Chlorine-based polymer

Abstract

Provided is a chlorine-based polymer excellent in thermal stability. The chlorine-based polymer has repeating structural units represented by chemical formula (I). In the formula, each of l, m, and n is a positive number. The order of repeating structural units, which are indicated by l, m, and n, is not limited. The bonding mode may be alternate, block, or random. R1 is an oxygen atom or a nitrogen atom. If R1 is an oxygen atom, R2 is an alkyl group, an aryl group or a heterocyclic group, where any of these groups optionally has a substituent. If R1 is a nitrogen atom, R2 is composed of the same or different two functional groups bonded to the nitrogen atom, where the functional groups are each a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, or R2 is a heterocyclic group containing R1, and these groups may each have a substituent.

Description

Chlorine-based polymers

[0001] This invention relates to a chlorine-based polymer which is a chlorosulfonated polyolefin derivative with excellent heat resistance.

[0002] As chlorosulfonated polyolefins, chlorosulfonated polyethylene (CSM) and alkylated chlorosulfonated polyethylene (ACSM) are commercially available and, due to their excellent mechanical properties, abrasion resistance, chemical resistance, and weather resistance, are used as the main component of adhesive layers in laminates (Patent Document 1) or as a material for rubber-like elastic bodies (Patent Document 2).

[0003] Japanese Patent Publication No. 2024-097662 Japanese Patent Publication No. 2024-052302

[0004] Chlorosulfonated polyolefins tend to generate acidic gases when heated, raising concerns about reduced workability and equipment corrosion. Therefore, there is a need to reduce the amount of acidic gases generated during thermal decomposition, in other words, to improve heat resistance.

[0005] The present invention is a chlorine-based polymer characterized by having a repeating structural unit represented by the following chemical formula (I).

[0006]

[0007] In the above chemical formula (I), l, m, and n are all positive numbers, the order of each repeating structural unit represented by l, m, and n is not limited, and the bonding pattern may be alternating, block-like, or random. １ R is an oxygen atom or a nitrogen atom. １ When R is an oxygen atom, ２ R is an alkyl group, an aryl group, or a heterocyclic group, and these groups may have substituents. １ When R is a nitrogen atom, ２ It consists of two identical or distinct functional groups bonded to a nitrogen atom, each functional group being a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these groups may have substituents. Or, R １ When R is a nitrogen atom, ２ is R １It is a heterocyclic group containing, and this heterocyclic group may have a substituent.

[0008] The chlorine-based polymer can be composed of a repeating structural unit represented by the following chemical formula (II) or the following chemical formula (III).

[0009]

[0010] In the above chemical formula (II), R ３ is an alkyl group, an aryl group, a pyridyl group, a quinolyl group or an isoquinolyl group, and these groups may have a substituent. In the above chemical formula (III), R ４ , R ５ are the same or different functional groups, which are a hydrogen atom or an alkyl group, and these groups may have a substituent, and R ４ and R ５ may have a ring structure in which they are bonded to each other. Here, each of l, m, and n is a positive number, and the order of each repeating structural unit represented by l, m, and n is not limited, and the bonding mode may be alternating, block, or random.

[0011] The chlorine-based polymer can be composed of a repeating structural unit represented by the following chemical formula (IV), (V), (VI), (VII) or the following chemical formula (VIII). Here, similar to the above chemical formula (I), each of l, m, and n is a positive number, and the order of each repeating structural unit represented by l, m, and n is not limited, and the bonding mode may be alternating, block, or random.

[0012]

[0013] According to the present invention, a chlorine-based polymer having better heat resistance than chlorosulfonated polyolefin can be provided.

[0014] It is a diagram showing the results of thermogravimetric analysis. It is a diagram showing the behavior of weight loss in a part of the temperature range shown in FIG. 1. It is a diagram showing the residual rate of sulfur contained in the chlorine-based polymer.

[0015] (Chlorine-based polymer) The chlorine-based polymer of this embodiment has a repeating structural unit represented by the following chemical formula (1).

[0016]

[0017] In the above chemical formula (1), l, m, and n are positive numbers, and can be appropriately determined according to the uses of the chlorine-based polymer, etc. The order of each repeating structural unit represented by l, m, and n is not limited, and the bonding mode may be alternating, block, or random. Here, in the chlorine-based polymer, the chlorine content can be 20 to 50% by mass, and the sulfur content can be 0.1 to 3.0% by mass.

[0018] In the above chemical formula (1), R １ is an oxygen atom or a nitrogen atom. When R １ is an oxygen atom, R ２ is an alkyl group, an aryl group, or a heterocyclic group, and these groups may have substituents. Examples of the alkyl group include linear, branched, and cyclic alkyl groups having 1 to 18 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, etc. Examples of the heterocyclic group include a pyridyl group, a quinolyl group, an isoquinolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a furanyl group, a pyrrolidyl group, a thienyl group, a piperazinyl group, a piperidyl group, a morpholyl group, etc.

[0019] On the other hand, when R １ is a nitrogen atom, R ２ are two identical or different functional groups bonded to the nitrogen atom. Each functional group R ２ is a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these groups may have substituents. Examples of the alkyl group include linear, branched, and cyclic alkyl groups having 1 to 18 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, etc. Examples of the heterocyclic group include a pyridyl group, a quinolyl group, an isoquinolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a furanyl group, a pyrrolidyl group, a thienyl group, a piperazinyl group, a piperidyl group, a morpholyl group, etc. Also, when R １ is a nitrogen atom, the functional groups R １ and R ２ are a heterocyclic ring (R２ is R １ (which may form a heterocyclic group containing R), and examples of the heterocyclic ring include a pyrrolidyl group, a piperazinyl group, a piperidyl group, a morpholyl group, etc. These groups may have substituents.

[0020] When the above-mentioned substituents may be present, the substituents are not particularly limited. For example, an alkyl group, an amino group, an aminoalkyl group, a carboxy group, a carboxyalkyl group, an acyl group, a hydroxyl group, an alkoxy group, an aryl group, an aryloxy group, a nitro group, a nitrile group, a heterocyclic group, a halogen atom, etc. may be mentioned.

[0021] Specific examples of the chlorine-based polymer include a chlorine-based polymer having a repeating structural unit represented by the following chemical formula (2) or chemical formula (3).

[0022]

[0023] In the above chemical formula (2), R ３ is an alkyl group, an aryl group, a pyridyl group, a quinolyl group or an isoquinolyl group, and these groups may have substituents. In the above chemical formula (3), R ４ , R ５ are the same or different functional groups, which are a hydrogen atom or an alkyl group, and these groups may have substituents. Also, R ４ and R ５ may have a ring structure in which they are bonded to each other. Note that each of l, m, and n is a positive number, and the order of each repeating structural unit represented by l, m, and n is not limited, and the bonding mode may be alternating, block, or random.

[0024] In the above chemical formula (2) or (3), when the substituents may be present, the substituents are not particularly limited. For example, an alkyl group, an amino group, an aminoalkyl group, a carboxy group, a carboxyalkyl group, an acyl group, a hydroxyl group, an alkoxy group, an aryl group, an aryloxy group, a nitro group, a nitrile group, a heterocyclic group, a halogen atom, etc. may be mentioned.

[0025] More specifically, chlorine-based polymers include chlorine-based polymers having repeating structural units represented by the following chemical formulas (4), (5), (6), (7), or (8). In the following chemical formulas (4), (5), (6), (7), or (8), l, m, and n are all positive numbers, the order of the repeating structural units represented by l, m, and n is not limited, and the bonding pattern may be alternating, block-like, or random.

[0026]

[0027] (Method for producing chlorine-based polymers) Chlorine-based polymers are produced by chlorosulfonated polyethylene (hereinafter referred to as CSM) containing SO ２ The chlorine atom of the Cl group is R １ R ２ It is obtained by modifying the base. CSM is produced by dissolving or suspending polyolefin in a solvent, followed by chlorination and chlorosulfonation.

[0028] The reagent used for modifying CSM is R shown in the above chemical formula (1). １ R ２ It includes SO2, which is included in CSM. ２ The chlorine atom of the Cl group is R １ R ２ Anything that can be substituted for it is acceptable.

[0029] R shown in the above chemical formula (1) １ When is an oxygen atom, the reactant is R ２ Alcohols and phenols represented by OH, or R ２ Alkoxides and phenoxides represented by OM can be used. Here, R ２The M in OM is a metal atom such as a sodium atom or a potassium atom. Specifically, these include sodium methoxide, sodium ethoxide, sodium phenoxide, potassium methoxide, potassium ethoxide, and potassium phenoxide. When producing a chlorine-based polymer having the repeating structural unit represented by the above chemical formula (6), ethanol (alcohols) can be used as a reactant. When producing a chlorine-based polymer having the repeating structural unit represented by the above chemical formula (4), 3-hydroxypyridine can be used as a reactant. When producing a chlorine-based polymer having the repeating structural unit represented by the above chemical formula (7), p-ethylphenol (phenols) can be used as a reactant.

[0030] R shown in the above chemical formula (1) １ When is a nitrogen atom, the reactants include amines (NHR) such as primary or secondary aliphatic amines, heterocyclic amines, and aromatic amines. ２ ) can be used. When producing a chlorine-based polymer having a repeating structural unit represented by the above chemical formula (5), 1-methylpiperazine (heterocyclic amine) can be used as a reactant, and when producing a chlorine-based polymer having a repeating structural unit represented by the above chemical formula (8), furfurylamine (aliphatic amine) can be used as a reactant.

[0031] The solvent used for the modification of CSM can be any solvent that dissolves the CSM without inhibiting the progress of the modification reaction. Examples of such solvents include aromatic hydrocarbon compounds (benzene, toluene, xylene, etc.), chlorine compounds (dichloromethane, chloroform, 1,1,2-trichloroethane, trichloroethylene, tetrachloroethylene, etc.), ether compounds (tetrahydrofuran, 1,4-dioxane, etc.), ester compounds (ethyl acetate, butyl acetate, etc.), and ketone compounds (methyl ethyl ketone, methyl isobutyl ketone, etc.).

[0032] When denaturing CSM, it is preferable to capture the acid generated in the denaturation reaction. Examples of such capture agents include inorganic salts (sodium carbonate, potassium carbonate, magnesium oxide, etc.) and organic bases (triethylamine, pyridine, etc.).

[0033] The reaction conditions (reaction temperature, reaction pressure, reaction time) for the denaturation of CSM can be set as appropriate, but for example, the reaction conditions can be set as follows: Reaction temperature: 0°C to 140°C Reaction pressure: atmospheric pressure to 1 MPa Reaction time: 1 to 24 hours

[0034] On the other hand, CSM can also be modified without using a solvent. Specifically, CSM and the reactant can be mixed using a kneader. Heating can be performed during mixing as needed.

[0035] The present invention will be specifically described by the following embodiments. However, the present invention is not limited to these embodiments.

[0036] (Example 1) A chlorine-based polymer having a repeating structural unit represented by the above chemical formula (4) was prepared. Specifically, 25 g of CSM (product name "TOSO-CSM TS-530", manufactured by Tosoh Corporation) and 332 g of toluene were added to a flask (volume: 1 L) and dissolved. Next, 2.9 g of 3-hydroxypyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask and stirred under reflux conditions for 6 hours.

[0037] Next, the solution in the flask was cooled to room temperature, and then the solution was added dropwise to methanol to obtain a precipitate. The obtained precipitate was washed with acetone, and the solvent was removed by vacuum drying to obtain a chlorine-based polymer having repeating structural units represented by the above chemical formula (4). Elemental analysis of this chlorine-based polymer revealed that the nitrogen content was 0.4% by mass, the chlorine content was 34% by mass, and the sulfur content was 0.9% by mass.

[0038] (Example 2) A chlorine-based polymer having a repeating structural unit represented by the above chemical formula (5) was prepared. Specifically, 25 g of CSM (product name "TOSO-CSM TS-530", manufactured by Tosoh Corporation) and 192 g of toluene were added to a flask (volume: 1 L) and dissolved. Next, 6.2 g of 1-methylpiperazine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the flask and stirred at 80°C for 3.5 hours.

[0039] Next, the solution in the flask was cooled to room temperature, and then the solution was added dropwise to methanol to obtain a precipitate. The obtained precipitate was washed with acetone, and the solvent was removed by vacuum drying to obtain a chlorine-based polymer having repeating structural units represented by the above chemical formula (5). Elemental analysis of this chlorine-based polymer revealed that the nitrogen content was 0.9% by mass, the chlorine content was 34% by mass, and the sulfur content was 1.0% by mass.

[0040] (Example 3) A chlorine-based polymer having a repeating structural unit represented by the above chemical formula (6) was prepared. Specifically, 1 g of CSM (product name "TOSO-CSM TS-530", manufactured by Tosoh Corporation) and 9 g of toluene were added to a flask (volume: 0.1 L) and dissolved. Next, 0.72 g of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.30 g of N-ethyldiisopropylamine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to the flask, and the mixture was stirred at 60°C for 4 hours.

[0041] Next, the solution in the flask was cooled to room temperature, and then the solution was added dropwise to methanol to obtain a precipitate. The obtained precipitate was washed with acetone, and the solvent was removed by vacuum drying to obtain a chlorine-based polymer having repeating structural units represented by the above chemical formula (6). Elemental analysis of this chlorine-based polymer revealed that the chlorine content was 34% by mass and the sulfur content was 1.0% by mass.

[0042] (Example 4) A chlorine-based polymer having a repeating structural unit represented by the above chemical formula (7) was prepared. Specifically, 1 g of CSM (product name "TOSO-CSM TS-530", manufactured by Tosoh Corporation) and 9 g of tetrahydrofuran were added to a flask (volume: 0.1 L) and dissolved. Next, 0.57 g of p-ethylphenol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.32 g of potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to the flask, and the mixture was stirred at 50°C for 8 hours.

[0043] Next, the solution in the flask was cooled to room temperature, and then the solution was added dropwise to water to obtain a precipitate. The obtained precipitate was washed with methanol and acetone, and the solvent was removed by vacuum drying to obtain a chlorine-based polymer having repeating structural units represented by the above chemical formula (7). Elemental analysis of this chlorine-based polymer revealed that the chlorine content was 34% by mass and the sulfur content was 1.0% by mass.

[0044] (Example 5) A chlorine-based polymer having a repeating structural unit represented by the above chemical formula (8) was prepared. Specifically, 1 g of CSM (product name "TOSO-CSM TS-530", manufactured by Tosoh Corporation) and 9 g of toluene were added to a flask (volume: 0.1 L) and dissolved. Next, 0.23 g of furfurylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the flask and stirred at room temperature for 24 hours.

[0045] Next, the solution in the flask was cooled to room temperature, and then the solution was added dropwise to methanol to obtain a precipitate. The obtained precipitate was washed with acetone, and the solvent was removed by vacuum drying to obtain a chlorine-based polymer having repeating structural units represented by the above chemical formula (8). Elemental analysis of this chlorine-based polymer revealed that the nitrogen content was 0.4% by mass, the chlorine content was 34% by mass, and the sulfur content was 0.9% by mass.

[0046] (Comparative Example) As a comparative example, CSM (product name "TOSO-CSM TS-530", manufactured by Tosoh Corporation) was used.

[0047] (Measurement of acid gas generation) Examples 1, 2, 3, 4, 5 and the comparative example, which are chlorine-based polymers, were heated to generate acid gas (HCl and SO₂). ２ The amount of Cl generated was measured. Specifically, 0.1 g of chlorine polymer was placed in a test tube set up in an oven, sealed, and heated at 160°C for 30 minutes under a helium stream. The generated gas was collected by passing it through 1% hydrogen peroxide solution cooled with ice, and then measured using an ion chromatograph IC-2010 (manufactured by Tosoh Corporation). － SO ４ ２－ The quantified values ​​were obtained as HCl and SO2. ２ The values ​​were converted to [value]. For each chlorine-based polymer, the amount of each acidic gas generated was measured twice, and the average of these amounts was calculated. The measurement results are shown in Table 1 below.

[0048]

[0049] In Table 1 above, each acidic gas (HCl and SO) ２ The amount of generated ) is the amount of acidic gas generated per gram of chlorine-based polymer [μg], and the relative generation rate is the ratio of the amount of generated Mpe of each acidic gas in each of Examples 1 to 5 when the amount of generated Mce of each acidic gas in the comparative example is set to 100% (ratio = 100 × Mpe / Mce).

[0050] As can be seen from Table 1 above, in Examples 1, 2, 3, 4, and 5, the amount of acidic gas generated was significantly reduced compared to the comparative example (CSM). From this, it was found that in Examples 1, 2, 3, 4, and 5, the thermal decomposition that generates acidic gas was suppressed, and the thermal stability was excellent.

[0051] (Measurement of weight loss of chlorine-based polymers) Thermogravimetric analysis (TGA: Thermogravimetric Analysis, SDT Q600 (manufactured by T.A. Instruments Japan Co., Ltd.)) was performed on the chlorine-based polymers of Examples 1 and 2 and the comparative example in accordance with the provisions of JIS K7120 (1987). The analysis results under a nitrogen atmosphere are shown in Figures 1 and 2. In Figures 1 and 2, the horizontal axis is temperature [°C] and the vertical axis is the weight [mass%] of the chlorine-based polymer. Figure 2 is an enlarged view of the weight loss behavior in the temperature range of 180 to 320°C in Figure 1.

[0052] As can be seen from Figure 2, in the comparative example (CSM), the weight began to decrease from 180°C, whereas in Example 1, no weight loss occurred until 220°C, and in Example 2, no weight loss occurred until 240°C. Thus, in Examples 1 and 2, the temperature at which weight loss began was higher than in the comparative example (CSM), indicating superior thermal stability.

[0053] (Measurement of Sulfur Content) The chlorine-based polymers of Examples 1 and 2 and the Comparative Example were heated at 160°C, and the sulfur content (residual rate) contained in the chlorine-based polymers was measured in accordance with the provisions of JIS K6222 (1998). Specifically, the chlorine-based polymers were burned in a combustion flask, absorbed into hydrogen peroxide solution, and then a solution of acetic acid, Arsenazo III indicator, and isopropanol was prepared. The sulfur content was measured using an automatic titrator COM-A19 (manufactured by HIRANUMA Corporation). The measurement results are shown in Figure 3. In Figure 3, the horizontal axis represents the heating time [h], and the vertical axis represents the residual sulfur rate [mass%].

[0054] In measuring the residual rate, the sulfur content MS1 in the chlorine-based polymer was first measured, and then the sulfur content MS2 was measured when the heating time was 3 [h] and 6 [h]. The residual rate was calculated based on "(MS2 / MS1) × 100". By focusing on the residual rate, the thermal stability of the chlorine-based polymer can be evaluated.

[0055] As shown in Figure 3, in the comparative example (CSM), the residual sulfur rate decreased significantly as the heating time increased. In Example 1, although the residual sulfur rate decreased with the passage of heating time, it showed a higher residual rate than the comparative example (CSM). In Example 2, the residual sulfur rate hardly decreased regardless of the heating time. This indicates that Examples 1 and 2 have superior thermal stability compared to the comparative example (CSM).

Claims

1. A chlorine-based polymer characterized by having repeating structural units represented by the following chemical formula (I). In equation (I), l, m, and n are all positive numbers, the order of each repeating structural unit represented by l, m, and n is not limited, and the mode of combination may be alternating, block, or random. １ is an oxygen atom or a nitrogen atom, R １ When is an oxygen atom, R ２ R is an alkyl group, an aryl group, or a heterocyclic group, and these groups may have substituents. １ When is a nitrogen atom, R ２ It consists of two identical or different functional groups bonded to a nitrogen atom, and each functional group is either a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, or R ２ is R １ These are heterocyclic groups containing these groups, and these groups may have substituents.

2. The chlorine-based polymer according to claim 1, characterized in that the chlorine-based polymer has a repeating structural unit represented by the following chemical formula (II). In equation (II), l, m, and n are all positive numbers, the order of each repeating structural unit represented by l, m, and n is not limited, and the mode of combination may be alternating, block, or random. ３ These are alkyl groups, aryl groups, pyridyl groups, quinolyl groups, or isoquinolyl groups, and these groups may have substituents.

3. The chlorine-based polymer according to claim 1, characterized in that it has a repeating structural unit represented by the following chemical formula (III). In formula (III), each of l, m, and n is a positive number, and the order of each repeating structural unit represented by l, m, and n is not limited. The bonding mode may be alternating, block, or random. ４ R ５ and R ４ are the same or different functional groups, which are a hydrogen atom or an alkyl group, and these groups may have substituents. R ５ and R may have a ring structure bonded to each other.

4. The chlorine-based polymer according to claim 2, characterized in that the chlorine-based polymer has a repeating structural unit represented by the following chemical formula (IV). In formula (IV), l, m, and n are all positive numbers, the order of each repeating structural unit represented by l, m, and n is not limited, and the mode of combination may be alternating, block-like, or random.

5. The chlorine-based polymer according to claim 3, characterized in that the chlorine-based polymer has a repeating structural unit represented by the following chemical formula (V). In equation (V), l, m, and n are all positive numbers, the order of each repeating structural unit represented by l, m, and n is not limited, and the combination pattern may be alternating, block-like, or random.

6. The chlorine-based polymer according to claim 2, characterized in that the chlorine-based polymer has a repeating structural unit represented by the following chemical formula (VI). In formula (VI), l, m, and n are all positive numbers, the order of each repeating structural unit represented by l, m, and n is not limited, and the joining pattern may be alternating, block-like, or random.

7. The chlorine-based polymer according to claim 2, characterized in that the chlorine-based polymer has a repeating structural unit represented by the following chemical formula (VII). In equation (VII), l, m, and n are all positive numbers, the order of each repeating structural unit represented by l, m, and n is not limited, and the mode of combination may be alternating, block-like, or random.

8. The chlorine-based polymer according to claim 3, characterized in that the chlorine-based polymer has a repeating structural unit represented by the following chemical formula (VII). In equation (VIII), l, m, and n are all positive numbers, the order of the repeating structural units represented by l, m, and n is not limited, and the combination can be alternating, block-like, or random.

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