Halogen-containing polymer and method for producing the same

Abstract

To provide a halogen-containing polymer having a higher halogen content than that of conventionally known halogen-containing polymers.SOLUTION: A halogen-containing polymer is used having at least one or more repeating units represented by the General Formula (1), where the polymer has, at a polymer chain end, at least one terminal group selected from a specific group of terminal groups including a halogen-containing phenoxy terminal group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a halogen-containing polymer used as a flame retardant, etc., and a method for producing the same. [Background technology]

[0002] Flame retardants are well known as additives that impart flame retardancy to resins when mixed with them. For example, compounds containing multiple halogen atoms have long been used as halogenated flame retardants. However, some low-molecular-weight halogenated flame retardants (e.g., polybrominated biphenyls) are subject to regulation under the PoPs Convention due to their harmful properties. For this reason, polymeric halogenated flame retardants with high biological safety have been developed in recent years.

[0003] Known polymeric bromine-based flame retardants include, for example, halogen-containing polymers with high heat resistance in which tetrabromobisphenol A is linked via ethylene groups (Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-77857 Summary of the Invention [Problem to be solved by the invention]

[0005] There is a demand for halogen-containing polymers with a higher halogen content than known halogen-containing polymers. [Means for solving the problem]

[0006] As a result of extensive investigations, the present inventors have found that the invention described below can solve the above problems, and have completed the present invention.

[0007] That is, the present invention relates to the following halogen-containing polymer and a method for producing the same.

[0008] [1] The following general formula (1)

[0009] [ka]

[0010] (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-. n represents the average number of repetitions and is represented by a real number.) and a halogen-containing polymer having at least one repeating unit represented by the following general formulas (2) to (6) at the polymer chain terminal:

[0011] [ka]

[0012] (In the formula, Y and Z represent halogen atoms, and m is a real number of 1 to 5.) A halogen-containing polymer having at least one terminal group selected from the group consisting of:

[0013] [2] The halogen-containing polymer according to [1], wherein the proportion of phenoxy terminal groups represented by general formula (2) among the terminal groups represented by general formulas (2) to (6) is 50 to 100%.

[0014] [3] The halogen-containing polymer according to [1], wherein the proportion of phenoxy terminal groups represented by general formula (2) among the terminal groups represented by general formulas (2) to (6) is 80 to 100%.

[0015] [4] The halogen-containing polymer according to any one of [1] to [3], wherein in general formula (1), R is an alkylene group having 1 to 6 carbon atoms.

[0016] [5] The halogen-containing polymer according to any one of [1] to [3], wherein in general formula (1), R is a 2,2-propylene group.

[0017] [6] The halogen-containing polymer according to any one of [1] to [5], wherein Y is a chlorine atom, Z is a bromine atom, and m is 2, 3, 4, or 5.

[0018] [7] The halogen-containing polymer according to any one of [1] to [6], characterized in that the weight-average molecular weight, measured by gel permeation chromatography and converted into standard polystyrene, is 1,000 to 8,000.

[0019] [8] The halogen-containing polymer according to any one of [1] to [6], characterized in that the weight-average molecular weight, measured by gel permeation chromatography and converted into standard polystyrene, is 1,000 to 6,000.

[0020] [9] The halogen-containing polymer according to any one of [1] to [6], characterized in that the weight-average molecular weight, measured by gel permeation chromatography and converted into standard polystyrene, is 1,000 to 4,000.

[0021]

[10] A method for producing a halogen-containing polymer according to [1], characterized in that a compound represented by the following general formula (7) is reacted with a compound represented by the following general formula (8) in the presence of a base, a radical trapping agent, and a solvent to synthesize a polymer, and then the polymer is reacted with a compound represented by the following general formula (9) in the presence of a base.

[0022] [ka]

[0023] (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-.)

[0024] [ka]

[0025] (In the formula, X and Y represent halogen atoms.)

[0026] [ka]

[0027] (In the formula, Z represents a halogen atom, and m represents a real number of 1 to 5.) [Effects of the Invention]

[0028] The halogen-containing polymer of the present invention is characterized by a higher halogen content than conventionally known halogen-containing polymers.

[0029] Furthermore, the polymer of the present invention has a high halogen content, and therefore exhibits the effect of being able to impart superior flame retardancy compared to conventionally known halogen-containing polymers. DETAILED DESCRIPTION OF THE INVENTION

[0030] The present invention will be described in more detail below. In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. Furthermore, unless specifically stated otherwise, the units of the numerical values ​​before and after "to" are the same.

[0031] One aspect of the present invention is a compound represented by the following general formula (1):

[0032] [ka]

[0033] (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-. n represents the average number of repetitions and is represented by a real number.) and a halogen-containing polymer having at least one repeating unit represented by the following general formulas (2) to (6) at the polymer chain terminal:

[0034] [ka]

[0035] (In the formula, Y and Z represent halogen atoms, and m is a real number of 1 to 5.) The present invention relates to a halogen-containing polymer having at least one terminal group selected from the group consisting of the following, and characterized in that it contains a phenoxy terminal group represented by general formula (2) among the terminal groups represented by general formulas (2) to (6).

[0036] The halogen atom represented by Y or Z is not particularly limited, but examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Furthermore, the halogen atom represented by Z may include multiple types of halogen atoms.

[0037] From the viewpoint of excellent heat resistance and flame retardancy, the above Y and Z are preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a chlorine atom or a bromine atom. Note that Y is more preferably a chlorine atom, and Z is more preferably a bromine atom.

[0038] In the above general formula (2), m is a real number of 1 to 5. From the viewpoint of excellent heat resistance and flame retardancy, m is preferably 2, 3, 4, or 5, more preferably 2, 3, or 4, and most preferably 3.

[0039] The phenoxy terminal group represented by the above general formula (2) is not particularly limited, but examples thereof include a 2-bromophenoxy group, a 3-bromophenoxy group, a 4-bromophenoxy group, a 2-iodophenoxy group, a 3-iodophenoxy group, a 4-iodophenoxy group, a 2,3-dichlorophenoxy group, a 2,3-dibromophenoxy group, a 2,3-diiodophenoxy group, a 2-chloro-3-bromophenoxy group, a 2-chloro-3-iodophenoxy group, a 2-bromo-3-chlorophenoxy group, a 2-bromo-3-iodophenoxy group, and a 2-iodo-3-chlorophenoxy group. phenoxy group, 2-iodo-3-bromophenoxy group, 2,4-dichlorophenoxy group, 2,4-dibromophenoxy group, 2,4-diiodophenoxy group, 2-chloro-4-bromophenoxy group, 2-chloro-4-iodophenoxy group, 2-bromo-4-chlorophenoxy group, 2-bromo-4-iodophenoxy group, 2-iodo-4-chlorophenoxy group, 2-iodo-4-bromophenoxy group, 2,5-dichlorophenoxy group, 2,5-dibromophenoxy group, 2,5-diiodophenoxy group, 2-chloro-5-bromophenoxy group, 2-chloro-5 -iodophenoxy group, 2-bromo-5-chlorophenoxy group, 2-bromo-5-iodophenoxy group, 2-iodo-5-chlorophenoxy group, 2-iodo-5-bromophenoxy group, 2,6-dichlorophenoxy group, 2,6-dibromophenoxy group, 2,6-diiodophenoxy group, 2-bromo-6-chlorophenoxy group, 2-chloro-6-iodophenoxy group, 2-bromo-6-iodophenoxy group, 3,4-dichlorophenoxy group, 3,4-dibromophenoxy group, 3,4-diiodophenoxy group, 3-chloro-4-bromophenoxy group, 3 -chloro-4-iodophenoxy group, 3-bromo-4-chlorophenoxy group, 3-bromo-4-iodophenoxy group, 3-iodo-4-chlorophenoxy group, 3-iodo-4-bromophenoxy group, 3,5-dichlorophenoxy group, 3,5-dibromophenoxy group, 3,5-diiodophenoxy group, 3-bromo-4-chlorophenoxy group, 3-chloro-5-iodophenoxy group, 3-bromo-5-iodophenoxy group, 2,3,4-trichlorophenoxy group, 2,3,4-tribromophenoxy group, 2,3-dichloro-4-bromophenoxy group, 2,3-dichloro-4-iodophenoxy group, 2,4-dichloro-3-bromophenoxy group, 2-chloro-3-iodo-4-bromophenoxy group, 2,3-dibromo-4-iodophenoxy group, 2-bromo-3,4-dichlorophenoxy group, 2,4-dibromo-3-chlorophenoxy group, 2-iodo-3,4-dichlorophenoxy group, 2-iodo-3-chloro-4-bromophenoxy group, 2-iodo-3-bromo-4-chlorophenoxy group, 2,3,5-trichlorophenoxy group, 2,3,5-tribromophenoxy group, 2,3,5-triiodophenoxy group , 2,5-dichloro-3-bromophenoxy group, 2-chloro-3,5-dibromophenoxy group, 2-bromo-3,5-dichlorophenoxy group, 2-iodo-3,5-dichlorophenoxy group, 2-iodo-3,5-dibromophenoxy group, 2-iodo-3-chloro-5-bromophenoxy group, 2-iodo-3-bromo-5-chlorophenoxy group, 2,3,6-trichlorophenoxy group, 2,3,6-tribromophenoxy group, 2,3-dichloro-6-bromophenoxy group, 2,6-dichloro-3-bromophenoxy group, 2,6-dichloro-3-iodophenoxy 2,6-dibromo-3-chlorophenoxy group, 2-bromo-3,6-dichlorophenoxy group, 2-bromo-3-chloro-6-iodophenoxy group, 2-iodo-3-chloro-6-bromophenoxy group, 2-iodo-3-bromo-6-chlorophenoxy group, 2,4,6-trichlorophenoxy group, 2,4,6-tribromophenoxy group, 2,4,6-triiodophenoxy group, 2,4-dichloro-6-bromophenoxy group, 2,4-dichloro-6-iodophenoxy group, 2,6-dichloro-4-bromophenoxy group, 2,6-dichloro-4-iodofenoxy group phenoxy group, 2-chloro-4,6-diiodophenoxy group, 2-chloro-4-bromo-6-iodophenoxy group, 2,4-dibromo-6-chlorophenoxy group, 2,4-dibromo-6-iodophenoxy group, 2,6-dibromo-4-chlorophenoxy group, 2,6-dibromo-4-iodophenoxy group, 2-bromo-4,6-diiodophenoxy group, 2-bromo-4-chloro-6-iodophenoxy group, 2-bromo-4-iodo-6-chlorophenoxy group, 2,6-diiodo-4-chlorophenoxy group, 2,6-diiodo-4-chlorophenoxy group, 3,4,5-trichlorophenoxy group, 3,4,5-tribromophenoxy group, 3,4,5-triiodophenoxy group, 3,4-dichloro-5-bromophenoxy group, 3,5-dichloro-4-bromophenoxy group, 3,5-dichloro-4-iodophenoxy group, 3,4-dibromo-5-chlorophenoxy group, 3,5-dibromo-4-chlorophenoxy group, 3,5-dibromo-4-iodophenoxy group, 3-bromo-4-iodo-5-chlorophenoxy group, 2,3,4,5-tetrachlorophenoxy group, 2,3,4,5-tetrabromophenoxy group, 2,3 ,4-trichloro-5-iodophenoxy group, 2,4-dibromo-3,5-dichlorophenoxy group, 2-bromo-3,4,5-trichlorophenoxy group, 2,3,4,6-tetrachlorophenoxy group, 2,3,4,6-tetrabromophenoxy group, 2,3,4-trichloro-6-bromophenoxy group, 2,3,6-trichloro-4-bromophenoxy group, 2,4,6-trichloro-3-bromophenoxy group, 2,3-dichloro-4,6-dibromophenoxy group, 2,4-dichloro-3,6-dibromophenoxy group, 2-chloro-3,4,6-tri Bromophenoxy group, 2,4,6-tribromo-3-chlorophenoxy group, 2,4,6-tribromo-3-iodophenoxy group, 2,4-dibromo-3,6-dichlorophenoxy group, 2,6-dichloro-3,4-dibromophenoxy group, 2-bromo-3,4,6-trichlorophenoxy group, 2,4,6-triiodo-3-chlorophenoxy group, 2,4,6-triiodo-3-bromophenoxy group, 2,6-diiodo-3-chloro-4-bromophenoxy group, 2-iodo-3,4,6-trichlorophenoxy group, 2,3,5,6-tetrachlorophenoxy group phenoxy group, 2,3,5,6-tetrabromophenoxy group, 2,3,5-trichloro-6-bromophenoxy group, 2,3,6-trichloro-5-bromophenoxy group, 2,3,5-tribromo-6-chlorophenoxy group, 2,3,6-tribromo-5-chlorophenoxy group, 2,5-dibromo-3,6-dichlorophenoxy group, 2,6-dibromo-3,5-dichlorophenoxy group, 2,5-dibromo-3,6-dichlorophenoxy group, 2,3,4,5,6-pentachlorophenoxy group, 2,3,4,5,6-pentabromophenoxy group, 2,4,5,Examples thereof include a 6-tetrachloro-3-bromophenoxy group, a 2,3,5,6-tetrachloro-4-bromophenoxy group, a 2,4,6-trichloro-3,5-dibromophenoxy group, a 2,3,4,6-tetrabromo-5-chlorophenoxy group, a 2,3,5-tribromo-4,6-dichlorophenoxy group, a 2,4,5-tribromo-3,6-dichlorophenoxy group, a 2,4,6-trichloro-3-chloro-5-iodophenoxy group, a 2,5-dibromo-3,4,6-trichlorophenoxy group, a 2,6-dibromo-3,4,5-trichlorophenoxy group, and a 2,4,6-triiodo-3-bromo-5-bromophenoxy group. Among these, 2,4,6-trichlorophenoxy group, 2,4,6-tribromophenoxy group, 2,4,6-triiodophenoxy group, 2,3,4,5,6-pentachlorophenoxy group, and 2,3,4,5,6-pentabromophenoxy group are preferred, as they can produce halogen-containing polymers with excellent flame retardancy.

[0040] A halogen-containing polymer according to one embodiment of the present invention is characterized in that it has at least one terminal group selected from the group consisting of the general formulas (2) to (6) at its polymer terminal, and that the terminal groups represented by the general formulas (2) to (6) include the phenoxy terminal group represented by the general formula (2). Based on these characteristics, when blended with a resin, it is possible to provide a halogen-containing polymer with unprecedented excellent flame retardancy.

[0041] The terminal groups represented by the general formulae (2) to (6) can be identified by NMR analysis, and the abundance ratios of the elements can be quantified by analyzing the abundance ratios calculated from the area ratios of the NMR charts.

[0042] In addition, the proportion of the terminal groups represented by general formula (2) is preferably 1 to 100%, more preferably 50 to 100%, and even more preferably 80 to 100%, based on the total of the terminal groups represented by general formulas (2) to (6) being 100%, in terms of excellent flame retardancy of the halogen-containing polymer.

[0043] In the general formula (1), R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-.

[0044] In general formula (1), the alkylene group having 1 to 6 carbon atoms represented by R is not particularly limited, but examples thereof include a methylene group, an ethylene group, a 2,2-propylene group, a 2,2-butylene group, a hexadiene group, and a 1,1-cyclohexylene group.

[0045] R is preferably an alkylene group having 1 to 6 carbon atoms, more preferably a 2,2-propylene group, in view of excellent heat resistance.

[0046] In the general formula (1), n ​​represents the average number of repeating units of the halogen-containing polymer, and in the present invention, n represents a real number.

[0047] The n is preferably a real number of 2 to 33, more preferably a real number of 3 to 19, and even more preferably a real number of 3 to 6, in terms of excellent heat resistance.

[0048] For example, when R is a 2,2-propylene group, the terminal structures are 2-chloroethyl groups and 2,4,6-tribromophenoxy groups, and n is 5, the theoretical average molecular weight of the halogen-containing polymer of the present invention is 3,243.

[0049] The halogen-containing polymer of the present invention preferably has a weight average molecular weight, calculated as standard polystyrene, of 1,000 to 8,000, more preferably 1,000 to 6,000, and even more preferably 1,000 to 4,000, as determined by gel permeation chromatography, in order to achieve a more excellent flame retardant effect.

[0050] The halogen-containing polymer of the present invention preferably has a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) in terms of standard polystyrene, measured by gel permeation chromatography, of 1.0 to 4.0. However, the smaller the Mw / Mn, the narrower the molecular weight distribution of the polymer, and the higher the flame retardancy and heat resistance of the polymer itself. Therefore, Mw / Mn is more preferably 1.0 to 3.0, and more preferably 1.0 to 2.0.

[0051] The method and conditions for measuring the molecular weight of the halogen-containing polymer of the present invention by gel permeation chromatography were in accordance with ISO 16014-3:2012 (JIS K 7252-3:2016), and the detailed conditions are as shown in the examples.

[0052] The halogen-containing polymer of the present invention preferably has a bromine content of 55 to 60% by weight, but from the viewpoint that the higher the bromine content, the more improved the flame retardancy of the flame retardant itself, so the bromine content is preferably 56 to 60% by weight.

[0053] The bromine content (wt%) of the halogen-containing polymer of the present invention can be determined by combustion-ion chromatography, although this is not particularly limited. Specific analytical methods and conditions for combustion-ion chromatography are described in IEC 62321-3-2. Detailed conditions are as shown in the examples.

[0054] The method for producing a halogen-containing polymer of the present invention is characterized by synthesizing a polymer by reacting a compound represented by the following general formula (7) with a compound represented by the following general formula (8) in the presence of a base, a radical trapping agent, and a solvent, and then reacting the polymer with a compound represented by the following general formula (9) in the presence of a base.

[0055] [ka]

[0056] (In the formula, R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-.)

[0057] [ka]

[0058] (In the formula, X and Y represent halogen atoms.)

[0059] [ka]

[0060] (In the formula, Z represents a halogen atom, and m represents a real number of 1 to 5.) In the above general formula (7), R represents an alkylene group having 1 to 6 carbon atoms, -S-, or -SO2-. The definition and preferred range of R in general formula (7) are the same as the definition and preferred range of R in general formula (1).

[0061] The compound represented by the general formula (7) is not particularly limited, but examples thereof include tetrabromobisphenol A, tetrabromobisphenol F, and bis(4'-hydroxy-3',5'-dibromophenyl)sulfone. Among these, tetrabromobisphenol A is preferred because it can give a halogen-containing polymer with excellent heat resistance.

[0062] In the above general formula (8), X and Y represent halogen atoms.

[0063] The halogen atom represented by X or Y is not particularly limited, but examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0064] The above X and Y are preferably a chlorine atom, a bromine atom, or an iodine atom, more preferably a chlorine atom or a bromine atom, and even more preferably a chlorine atom, in terms of excellent heat resistance and flame retardancy of the resulting polymer.

[0065] The compound represented by the general formula (8) is not particularly limited, but examples thereof include ethane dichloride, ethane dibromide, ethane diiodide, 1-bromo-2-chloroethane, 1-chloro-2-iodoethane, and 1-bromo-2-iodoethane.

[0066] In the above general formula (9), Z represents a halogen atom, and m represents a real number of 1 to 5.

[0067] The halogen atom represented by Z is not particularly limited, but examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0068] When the above m exceeds 1, it means that a plurality of halogen atoms represented by Z are bonded to the benzene ring represented by general formula (9). When a plurality of Z are bonded to one benzene ring in this way, the Z may be a single halogen atom or two or more types of halogen atoms. In other words, the halogen atom represented by Z may include a plurality of types of halogen atoms.

[0069] The above Z is preferably a chlorine atom, a bromine atom, or an iodine atom, and more preferably a bromine atom, in view of the excellent heat resistance and flame retardancy of the resulting polymer.

[0070] The compound represented by the above general formula (9) is not particularly limited, but examples thereof include 2-bromophenol, 3-bromophenol, 4-bromophenol, 2-iodophenol, 3-iodophenol, 4-iodophenol, 2,3-dichlorophenol, 2,3-dibromophenol, 2,3-diiodophenol, 2-chloro-3-bromophenol, 2-chloro-3-iodophenol, 2-bromo-3-chlorophenol, 2-bromo-3-iodophenol, 2-iodo-3-chlorophenol, and 2-iodo-3-bromophenol. phenol, 2,4-dichlorophenol, 2,4-dibromophenol, 2,4-diiodophenol, 2-chloro-4-bromophenol, 2-chloro-4-iodophenol, 2-bromo-4-chlorophenol, 2-bromo-4-iodophenol, 2-iodo-4-chlorophenol, 2-iodo-4-bromophenol, 2,5-dichlorophenol, 2,5-dibromophenol, 2,5-diiodophenol, 2-chloro-5-bromophenol, 2-chloro-5-iodophenol, 2-bromo-5-chlorophenol, 2-bromo-5 -Iodophenol, 2-iodo-5-chlorophenol, 2-iodo-5-bromophenol, 2,6-dichlorophenol, 2,6-dibromophenol, 2,6-diiodophenol, 2-bromo-6-chlorophenol, 2-chloro-6-iodophenol, 2-bromo-6-iodophenol, 3,4-dichlorophenol, 3,4-dibromophenol, 3,4-diiodophenol, 3-chloro-4-bromophenol, 3-chloro-4-iodophenol, 3-bromo-4-chlorophenol, 3-bromo-4-iodophenol , 3-iodo-4-chlorophenol, 3-iodo-4-bromophenol, 3,5-dichlorophenol, 3,5-dibromophenol, 3,5-diiodophenol, 3-bromo-4-chlorophenol, 3-chloro-5-iodophenol, 3-bromo-5-iodophenol, 2,3,4-trichlorophenol, 2,3,4-tribromophenol, 2,3-dichloro-4-bromophenol, 2,3-dichloro-4-iodophenol, 2,4-dichloro-3-bromophenol, 2-chloro-3-iodo-4-bromophenol, 2,3-Dibromo-4-iodophenol, 2-bromo-3,4-dichlorophenol, 2,4-dibromo-3-chlorophenol, 2-iodo-3,4-dichlorophenol, 2-iodo-3-chloro-4-bromophenol, 2-iodo-3-bromo-4-chlorophenol, 2,3,5-trichlorophenol, 2,3,5-tribromophenol, 2,3,5-triiodophenol, 2,5-dichloro-3-bromophenol, 2-chloro-3,5-dibromophenol, 2-bromo-3,5-dichlorophenol, 2-iodo-3,5-dichloro Phenol, 2-iodo-3,5-dibromophenol, 2-iodo-3-chloro-5-bromophenol, 2-iodo-3-bromo-5-chlorophenol, 2,3,6-trichlorophenol, 2,3,6-tribromophenol, 2,3-dichloro-6-bromophenol, 2,6-dichloro-3-bromophenol, 2,6-dichloro-3-iodophenol, 2,6-dibromo-3-chlorophenol, 2-bromo-3,6-dichlorophenol, 2-bromo-3-chloro-6-iodophenol, 2-iodo-3-chloro-6-bromophenol phenol, 2-iodo-3-bromo-6-chlorophenol, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,4,6-triiodophenol, 2,4-dichloro-6-bromophenol, 2,4-dichloro-6-iodophenol, 2,6-dichloro-4-bromophenol, 2,6-dichloro-4-iodophenol, 2-chloro-4,6-diiodophenol, 2-chloro-4-bromo-6-iodophenol, 2,4-dibromo-6-chlorophenol, 2,4-dibromo-6-iodophenol, 2,6-dibromo- 4-Chlorophenol, 2,6-dibromo-4-iodophenol, 2-bromo-4,6-diiodophenol, 2-bromo-4-chloro-6-iodophenol, 2-bromo-4-iodo-6-chlorophenol, 2,6-diiodo-4-chlorophenol, 2,6-diiodo-4-chlorophenol, 2,6-diiodo-4-chlorophenol, 3,4,5-trichlorophenol, 3,4,5-tribromophenol, 3,4,5-triiodophenol, 3,4-dichloro-5-bromophenol, 3,5-dichloro-4-bromophenol, 3,5-dichloro-4-iodophenol, 3,4-Dibromo-5-chlorophenol, 3,5-dibromo-4-chlorophenol, 3,5-dibromo-4-iodophenol, 3-bromo-4-iodo-5-chlorophenol, 2,3,4,5-tetrachlorophenol, 2,3,4,5-tetrabromophenol, 2,3,4-trichloro-5-iodophenol, 2,4-dibromo-3,5-dichlorophenol, 2-bromo-3,4,5-trichlorophenol, 2,3,4,6-tetrachlorophenol, 2,3,4,6-tetrabromophenol, 2,3,4-trichloro-6-bromophenol Bromophenol, 2,3,6-trichloro-4-bromophenol, 2,4,6-trichloro-3-bromophenol, 2,3-dichloro-4,6-dibromophenol, 2,4-dichloro-3,6-dibromophenol, 2-chloro-3,4,6-tribromophenol, 2,4,6-tribromo-3-chlorophenol, 2,4,6-tribromo-3-iodophenol, 2,4-dibromo-3,6-dichlorophenol, 2,6-dichloro-3,4-dibromophenol, 2-bromo-3,4,6-trichlorophenol, 2,4,6-tribromo-3-iodophenol, Iodo-3-chlorophenol, 2,4,6-triiodo-3-bromophenol, 2,6-diiodo-3-chloro-4-bromophenol, 2-iodo-3,4,6-trichlorophenol, 2,3,5,6-tetrachlorophenol, 2,3,5,6-tetrabromophenol, 2,3,5-trichloro-6-bromophenol, 2,3,6-trichloro-5-bromophenol, 2,3,5-tribromo-6-chlorophenol, 2,3,6-tribromo-5-chlorophenol, 2,5-dibromo-3,6-dichlorophenol, 2,6- Dibromo-3,5-dichlorophenol, 2,5-dibromo-3,6-dichlorophenol, 2,3,4,5,6-pentachlorophenol, 2,3,4,5,6-pentabromophenol, 2,4,5,6-tetrachloro-3-bromophenol, 2,3,5,6-tetrachloro-4-bromophenol, 2,4,6-trichloro-3,5-dibromophenol, 2,3,4,6-tetrabromo-5-chlorophenol, 2,3,5-tribromo-4,6-dichlorophenol, 2,4,5-tribromo-3,6-dichlorophenol, 2,4,Examples include 6-trichloro-3-chloro-5-iodophenol, 2,5-dibromo-3,4,6-trichlorophenol, 2,6-dibromo-3,4,5-trichlorophenol, and 2,4,6-triiodo-3-bromo-5-bromophenol. Among these, 2,4,6-trichlorophenol, 2,4,6-tribromophenol, 2,4,6-triiodophenol, 2,3,4,5,6-pentachlorophenol, and 2,3,4,5,6-pentabromophenol are preferred, as they can produce halogen-containing polymers with excellent flame retardancy.

[0071] In the method for producing a halogen-containing polymer of the present invention, the base is not particularly limited, and examples thereof include lithium hydroxide, potassium hydroxide, sodium hydroxide, cesium hydroxide, lithium hydrogen carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, cesium hydrogen carbonate, lithium carbonate, potassium carbonate, sodium carbonate, cesium carbonate, calcium hydroxide, strontium hydroxide, barium hydroxide, etc. Among these, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate is preferred, and potassium carbonate is more preferred, in that a halogen-containing polymer having excellent heat resistance can be obtained.

[0072] In the method for producing a halogen-containing polymer of the present invention, the solvent is not particularly limited as long as it does not react with the substrate, and examples thereof include aprotic polar solvents.

[0073] The solvent is not particularly limited, but examples thereof include tetrahydrofuran, dioxane, pyridine, N-methylpyrrolidone, propylene carbonate, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, etc. Among these, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, and dimethyl sulfoxide are preferred in that they can produce a halogen-containing polymer having excellent heat resistance.

[0074] The radical trapping agent is not particularly limited, but examples thereof include at least one radical trapping agent selected from the group consisting of phenol-based radical trapping agents, quinone-based radical trapping agents, phosphite-based radical trapping agents, amine-based radical trapping agents, and sulfur-based radical trapping agents. More specifically, examples of the phenol include, but are not limited to, 4-methoxyphenol, 6-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butylphenol, 2-tert-butyl-4-methoxyphenol, 4-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol (also known as dibutylhydroxytoluene), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 3,6-dihydroxybenzonorbornane, 2,2'-methylenebis(6-cyclohexyl-p-cresol), hydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 1,4-benzoquinone, 2-tert-butyl-1,4-benzoquinone, 4-tert-butylcatechol, phenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], diphenylamine, N,N-diethylhydroxylamine, ammonium nitrosophenylhydroxylamine, 2,2,6,6-tetramethylpiperidine-1-oxyl, 2-benzimidazolethiol, phenothiazine, didodecyl 3,3'-thiodipropionate, dioctadecyl 3,3'-thiodipropionate, triethyl phosphite, trihexyl phosphite, tris(1,1,1-hexafluoro-2-propyl) phosphite, triphenyl phosphite, tris(2-methylphenyl) phosphite, tris(4-methylphenyl) phosphite, tris(4-nonylphenyl) phosphite, pentaerythritol bis(2,4-di-tert-butylphenyl phosphite), and tris(2,4-di-tert-butylphenyl) phosphite.

[0075] In the method for producing a halogen-containing polymer of the present invention, the mixing ratio of the compound represented by the general formula (7) to the compound represented by the general formula (8) is preferably 0.8 to 2.0 molar parts, more preferably 1.3 to 1.9 molar parts, and even more preferably 1.5 to 1.8 molar parts, of the compound represented by the general formula (8) per 1 molar part of the compound represented by the general formula (7), in order to obtain a halogen-containing polymer having excellent flame retardancy.

[0076] In the method for producing a halogen-containing polymer of the present invention, the amount of base used when reacting the compound represented by the general formula (7) with the compound represented by the general formula (8) is preferably 0.8 to 2.5 molar parts, more preferably 0.9 to 2.0 molar parts, and even more preferably 1.0 to 1.8 molar parts, relative to 1 molar part of the compound represented by the general formula (7), in order to obtain a halogen-containing polymer having excellent flame retardancy.

[0077] In the method for producing a halogen-containing polymer of the present invention, the amount of the radical trapping agent used is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 8 parts by mass, and even more preferably 0.01 to 5 parts by mass, relative to 100 parts by mass of the compound represented by general formula (7), in that a halogen-containing polymer having excellent flame retardancy can be obtained.

[0078] In the method for producing a halogen-containing polymer of the present invention, the amount of the solvent used is preferably 200 to 2,000 parts by mass, more preferably 250 to 1,000 parts by mass, and even more preferably 250 to 500 parts by mass, relative to 100 parts by mass of the compound represented by general formula (7), in that a halogen-containing polymer having excellent flame retardancy can be obtained.

[0079] In the method for producing a halogen-containing polymer of the present invention, the amount of the compound represented by the general formula (9) used is preferably 0.3 to 1.5 parts by mole, more preferably 0.4 to 1.4 parts by mole, and even more preferably 0.4 to 1.3 parts by mole, per part by mole of the compound represented by the general formula (7), in order to obtain a halogen-containing polymer having excellent flame retardancy.

[0080] In the method for producing a halogen-containing polymer of the present invention, the amount of base used when reacting the polymer, which is a reaction product of the compound represented by the general formula (7) and the compound represented by the general formula (8), with the compound represented by the general formula (9) is preferably 0.8 to 2.5 molar parts, more preferably 0.9 to 2.0 molar parts, and even more preferably 1.0 to 1.8 molar parts, relative to 1 molar part of the compound represented by the general formula (9), in order to obtain a halogen-containing polymer having excellent flame retardancy.

[0081] In the method for producing a halogen-containing polymer of the present invention, the reaction temperature is preferably in the range of 110 to 150°C, more preferably in the range of 120 to 145°C.

[0082] An example of the method for producing the halogen-containing polymer of the present invention is a method in which a mixture containing a compound represented by the general formula (7), a compound represented by the general formula (8), a base, a radical trapping agent, and a solvent is heated at a temperature in the range of 110 to 150°C while stirring (a polymer is obtained at this stage), and then a compound represented by the general formula (9) and a base are further added, and the mixture is heated at a temperature in the range of 110 to 150°C while stirring.

[0083] The method for producing the halogen-containing polymer of the present invention may be carried out as a one-pot reaction, or may be carried out in two stages by isolating the polymer, which is a reaction intermediate product.

[0084] The halogen-containing polymer of the present invention can impart flame retardancy to a resin by blending it with the resin.

[0085] The resin is not particularly limited, but examples thereof include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyvinyl vinyl acetate, polyurethane, acrylonitrile butadiene styrene resin, acrylic resin, phenolic resin, epoxy resin, melamine resin, urea resin, polyester resin, alkyd resin, polyurea, polyimide, polyamide, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyethersulfone, polyetheretherketone, and polyamideimide.

[0086] The amount of the halogen-containing polymer of the present invention mixed with the resin is preferably 5 to 30 parts by mass, more preferably 10 to 28 parts by mass, and even more preferably 12 to 25 parts by mass, per 100 parts by mass of the resin, in order to impart high flame retardancy.

[0087] Furthermore, the halogen-containing polymer of the present invention can impart flame retardancy to fibers by impregnating the fibers with the polymer.

[0088] The fibers are not particularly limited, but examples thereof include polyethylene, polypropylene, polyvinyl chloride, acrylic, modacrylic, acrylate, acetate, rayon, melamine, polyurethane, polyimide, polyamide, polyacetal, polyester, polylactic acid, polyarylate, polyphenylene sulfide, and polyether ester.

[0089] As a method for impregnating fibers with the halogen-containing polymer of the present invention, a method in which the flame retardant is dispersed in water or the like, fibers are immersed in the liquid, and then heated and dried to adhere the flame retardant to the fibers. [Example]

[0090] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples at all. <Measurement of weight average molecular weight> Regarding the halogen-containing polymer synthesized in Examples and the like, a molecular weight measurement column (TSKgel (registered trademark) SuperH1000 + 2000 + 3000 + 5000, manufactured by Tosoh Corporation) was connected to a gel permeation chromatography apparatus (HLC-8320GPC, manufactured by Tosoh Corporation), and measurement was performed under the detection conditions of a flow rate of 0.6 mL / min, a temperature of 40 °C, and UV (254 nm) using a tetrahydrofuran eluent. Further, using standard polystyrene, the weight average molecular weight of the sample in terms of standard polystyrene was measured. Other matters were carried out in accordance with JIS-K-7252. <Quantification of bromine content> Analysis method: Combustion-ion chromatography -Combustion conditions- Measuring device: AQF-2100H manufactured by Mitsubishi Chemical Analytech Co., Ltd. Sample amount: 4 mg Combustion temperature: Inlet side 900 °C, outlet side 1000 °C Absorbent composition: 30 mg / L hydrogen peroxide solution Absorbent amount: 30 mL -IC conditions- Measuring device: IC-2010 manufactured by Tosoh Corporation Analysis column: TSKgel SuperIC-Anion HS Guard column: TSKguardcolumn SuperIC-A HS Eluent: 7.5 mmol / L aqueous sodium hydrogen carbonate solution + 0.8 mmol / L aqueous sodium carbonate solution Flow rate: 1.5 mL / min Column temperature: 40 °C Injection volume: 30 μL Suppressor gel: TSKgel suppress IC-A Detection: Electrical conductivity <Ratio analysis of polymer terminal structure by NMR> ·Device: JNM-EC 400YH manufactured by JEOL Ltd. Probe: 5 mmφ OPTIMA Solvent: 1,1,2,2-tetrachloroethane-d2 Sample concentration: approximately 10% (w / v) · 1 H NMR (400 MHz), number of accumulations: 32 The polymer samples synthesized in the examples were measured by 1H NMR under the above measurement conditions, and the terminal structures were analyzed from the average integral values ​​of each peak. <Synthesis of halogen-containing polymers> Example 1 A 5 L cylindrical glass separable flask equipped with a stirrer and a reflux condenser was charged with 800.0 g (1.471 mol) of tetrabromobisphenol A, 254.1 g (1.839 mol) of potassium carbonate, 4.00 g (26.6 mmol) of 4-tert-butylphenol, 4.01 g (6.19 mmol) of tris(2,4-di-tert-butylphenyl)phosphite, and 2100 g of dimethylformamide, and the mixture was heated to 130°C with stirring. At this temperature, 218.3 g (2.207 mol) of ethane dichloride was added, and the mixture was stirred at 130°C for another 4 hours and then allowed to cool to room temperature. Next, 486.6 g (1.471 mol) of 2,4,6-tribromophenol and 203.3 g (1.471 mol) of potassium carbonate were added to the reaction solution, and the mixture was stirred at 130°C for 24 hours and then allowed to cool to room temperature. Methanol was added to the reaction solution to precipitate a solid. The precipitated solid was filtered, washed with water, and then dried at 110°C using a tray dryer. A white solid halogen-containing polymer (A) was obtained in a yield of 63%.

[0091] The resulting halogen-containing polymer (A) had a weight-average molecular weight of 5,000 and a bromine content of 56.5% by weight.

[0092] Furthermore, as a result of analyzing the ratio of the polymer terminal structure by NMR, the ratio of the phenoxy terminal group represented by the above general formula (2) in the halogen-containing polymer of this example was 65.4%, with the total of the terminal groups represented by the general formulas (2) to (6) being 100%.

[0093] Example 2 The same procedure as in Example 1 was carried out, except that 232.9 g (2.354 mol) of dichloroethane was used instead of 218.3 g (2.207 mol) of dichloroethane in Example 1, to obtain a white solid halogen-containing polymer (B) in a yield of 59%. The evaluation results of the obtained halogen-containing polymer (B) are shown in Table 1.

[0094] Example 3 The same procedure as in Example 1 was carried out, except that 240.2 g (2.427 mol) of dichloroethane was used instead of 218.3 g (2.207 mol) of dichloroethane in Example 1, to obtain a white solid halogen-containing polymer (C) in a yield of 59%. The evaluation results of the obtained halogen-containing polymer (C) are shown in Table 1.

[0095] Comparative Example 1 A halogen-containing polymer (D) was synthesized according to the method of Example 14 described in JP 2019-77857 A. The analytical results of the obtained halogen-containing polymer (D) are shown in Table 1.

[0096] [Table 1]

[0097] The results shown in Table 1 show that the halogen-containing polymer of the present invention has a higher halogen content than conventional halogen-containing polymers, and is therefore expected to impart excellent flame retardancy when blended into resins.

Claims

1. The following general formula (1) 【Chemistry 1】 (wherein R represents an alkylene group having 1 to 6 carbon atoms, —S—, or —SO ２ -. n represents the average number of repetitions and is expressed as a real number.) and a halogen-containing polymer having at least one repeating unit represented by the following general formulas (2) to (6) at the polymer chain terminal: 【Chemistry 2】 (In the formula, Y and Z represent halogen atoms, and m is a real number of 1 to 5.) and wherein the halogen-containing polymer has at least one terminal group selected from the group consisting of:

2. 2. The halogen-containing polymer according to claim 1, wherein the proportion of phenoxy terminal groups represented by general formula (2) among the terminal groups represented by general formulas (2) to (6) is 50 to 100%.

3. 2. The halogen-containing polymer according to claim 1, wherein the proportion of phenoxy terminal groups represented by general formula (2) among the terminal groups represented by general formulas (2) to (6) is 80 to 100%.

4. 4. The halogen-containing polymer according to claim 1, wherein in general formula (1), R is an alkylene group having 1 to 6 carbon atoms.

5. 4. The halogen-containing polymer according to claim 1, wherein in general formula (1), R is a 2,2-propylene group.

6. 4. The halogen-containing polymer of claim 1, wherein Y is a chlorine atom, Z is a bromine atom, and m is 2, 3, 4, or 5.

7. 4. The halogen-containing polymer according to claim 1, wherein the weight average molecular weight, measured by gel permeation chromatography in terms of standard polystyrene, is 1,000 to 8,000.

8. 4. The halogen-containing polymer according to claim 1, wherein the weight-average molecular weight, measured by gel permeation chromatography in terms of standard polystyrene, is 1,000 to 6,000.

9. 4. The halogen-containing polymer according to claim 1, wherein the weight average molecular weight, measured by gel permeation chromatography in terms of standard polystyrene, is 1,000 to 4,000.

10. 2. A method for producing a halogen-containing polymer according to claim 1, characterized in that a compound represented by the following general formula (7) and a compound represented by the following general formula (8) are reacted in the presence of a base, a radical trapping agent, and a solvent to synthesize a polymer, and then the polymer is reacted with a compound represented by the following general formula (9) in the presence of a base: 【Transformation 3】 (wherein R represents an alkylene group having 1 to 6 carbon atoms, —S—, or —SO ２ - indicates.) 【Chemistry 4】 (In the formula, X and Y represent halogen atoms.) 【Transformation 5】 (In the formula, Z is a halogen atom, and m is a real number from 1 to 5.)

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