3>>, and polymer <<4>>.

[0042] Polymer 3: Unit connecting group R 5 A polymer having second units connected to each other via [ka]

[0043] When the number of first units is n and the number of second units is m in the polymer 3, the abundance ratio of the first units to the second units is m / (n+m)=1. The range of m in the formula (10) is not limited, but may be, for example, 1 to 3,000. In addition, in formula (10), the second unit is a unit connecting group R 5 The number of repeating units with m is expressed as m. Since this heat-resistant polymer has a structure having units via unit connecting groups, the number of repeating units is equal to the number of second units, so it can be expressed in this way.

[0044] R in Equation (10) 21 and R 31 As mentioned above, R in formula (10) 5 is as described above as a unit connecting group. Furthermore, R E1 is usually a hydrogen atom. E2 is usually a structure in which a hydrogen atom is bonded to the end of the second unit (the second unit represented by formula (2)), provided that R 22 and R 32 That is, in the raw material resin, the second unit can also form a polymerization terminal.

[0045] R in Equation (10) 22, R in Eq. (10) 32 is at least partially a substituent R 02 (i.e., R 22 and R 32 are each independently at least a part of which is a substituent R 02 As described above, the polymer 3 has a plurality of second units. Therefore, the polymer 3 has R 22 and R 32 Each of these R 22 and R 32 are all substituents R 02 may be, but only a part of which may be the substituent R 02 That is, there may be multiple R 22 Only a part of the substituent R 02 There can be multiple R 32 Only a part of the substituent R 02 It can be.

[0046] Polymer 4: Unit connecting group R 4 and R 5 wherein the number of first units is n and the number of second units is m, and the polymer satisfies 0.05≦m / (n+m)<1. [ka]

[0047] The range of m in formula (11) is not limited, but can be, for example, 1 to 3,000. In addition, in formula (11), the first unit is a unit connecting group R 4 The number of repeating units with the unit connecting group R is expressed as n, and the second unit is 5 The number of repeating structures with the unit is expressed as m. Since the present heat-resistant polymer has a structure having each unit via a unit connecting group, the number of each repeating structure described above coincides with the number of the first unit or the number of the second unit, and therefore it can be expressed in this way.

[0048] R in Equation (11) 11, R 21 and R 31 is as described above. R in formula (11) 12 , R 22 and R 32 is at least partially a substituent R 02 That is, the polymer 4 has a plurality of first units and a plurality of second units. At least a part of the plurality of first units has a substituent R 02 Furthermore, at least some of the second units have one or two substituents R 02 Therefore, multiple R 12 At least a part of the substituents R 02 If multiple R 22 At least a part of the substituents R 02 If multiple R 32 At least a part of the substituents R 02 Furthermore, if R 12 As the substituent R 02 If R 22 and R 32 is the substituent R 02 Similarly, R 22 As the substituent R 02 If R 12 and R 32 is the substituent R 02 Similarly, R 32 As the substituent R 02 If R 12 and R 22 is the substituent R 02 The substituent R 02 The case where R 02 is a hydrogen atom.

[0049] Furthermore, R in formula (11) E1 is usually a hydrogen atom. Also, R in (11) E2 is usually a structure in which a hydrogen atom is bonded to the end of the first unit (the first unit represented by formula (1)), provided that R 12or a second unit (a structure in which a hydrogen atom is bonded to the terminal of the second unit represented by formula (2), provided that R 22 and R 32 That is, in the raw material resin, the first unit and the second unit can form a polymerization terminal.

[0050] In addition, it is convenient to express polymer 《4》 as the above formula (11). However, like polymer 《2》, formula (11) does not mean that each unit (the same applies to the repeating structure described above) exists as a block. That is, the first unit (the same applies to the repeating structure containing the first unit described above) may be present in a block form or randomly, and among these, it is more preferable that the first unit is present randomly. Similarly, the second unit (the same applies to the repeating structure containing the second unit described above) may be present in a block form or randomly, and among these, it is more preferable that it is present randomly.

[0051] The abundance ratio of the first units to the second units in polymer 《4》 is 0.05≦m / (n+m)<1, where n is the number of the first units and m is the number of the second units. This is the same as in the case of polymer 《2》. In this range, it can have better heat resistance than other heat-resistant polymers. The lower limit of m / (n+m) can be 0.10 or more, 0.15 or more, 0.20 or more, or 0.25 or more. On the other hand, the upper limit of m / (n+m) is not limited and can be 0.99, 0.95, 0.90, 0.85, or 0.80. These upper and lower limits can be appropriately combined. Therefore, for example, it can be 0.05 to 0.99, 0.10 to 0.95, 0.15 to 0.90, 0.20 to 0.85, or 0.25 to 0.80.

[0052] In addition, the substituent R 02 (R 12 , R 22 , R 32 ) is a group selected from the group consisting of alkyl groups having 1 to 5 carbon atoms and alkoxyalkyl groups having 2 to 10 carbon atoms. Among these, examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group (n-propyl group, isopropyl group), a butyl group (n-butyl group, isobutyl group, tert-butyl group), a pentyl group (n-pentyl group, isopentyl group, tert-pentyl group, etc.), etc. These may be used alone or in combination of two or more kinds.

[0053] The alkoxyalkyl group is, for example, a group selected from the group consisting of alkoxyalkyl groups having 2 to 10 carbon atoms. 81 -OR 82 -" In this formula, R 81 and R 82 The total number of carbon atoms in R may be 10 or less. 81 and R 82 can be a hydrocarbon group having 1 to 9 carbon atoms. Examples of such alkoxyalkyl groups include R 81 is a methyl group and R 82 is an alkyl group having 1 to 9 carbon atoms (such as a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, a methoxyhexyl group, a methoxyheptyl group, a methoxyoctyl group, or a methoxynonyl group); R 81 is an ethyl group and R 82 is an alkyl group having 1 to 8 carbon atoms (such as an ethoxymethyl group, an ethoxyethyl group, an ethoxypropyl group, an ethoxybutyl group, an ethoxypentyl group, an ethoxyhexyl group, an ethoxyheptyl group, or an ethoxyoctyl group); R 81 is a propyl group and R 82is an alkyl group having 1 to 7 carbon atoms (such as a propoxymethyl group, a propoxyethyl group, a propoxypropyl group, a propoxybutyl group, a propoxypentyl group, a propoxyhexyl group, or a propoxyheptyl group); R 81 is a butyl group and R 82 is an alkyl group having 1 to 6 carbon atoms (such as butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxypentyl, and butoxyhexyl); R 81 is a pentoxy group and R 82 is an alkyl group having 1 to 5 carbon atoms (e.g., pentoxymethyl, pentoxyethyl, pentoxypropyl, pentoxybutyl, pentoxypentyl, etc.); R 81 is a hexoxy group and R 82 is an alkyl group having 1 to 4 carbon atoms (e.g., a hexoxymethyl group, a hexoxyethyl group, a hexoxypropyl group, a hexoxybutyl group, etc.); R 81 is a heptoxy group and R 82 is an alkyl group having 1 to 3 carbon atoms (e.g., a heptoxymethyl group, a heptoxyethyl group, a heptoxypropyl group, etc.); R 81 is an octoxy group and R 82 is an alkyl group having 1 to 2 carbon atoms (e.g., octoxymethyl group, octoxyethyl group); R 81 is a nonoxy group and R 82 is a methyl group (such as nonoxymethyl group); etc. These may be used alone or in combination of two or more.

[0054] Substituent R in polymer 3 and polymer 4 02 The modification rate by the substituent R is not limited, but can be 10% or more. 02The benefits of the introduction of the modified polysaccharide can be enjoyed more. The lower limit of the modified polysaccharide ratio can be 12% or more, and 15% or more. On the other hand, the upper limit of the modified polysaccharide ratio can be 50% or less, 48% or less, and 45% or more. These upper and lower limits can be appropriately combined. Therefore, for example, the modified polysaccharide ratio can be 10 to 50%, 10 to 48%, 12 to 48%, 12 to 45%, or 15 to 45%. The modification rate is the total number N0 of structural units derived from phenolic compounds, and the ratio of the substituents R 02 When the number of structural units having the above structure is N1, it is calculated as (N1 / N0)×100.

[0055] The heat-resistant polymer may be composed of only the first unit, the second unit, and the unit connecting group as the structural units, but may contain other structural units (other units) other than these. When the other structural units are contained, t / (n+m+s+t)<0.05, t / (n+m+s+t)<0.03, or t / (n+m+s+t)<0.01 can be satisfied, where n is the number of the first units, m is the number of the second units, s is the number of the unit connecting groups, and t is the number of the other structural units.

[0056] Examples of other structural units include structural units derived from phenolic compounds other than phenol and the above-mentioned phenol derivatives, structural units derived from dihydroxybiphenyl and other dihydroxybiphenyl derivatives other than the above-mentioned dihydroxybiphenyl derivatives, and structural units derived from aldehyde compounds other than the above-mentioned aliphatic aldehydes and their product compounds. These may be used alone or in combination of two or more.

[0057] The other phenolic compounds include those having a monovalent substituent (R 11) is an amino group, a nitro group, an alkoxy group, or the like. Other examples include naphthols such as α-naphthol and β-naphthol, phenols (monohydric phenols) such as anthrols and hydroxypyrene, and their alkyl derivatives; polyhydric phenols such as resorcinol, hydroquinone, catechol, pyrogallol, and phloroglucin, and their alkyl derivatives; bisphenols such as bisphenol A, bisphenol F, bisphenol S, bisphenol M, bisphenol B, bisphenol C, and bisphenol S; trisphenols; tetraphenols; and the like. The number of phenolic hydroxyl groups possessed by the polyhydric phenol is not limited, but may be, for example, 2 to 3. These may be used alone or in combination of two or more. On the other hand, other dihydroxybiphenyl derivatives include those with monovalent substituents (R 21 Or R 31 ) is an amino group, a nitro group, an alkoxy group, etc. These may be used alone or in combination of two or more.

[0058] Examples of the other aldehyde compounds include aliphatic aldehydes that form a unit connecting group having 6 or more carbon atoms, aliphatic aldehydes that form a unit connecting group containing a hetero atom, aromatic aldehyde compounds, compounds that produce these compounds, etc. These compounds may be used alone or in combination of two or more. Among the above, examples of the aliphatic aldehyde forming a unit connecting group having 6 or more carbon atoms include 2-ethylbutanal, cyclohexylaldehyde, 5-norbornene-2-carboxaldehyde, etc. These may be used alone or in combination of two or more. Examples of the aliphatic aldehyde that forms a unit connecting group containing a hetero atom include chloral, etc. These may be used alone or in combination of two or more kinds.

[0059] Examples of aromatic aldehyde compounds include furfural, benzaldehyde, phenylacetaldehyde, tolualdehyde (o-tolualdehyde, m-tolualdehyde, p-tolualdehyde), diphenylacetaldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde, phenylbenzaldehyde, hydroxybenzaldehyde, etc. These may be used alone or in combination of two or more.

[0060] The heat-resistant polymer may be obtained in any manner, but as described above, it can be obtained as a copolymer (addition condensate) of a phenolic compound and an aldehyde compound. This polymerization can be carried out using a catalyst according to a conventional method. Examples of the catalyst include acidic catalysts, basic catalysts, and other catalysts. Among these, acidic catalysts are preferred. The reaction conditions can be appropriately selected depending on the components used, but can be, for example, 60 to 150°C for 2 to 30 hours.

[0061] Among the above, examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid (including polyphosphoric acids such as metaphosphoric acid, pyrophosphoric acid, orthophosphoric acid, triphosphoric acid, tetraphosphoric acid, and phosphoric anhydride), phosphorous acid, phosphonic acid, and the like; sulfates such as oxalic acid and diethyl sulfate, organic sulfonic acids, and organic phosphones, etc. These may be used alone or in combination of two or more kinds. Among the above, examples of the organic sulfonic acid include paratoluenesulfonic acid, benzenesulfonic acid, xylenesulfonic acid, etc. Furthermore, examples of the organic phosphonic acid include ethylenediaminetetrakismethylenephosphonic acid, ethylenediaminebismethylenephosphonic acid, aminotrismethylenephosphonic acid, β-aminoethylphosphonic acid N,N-diacetic acid, aminomethylphosphonic acid N,N-diacetic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, etc.

[0062] Examples of the basic catalyst include metal hydroxides, metal oxides, amine compounds, etc. These may be used alone or in combination of two or more. Among these, examples of the metal hydroxide include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; and the like. Examples of the metal oxide include alkaline earth metal oxides such as calcium oxide and magnesium oxide; and the like. Examples of the amine compound include aliphatic amines such as dimethylamine, triethylamine, butylamine, and the like; aromatic amines such as dimethylbenzylamine and naphthalenediamine; and the like. These may be used alone or in combination of two or more. Further examples include ammonia, ammonia generating compounds such as hexamethylenetetramine which generate ammonia by decomposition, naphthenates, etc. These may be used alone or in combination of two or more.

[0063] Other examples of the catalyst include metal compounds not included in the above. For example, divalent metal salts and divalent metal compounds, such as zinc compounds such as zinc oxide, zinc chloride, and zinc acetate, can be mentioned. These can be used alone or in combination of two or more.

[0064] In the synthesis, a reaction solvent can be used. Examples of the reaction solvent include ketone compounds, ester compounds, alcohol compounds, ether compounds, etc. These can be used alone or in combination of two or more. Among the above, examples of the ketone compound include methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, ethyl n-butyl ketone, diisopropyl ketone, diethyl ketone, di-n-propyl ketone, mesityl oxide, methyl n-amyl ketone, methyl n-butyl ketone, methyl n-propyl ketone, acetone, etc. These may be used alone or in combination of two or more.

[0065] Examples of the ester compound include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, n-butyl acetate, sec-butyl acetate, isobutyl acetate, ethyl ethoxyacetate, ethyl oxyacetate, amyl acetate, isoamyl acetate, allyl acetate, ethyl isovalerate, propyl formate, butyl formate, isobutyl formate, isoamyl formate, diethyl carbonate, methyl propionate, ethyl propionate, butyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, isopropyl butyrate, ethyl butyrate, methyl butyrate, γ-butyrolactone, ethyl lactate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl acetoacetate, and ethyl acetoacetate. These may be used alone or in combination of two or more.

[0066] Examples of the alcohol compound include amyl alcohol (n-amyl alcohol, s-amyl alcohol, t-amyl alcohol), isoamyl alcohol, 2-ethylbutanol, 3,5-dimethyl-1-hexyne 3-ol, neopentyl alcohol, 2-methyl-1-butanol, 4-methyl-2-pentanol, ethylene glycol monoalkyl ether (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc.), diethylene glycol monobutyl ether, etc.), diethylene glycol dialkyl ether (diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc.), propylene glycol monoalkyl ether (propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.), etc. These may be used alone or in combination of two or more.

[0067] Examples of ether compounds include diethyl ether, ethyl isoamyl ether, ethyl t-butyl ether, 1,2-epoxybutane, diisopropyl ether, diethyl acetal, dibutyl ether, 2-methylfuran, ethylene glycol monoalkyl ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, etc.), ethylene glycol dialkyl ethers (ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, etc.), diethylene glycol monoalkyl ethers (diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, etc.), diethylene glycol dialkyl ethers (diethylene glycol dimethyl ether, diethylene glycol Examples of the ethylene glycol alkyl ether include ethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc.), ethylene glycol alkyl ether acetate (methyl cellosolve acetate, ethyl cellosolve acetate, etc.), propylene glycol monoalkyl ether (propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, etc.), propylene glycol dialkyl ether (propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, etc.), propylene glycol alkyl ether acetate (propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc.), and cyclic ethers (tetrahydrofuran, dioxane, etc.). These may be used alone or in combination of two or more.

[0068] The compounding ratio F / P (molar compounding ratio) of the phenolic compound (P) to the aldehyde compound (F) when obtaining a heat-resistant polymer is not limited, but from the viewpoint of obtaining a novolak resin using an acidic catalyst, it is preferably 0.8≦F / P≦1.5, more preferably 0.90≦F / P≦1.30, and even more preferably 1.00≦F / P≦1.20.

[0069] The molecular weight of the heat-resistant polymer is not limited, but the lower limit of the weight-average molecular weight is preferably 2,500 or more from the viewpoint of heat resistance. The weight-average molecular weight can be 3,000 or more, 4,000 or more, 5,000 or more, or 6,000 or more. On the other hand, the upper limit of the weight-average molecular weight is preferably 50,000 or less from the viewpoint of handling. The weight-average molecular weight can be 40,000 or less, 35,000 or less, 30,000 or less, 25,000 or less, or 20,000 or less. These upper and lower limits can be appropriately combined with each other. Therefore, for example, it can be 1,000 to 50,000, further 2,000 to 40,000, further 3,000 to 35,000, further 4,000 to 30,000, further 5,000 to 25,000, and further 6,000 to 20,000. The method for measuring the weight average molecular weight will be described later.

[0070] The glass transition temperature of the heat-resistant polymer is not limited, but according to the present heat-resistant polymer, the glass transition temperature can be 85°C or higher. It can be 90°C or higher, 95°C or higher, 100°C or higher, 125°C or higher, 150°C or higher, or 180°C or higher. On the other hand, the upper limit of the glass transition temperature is not limited, but can be, for example, 300°C or lower, or 250°C or lower. These upper and lower limits can be appropriately combined. Therefore, for example, the glass transition temperature can be 85 to 300°C, 90 to 300°C, 95 to 300°C, 100 to 250°C, 125 to 250°C, 150 to 250°C, or 180 to 250°C. The method for measuring the glass transition temperature will be described later. EXAMPLES

[0071] The present invention will now be described in more detail with reference to examples. [1] Preparation of heat-resistant polymers The following eight types of heat-resistant polymers (Examples 1 to 4, Comparative Examples 1 to 3) were prepared. The weight average molecular weight (Mw) and glass transition temperature (Tg) of these heat-resistant polymers were measured. The results are shown in Table 1. The respective measurement methods will be described later.

[0072] [Example 1] Into a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 270 parts by mass of o-cresol as a phenolic compound, 229 parts by mass of 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 119 parts by mass of formaldehyde as an aldehyde compound, and an acidic catalyst were respectively charged and reacted at 100°C for 5 hours, and then a purification operation was carried out to obtain a heat-resistant polymer of Example 1. The weight-average molecular weight (Mw) of the obtained heat-resistant polymer of Example 1 was 3809, and the glass transition temperature (Tg) was 119°C.

[0073] [Example 2] Into a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 270 parts by mass of o-cresol as a phenolic compound, 229 parts by mass of 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 133 parts by mass of formaldehyde as an aldehyde compound, and an acidic catalyst were added and reacted at 100°C for 5 hours, and then a purification operation was carried out to obtain a heat-resistant polymer of Example 2. The weight-average molecular weight (Mw) of the obtained heat-resistant polymer of Example 2 was 6997, and the glass transition temperature (Tg) was 157°C.

[0074] [Example 3] Into a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts by mass of 4,4'-dihydroxy-3,3'-dimethylbiphenyl as a phenolic compound, 227 parts by mass of formaldehyde as an aldehyde compound, an acidic catalyst, and a reaction solvent were each charged and reacted at 100°C for 10 hours, and then a purification operation was carried out to obtain a heat-resistant polymer of Example 3. The weight-average molecular weight (Mw) of the obtained heat-resistant polymer of Example 4 was 11576, and the glass transition temperature (Tg) was 197°C.

[0075] [Example 4] Into a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts by mass of 4,4'-dihydroxy-3,3'-dimethylbiphenyl as a phenolic compound, 227 parts by mass of formaldehyde as an aldehyde compound, an acidic catalyst, and a reaction solvent were each charged and reacted at 100°C for 14.5 hours, and then a purification operation was carried out to obtain a heat-resistant polymer of Example 4. The weight-average molecular weight (Mw) of the obtained heat-resistant polymer of Example 5 was 14260, and the glass transition temperature (Tg) was 199°C.

[0076] [Comparative Example 1] Into a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts by mass of o-cresol as a phenolic compound, 158 parts by mass of formaldehyde as an aldehyde compound, and an acidic catalyst were each charged and reacted at 100°C for 5 hours, and then a purification operation was carried out to obtain a heat-resistant polymer of Comparative Example 1. The weight-average molecular weight (Mw) of the obtained heat-resistant polymer of Comparative Example 1 was 3795, and the glass transition temperature (Tg) was 95°C.

[0077] [Comparative Example 2] Into a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts by mass of o-cresol as a phenolic compound, 166 parts by mass of formaldehyde as an aldehyde compound, and an acidic catalyst were each charged and reacted at 100°C for 5 hours, and then a purification operation was carried out to obtain a heat-resistant polymer of Comparative Example 2. The weight-average molecular weight (Mw) of the obtained heat-resistant polymer of Comparative Example 2 was 4336, and the glass transition temperature (Tg) was 102°C.

[0078] [Comparative Example 3] Into a reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, 500 parts by mass of o-cresol as a phenolic compound, 169 parts by mass of formaldehyde as an aldehyde compound, and an acidic catalyst were each charged and reacted at 100°C for 5 hours, and then a purification operation was carried out to obtain a heat-resistant polymer of Comparative Example 3. The weight-average molecular weight (Mw) of the obtained heat-resistant polymer of Comparative Example 3 was 6828, and the glass transition temperature (Tg) was 108°C.

[0079] [Table 1]

[0080] [2] Evaluation (1) Weight average molecular weight (Mw) The weight average molecular weight was measured under the following conditions using a high-speed GPC device (manufactured by Tosoh Corporation, model number "HCL-8320GPC") and a column compatible with the high-speed GPC device (manufactured by Tosoh Corporation, product names "TSKGel G2000HXL, G4000HXL"), and was converted using a calibration curve of standard polystyrene (manufactured by Tosoh Corporation, product names "F-40, F-20, F-10, F-4, F-2, F-1, A5000, A2500, A1000", manufactured by Tokyo Chemical Industry Co., Ltd., product name "2,2-methylenebis(4-methylphenol)", and manufactured by Kanto Chemical Co., Ltd., product name "p-cresol"). Solvent: Tetrahydrofuran (THF) Measurement temperature: 40℃ Flow rate: 1mL / min Sample concentration: Example: 3 mg / THF 5 mL, Comparative Example: 30 mg / THF 5 mL Injection volume: 100μL

[0081] (2) Glass transition temperature (Tg) The glass transition temperature was measured using a differential scanning calorimeter (Rigaku Corporation, model "Thermo plus EVO2 DSC8231"). In this case, a DSC chart was obtained by heating in the range of 25 to 250°C at a heating rate of 5°C / min, cooling, and then heating again. The glass transition temperature was read as the inflection point (based on the glass transition) of the baseline in the obtained DSC chart. For measurement objects containing solvent, the solvent was removed before measurement.

[0082] [3] Effects of the embodiment In the polymer of Comparative Example 1 in Table 1, all units are the first unit, and in the polymer of Example 1 in Table 1, 70% of all units are the first unit and 30% are the second unit, and both have almost the same Mw of 3795 and 3809, but the Tg of Example 1 is 25% higher than that of Comparative Example 1. In the polymer of Comparative Example 3 in Table 1, all units are the first unit, and in the polymer of Example 2 in Table 1, 70% of all units are the first unit and 30% are the second unit, and both have almost the same Mw of 6828 and 6997, but the Tg of Example 2 is 45% higher than that of Comparative Example 3. A comparison between Comparative Example 1 and Comparative Example 3 shows that the change in Tg with an increase in Mw from 3795 to 6828 is from 95°C to 108°C, and the rate of change is 0.43%. On the other hand, a comparison between Example 1 and Example 2 shows that the change in Tg with an increase in Mw from 3809 to 6997 is from 119°C to 197°C, and the rate of change is 1.20%. That is, it is found that the introduction of the second unit can efficiently improve Tg. Furthermore, from the results of Examples 3 and 4, it is clear that the polymers in which all units are second units have extremely high Tg values ​​of 197° C. and 199° C., respectively.

Claims

1. The alkylene group has 1 to 5 carbon atoms and / or units connected to each other via a structure represented by the following formula (3): The unit includes a first unit represented by the following formula (1) and at least the second unit represented by the following formula (2): [Formula 1] R in the formula (1) １１ , R in the formula (2) ２１ , R in the formula (2) ３１ is at least partially a substituent R ０１ and The substituent R ０１ is a group selected from the group consisting of an alkyl group having 1 to 5 carbon atoms and an aryl group, R in the formula (1) １２ , R in the formula (2) ２２ , R in the formula (2) ３２ is at least partially a substituent R ０２ and The substituent R ０２ is selected from the group consisting of alkyl groups having 1 to 5 carbon atoms and alkoxyalkyl groups having 2 to 10 carbon atoms; R in the formula (3) ４１ , R in the formula (3) ４２ is at least partially a substituent R ０４ and The substituent R ０４ is selected from the group consisting of alkyl groups having 1 to 5 carbon atoms and aryl groups.

2. 2. The heat-resistant polymer according to claim 1, wherein, when the number of the first units is n and the number of the second units is m, 0.05≦m / (n+m)≦1 is satisfied.

3. 2. The heat-resistant polymer according to claim 1, which has a weight-average molecular weight of 2,500 or more.

4. 2. The heat-resistant polymer according to claim 1, which has a glass transition temperature of 85° C. or higher.

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