Biomass-derived chlorosulfonated polyethylene

Abstract

Provided is chlorosulfonated polyethylene with which it is possible to reduce an environmental load (emission of greenhouse gases) over its life cycle by using a plant-derived polyethylene as the raw material instead of a conventional polyethylene obtained from fossil fuels.　Provided is chlorosulfonated polyethylene having a biomass content of 10 to 100% as measured in accordance with ASTM D 6866.

Description

Biomass-derived chlorosulfonated polyethylene

[0001] The present invention relates to a biomass chlorosulfonated polyethylene obtained from plant-derived raw materials. More specifically, the present invention relates to a chlorosulfonated polyethylene characterized by comprising:

[0002] In recent years, with the growing demand for the creation of a recycling-oriented society, there has been a desire to move away from petroleum-based raw materials in the materials field, and the use of biomass has been attracting attention.Similarly, in the field of rubber materials, the production of rubber materials using raw materials derived from biomass has been attracting attention, and various studies are being conducted in this regard.

[0003] For example, Patent Document 1 describes the synthesis of polybutadiene rubber using raw materials derived from biomass.

[0004] Furthermore, Non-Patent Document 1 reports the development of ethylene propylene rubber (EPDM) using raw materials derived from biomass.

[0005] Japanese Patent Application Publication No. 2014-024915

[0006] NOK Corporation Press Release March 25, 2022

[0007] The present invention focuses on polyethylene, which is a raw material for chlorosulfonated polyethylene, and provides chlorosulfonated polyethylene that uses plant-derived polyethylene as its raw material instead of conventional polyethylene obtained from fossil fuels, thereby enabling a reduction in the environmental load (emission of greenhouse gases) throughout its life cycle.

[0008] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have completed the present invention. Specifically, the present invention relates to the following items [1] to

[11] . [1] A chlorosulfonated polyethylene having a biomass content of 10 to 100% as measured in accordance with ASTM D 6866. [2] The chlorosulfonated polyethylene according to [1], which has a chlorine content of 10 to 50% by weight. [3] The chlorosulfonated polyethylene according to [1] or [2], which has a sulfur content of 0.4 to 5% by weight. [4] The chlorosulfonated polyethylene according to any one of [1] to [3], which has a glass transition temperature (Tg) of -40 to 30°C as measured by differential scanning calorimetry (DSC). [5] The chlorosulfonated polyethylene according to any one of [1] to [4], which has a Mooney viscosity (ML(1+4)100°C) of 10 to 150. [6] The chlorosulfonated polyethylene according to any one of [1] to [5], having a viscosity of 100 to 10,000 mPa s in a 25 wt % toluene solution. [7] The chlorosulfonated polyethylene according to any one of [1] to [6], having a ratio Mw / Mn, which is the ratio of number average molecular weight Mn to weight average molecular weight Mw, measured by gel permeation chromatography (GPC), of 2.0 to 4.2. [8] The chlorosulfonated polyethylene according to any one of [1] to [7], having a crystalline melting point (Tm) of 30 to 50°C, as measured by differential scanning calorimetry (DSC), and a heat of fusion (ΔH) of 0.01 to 1 g / J, as calculated from the peak area at the melting point. [9] The chlorosulfonated polyethylene according to any one of [1] to [8], having a yellowness index YI of 20 to 60, as measured in accordance with ASTM D 1925.

[10] A method for producing the chlorosulfonated polyethylene according to any one of [1] to [9], which comprises chlorosulfonating polyethylene having a biomass content of 10 to 100% as measured in accordance with ASTM D 6866.

[11] A composition comprising the chlorosulfonated polyethylene according to any one of [1] to [9] and a compounding agent.

[0009] The chlorosulfonated polyethylene according to the present invention has mechanical properties equivalent to those of conventional chlorosulfonated polyethylene produced from raw materials obtained from fossil fuels, and can replace conventional chlorosulfonated polyethylene. Furthermore, since the biomass content as measured according to ASTM D 6866 is 10 to 100%, the environmental load (emission of greenhouse gases) over the life cycle can be reduced.

[0010] The present invention will be described in detail below.

[0011] The biomass-derived chlorosulfonated polyethylene according to one embodiment of the present invention is a chlorosulfonated polyethylene having a biomass degree of 10 to 100% as measured in accordance with ASTM D 6866. From the viewpoints of excellent processing stability and reduced environmental impact over the life cycle, chlorosulfonated polyethylene having a biomass degree of 30% or more is preferred.

[0012] Biomass refers to any renewable natural raw material or residue of plant or animal origin, including fungi, yeast, algae, and bacteria. The carbon of olefins obtained from biomass contains a certain amount of the C14 isotope derived from biomass (10 ―１２ (Proportion of the same).

[0013] Fossil fuels are oil, coal, natural gas, shale gas, and other materials made from the remains of plants and animals that have been deposited and pressurized over hundreds of millions of years and turned into fossils. The carbon in olefins derived from fossil fuels is much older than the half-life of the C14 isotope, which is 5,730 years, so the C14 isotope derived from biomass is not detectable.

[0014] The biomass ratio means the proportion of naturally derived raw materials contained in a product, and can be measured by measuring the amount of radioactive carbon C14 contained in a product, which is only found in naturally derived substances. In the present invention, the biomass ratio is determined by measuring the radioactive carbon C14 concentration of chlorosulfonated polyethylene using accelerator mass spectrometry (AMS) in accordance with ASTM D 6866, and calculating the ratio to carbon derived from fossil fuels that does not contain radioactive carbon C14.

[0015] The use of biomass-derived products, in contrast to those derived from fossil fuels, is an effective means of reducing the increase in atmospheric carbon dioxide concentration and effectively limiting the expansion of the greenhouse effect. In contrast to those derived from fossil fuels, biomass-derived products have the additional property that they can be incinerated at the end of their life cycle, producing only non-fossil carbon dioxide, the greater the biomass content, the greater this effect.

[0016] The chlorine content of the biomass-derived chlorosulfonated polyethylene of the present invention is preferably 10 to 50% by weight, more preferably 20 to 47% by weight, and even more preferably 25 to 45% by weight, because excellent flexibility and mechanical properties can be obtained.

[0017] The sulfur content of the biomass-derived chlorosulfonated polyethylene is preferably 0.4 to 5% by weight, more preferably 0.5 to 3% by weight, and even more preferably 0.7 to 2% by weight, since a vulcanizate with an appropriate vulcanization density can be obtained.

[0018] The Mooney viscosity (ML(1+4)100°C) of the biomass-derived chlorosulfonated polyethylene is preferably 10 to 150, and more preferably 20 to 120, since this achieves both particularly excellent mechanical properties and processability.

[0019] The glass transition temperature (Tg) of the biomass-derived chlorosulfonated polyethylene measured by differential scanning calorimetry (DSC) is preferably −40 to 30° C., more preferably −35 to 25° C., and even more preferably −30 to 20° C., because excellent flexibility and mechanical properties can be obtained.

[0020] The weight-average molecular weight of the biomass-derived chlorosulfonated polyethylene is preferably 5,000 to 600,000, and more preferably 10,000 to 500,000, in order to obtain excellent mechanical properties and processability. Furthermore, the ratio Mw / Mn of the number-average molecular weight Mn to the weight-average molecular weight Mw is preferably 2.0 to 4.2, and more preferably 3.0 to 4.0, in order to obtain excellent mechanical properties and process stability. The number-average molecular weight and weight-average molecular weight refer to values ​​(polystyrene equivalent) measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC).

[0021] It is preferable that the biomass-derived chlorosulfonated polyethylene has a crystalline melting point (Tm) of 30 to 50°C as measured by a differential scanning calorimeter (DSC) and a heat of fusion (ΔH) of 0.01 to 1 g / J as calculated from the peak area at the melting point, since this provides excellent mechanical properties and processing stability.

[0022] The yellowness index YI of the biomass-derived chlorosulfonated polyethylene measured in accordance with ASTM D 1925 is preferably 20 to 60, since this allows the chlorosulfonated polyethylene to be colored yellow.

[0023] When chlorosulfonated polyethylene is dissolved in an organic solvent and used for applications such as fabric coatings and adhesives, the viscosity of a 25 wt % toluene solution of biomass-derived chlorosulfonated polyethylene is preferably 100 to 10,000 mPa s, and more preferably 300 to 3,000 mPa s, in order to achieve both mechanical properties and handleability.

[0024] The polyethylene used as the raw material for biomass-derived chlorosulfonated polyethylene is polyethylene having a biomass content of 10 to 100% as measured in accordance with ASTM D 6866, and may be used alone or as a blend of two or more types of polyethylene. Furthermore, petroleum-derived polyethylene may be used as the polyethylene used for the blend, as long as the biomass content after blending is within the range of 10 to 100%.

[0025] The main chain structure of polyethylene used as a raw material for biomass-derived chlorosulfonated polyethylene is not particularly limited, and examples include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. A single polyethylene or a blend of two or more polyethylenes may be used as the raw material. When used for applications such as fabric coatings and adhesives, low-density polyethylene is preferred because it has excellent solubility in organic solvents.

[0026] Biomass-derived chlorosulfonated polyethylene can be synthesized by a conventional method. For example, it can be dissolved in a chlorine-based solvent such as carbon tetrachloride, chloroform, or 1,1,2-trichloroethane, and then blown with chlorine gas in the presence of a radical initiator. The reaction temperature is not particularly limited, but is usually between 60 and 180°C. The reaction pressure is not particularly limited, but is preferably between atmospheric pressure and 1.0 megapascals.

[0027] After the chlorination reaction is complete, the chlorine gas remaining in the solution and the by-product hydrogen chloride gas are removed from the reaction system by blowing in an inert gas such as nitrogen under reflux of the solvent. The polymer and the solvent of the obtained chlorosulfonated polyethylene are separated, if necessary, by steam distillation, drum drying, extrusion drying, etc.

[0028] The method for producing the biomass-derived chlorosulfonated polyethylene, which is one embodiment of the present invention, is not particularly limited, and examples thereof include a solution method in which polyethylene having a biomass degree of 10 to 100% measured in accordance with ASTM D 6866 is uniformly dissolved in an inert solvent and reacted, a suspension method in which polyethylene is suspended in a solvent and reacted, and a dissolution method in which polyethylene is dissolved and reacted in the absence of a solvent. Among these, the solution method, which allows for uniform chlorosulfonation of polyethylene, is preferred.

[0029] The solvent used for chlorosulfonation by the solution method is not particularly limited, and examples thereof include carbon tetrachloride, trichloroethane, tetrachloroethane, chloroform, chlorobenzene, and the like, from the viewpoints of solubility and reactivity, with trichloroethane being particularly preferred due to its favorable reactivity.

[0030] In the present invention, the chlorosulfonating agent used in chlorosulfonating polyethylene is not particularly limited, and sulfur dioxide, chlorine, sulfuryl chloride, and the like may be used alone or in combination. Furthermore, if necessary, a catalyst for accelerating the chlorosulfonation reaction may be used. Examples of the catalyst include azo compounds and organic peroxides. Examples of azo compounds include α,α'-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, and 2,2'-azobis(2,4-dimethylvaleronitrile). Examples of organic peroxides include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, and t-butyl perbenzoate. Azo compounds are preferred because of their high stability in handling, and α,α'-azobisisobutyronitrile is particularly preferred because it allows the chlorination and chlorosulfonation reactions to proceed appropriately. Furthermore, if necessary, amino compounds such as pyridine and quinoline, or phosphate ester compounds may be added as co-catalysts for accelerating the chlorosulfonation reaction.

[0031] The reaction temperature during chlorosulfonation is not particularly limited and can be appropriately selected depending on the melting point of the raw material polyethylene, and in particular, taking into consideration reactivity and handleability, it is preferably 50 to 150° C., and more preferably 60 to 130° C. Furthermore, the reaction pressure during chlorosulfonation is not particularly limited and is, for example, 0 to 1.0 MPa, and is preferably 0 to 0.6 MPa to ensure that chlorosulfonation proceeds appropriately.

[0032] After the chlorosulfonation reaction is completed, sulfur dioxide gas or hydrogen chloride remaining in the reaction solution can be removed by introducing nitrogen. There is no problem even if the sulfur dioxide gas or hydrogen chloride is removed under reduced pressure.

[0033] Furthermore, additives such as antioxidants and stabilizers may be added either before or after the chlorosulfonation reaction. The type of additive is not particularly limited, and examples include hindered phenol-based antioxidants such as 4-t-butylcatechol, 2,6-di-t-butyl-p-cresol, and triethylene glycol bis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], and epoxy compounds such as epoxidized polybutadiene and bisphenol A resin. These may be used alone or in combination of two or more types. The timing of adding the additive is not particularly limited, but considering the ease of operation and the efficiency of the additive, it is preferable to add the additive after the chlorosulfonation reaction and removal of residual gas.

[0034] The method for separating the polymer and the solvent from the chlorosulfonated product polymer solution is not particularly limited, but for example, steam distillation, a drum dryer, a vented extruder, or the like can be used.

[0035] A composition according to one embodiment of the present invention comprises the above-described chlorosulfonated polyethylene and compounding agents. The biomass-derived chlorosulfonated polyethylene of the present invention is primarily used as a vulcanizate. To obtain a vulcanized biomass-derived chlorosulfonated polyethylene of the present invention, the biomass-derived chlorosulfonated polyethylene and various compounding agents are blended or kneaded using a roll or Banbury mixer, followed by press vulcanization, steam vulcanization, high-frequency (UHF) vulcanization, or electron beam vulcanization. The vulcanization temperature is not particularly limited, but is 130 to 200°C, preferably 150 to 180°C. Secondary vulcanization can also be performed as needed. The secondary vulcanization is performed in a heating oven at 140 to 180°C for 2 to 6 hours. Examples of various compounding agents include vulcanizing agents, vulcanization accelerators, acid acceptors, plasticizers, reinforcing agents, fillers, processing aids, and antioxidants, which are used as needed.

[0036] Examples of vulcanizing agents include inorganic vulcanizing agents such as sulfur, and organic vulcanizing agents such as thiuram polysulfides, dithiocarbamates, oximes, nitroso compounds, and organic peroxides. Examples of vulcanization accelerators include thioureas, guanidines, thiazoles, sulfenamides, thiurams, dithiocarbamates, and xanthogenates. Examples of acid acceptors include magnesium oxide, zinc oxide, hydrotalcite, and litharge. Examples of plasticizers include mineral oil-based softeners, vegetable oil-based softeners, synthetic softeners, and synthetic plasticizers. Examples of reinforcing materials include carbon black and white carbon. Examples of fillers include calcium carbonates, basic magnesium carbonates, silicic acid and silicates. Examples of processing aids include fatty acids, fatty acid esters, fatty acid metal salts, and hydrocarbon waxes. Examples of the antioxidant include amine-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and waxes.

[0037] The applications of the biomass-derived chlorosulfonated polyethylene are not particularly limited, and it can be used for various industrial parts such as automobile hoses, gas hoses, industrial hoses, electric wire coatings, coated fabrics, packings, gaskets, rolls and linings, rubber boats, life jackets, windbreakers, escalator handrails, adhesives, shoe soles, etc.

[0038] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0039] The values ​​used in these examples were obtained in accordance with the following measurement methods.

[0040] (1) Raw Rubber Characteristics <Measurement of Biomass Degree> In accordance with ASTM D6866, the radiocarbon C14 concentration of chlorosulfonated polyethylene was measured by accelerator mass spectrometry (AMS) to calculate the biomass degree of the chlorosulfonated polyethylene.

[0041] ASTM D6866 specifies that the radiocarbon C14 concentration of a sample should be measured against a standard material for the 1950 atmospheric radiocarbon C14 concentration, and the ratio should be used to determine the biomass ratio. However, since the current atmospheric carbon C14 concentration has been increasing year by year, it is specified that this value should be multiplied by a coefficient to correct for this. In accordance with ASTM D6866-22, the current atmospheric C14 concentration was calculated as 100.0 pMC.

[0042] <Measurement of Chlorine Content and Sulfur Content> The chlorine content of biomass-derived chlorosulfonated polyethylene was measured by the combustion flask method. To measure the chlorine content, approximately 20 mg of chlorosulfonated polyethylene was combusted according to the oxygen flask combustion method, and 15 mL of a 1.7 wt% aqueous hydrazinium sulfate solution was allowed to stand as an absorption solution. After 40 minutes, the absorption solution was washed out with approximately 100 mL of pure water, and then the chloride ions were quantified by potentiometric titration with a 0.5 N aqueous silver nitrate solution using an automatic titrator (Hiranuma Sangyo Co., Ltd., MC-3000, TS-3000). The chlorine content was measured.

[0043] The sulfur content of biomass-derived chlorosulfonated polyethylene was measured by combusting approximately 20 mg of chlorosulfonated polyethylene using the oxygen flask combustion method, followed by allowing the mixture to stand with approximately 10 mL of 3 wt% hydrogen peroxide solution as an absorption solution. After 40 minutes, the absorption solution was washed out with approximately 40 mL of pure water, and then approximately 1 mL of acetic acid, approximately 100 mL of 2-propanol, and approximately 0.5 mL of Arsenazo III were added. The sulfate ions in this solution were quantified by photometric titration with a 0.01 N barium acetate solution, and the sulfur content was measured.

[0044] <Molecular weight measurement> 10 mg of biomass-derived chlorosulfonated polyethylene was dissolved in 10 mL of THF to obtain a polymer solution, and the molecular weight was measured by GPC. The number average molecular weight (Mn) and weight average molecular weight (Mw) were calculated in terms of polystyrene using standard polystyrene (manufactured by Tosoh Corporation). The measurement conditions are shown below.

[0045] Model: (trade name) HLC8420GPC Solvent: THF Column temperature: 40°C Measurement concentration: 10 mg / 10 mL Injection volume: 200 μL Column: TSKgel (registered trademark) G7000HXL (manufactured by Tosoh Corporation) → 2 TSKgel (registered trademark) GMHXL (manufactured by Tosoh Corporation) <Measurement of glass transition temperature> A differential scanning calorimeter (manufactured by NETZSCH, DSC3500Sirius) was used to measure the glass transition temperature (Tg) by heating from -100°C to 150°C at a rate of 10°C / min under a nitrogen gas flow. The starting point of the transition region in the DSC curve was taken as the glass transition temperature (Tg). The top of the endothermic peak that appeared between 10 and 100°C was taken as the crystalline melting point (Tm), and the heat of fusion (ΔH) was calculated from the peak area.

[0046] <Measurement of Solution Viscosity> Chlorosulfonated polyethylene was dissolved in toluene to a concentration of 10% or 25% by weight, and the viscosity was measured using a Brookfield viscometer. The sample container was immersed in a thermostatic bath at 23°C for 1 hour, and then the viscosity was measured using a No. 3 rotor at 30 rpm, and the value after 60 seconds was used.

[0047] <Measurement of Mooney Viscosity> Measurement was carried out in accordance with JIS K 6300 using an L-type rotor, with preheating for 1 minute and rotor rotation time of 4 minutes at 100°C.

[0048] <Measurement of Yellowness Index YI> The yellowness index YI of the chlorosulfonated polyethylene was measured using a color difference meter (CR-5, manufactured by KONICA MINOLTA) in accordance with ASTM D1925.

[0049] (2) Compound Properties <Measurement of Mooney Scorch> Chlorosulfonated polyethylene was kneaded in accordance with JIS-K 6299, and the Mooney scorch ML(1) 125°C of the resulting compound was measured in accordance with JIS-K 6300. Vm is the minimum Mooney viscosity after the rotor starts to rotate, and scorch time t5 is an index of processing stability and is the time it takes for the Mooney viscosity to increase by 5 from Vm.

[0050] <Rheometer Vulcanization Test> Measurement was carried out at 160°C for 45 minutes using a Rubber Process Analyzer RPA 2000 manufactured by Alpha Technologies, and the minimum torque value (ML), maximum torque value (MH), and 90% vulcanization time (Tc90) were determined in accordance with JIS K 6300.

[0051] (3) Vulcanized Rubber Properties <Normal Physical Properties> Chlorosulfonated polyethylene was kneaded in accordance with JIS-K 6299, and the resulting sample was vulcanized in a 2 mm thick mold. Thereafter, hardness (HS) was measured at 23°C using a durometer hardness tester in accordance with JIS-K 6253. Tensile strength (TB), elongation at break (EB), and 100% tensile stress (M100) were evaluated in accordance with JIS-K 6251 at a tension speed of 500 mm / min and 23°C.

[0052] <Heat Aging Resistance> Vulcanized rubber of chlorosulfonated polyethylene was aged in a Geer oven at 120° C. for 72 hours in accordance with JIS K6257, and then the changes in normal physical properties were evaluated.

[0053] The reagents used in the synthesis of chlorosulfonated polyethylene in the examples are as follows:

[0054] Raw material bio-polyethylene 1: Grade SPB208 manufactured by Braskem; Melt mass-flow rate (ASTM D 1238, temperature 190°C, load 2.16 kg): 22 g / 10 min; Low-density polyethylene (density 0.923 g / cm ３ Raw material bio-polyethylene 2: Grade name SEB853 manufactured by Braskem. Melt mass flow rate (ASTM D 1238, temperature 190°C, load 2.16 kg): 2.7 g / 10 min. Low density polyethylene (density 0.923 g / cm ３ Raw material bio-polyethylene 3: Grade name SHC7260 manufactured by Braskem. Melt mass flow rate (ASTM D 1238, temperature 190°C, load 2.16 kg): 7.2 g / 10 min. High density polyethylene (density 0.959 g / cm ３Petroleum-derived polyethylene 1: Petrothene (trademark) 228-1 manufactured by Tosoh Corporation Melt mass flow rate (JIS K6922-1 temperature 190 ° C load 2.16 kg) 1.5 g / 10 min Low density polyethylene (density 0.924 g / cm ３ Petroleum-derived polyethylene 2: Petrothene (trademark) 208 manufactured by Tosoh Corporation. Melt mass flow rate (JIS K6922-1, temperature 190°C, load 2.16 kg) 23 g / 10 min. Low-density polyethylene (density 0.918 g / cm ３ Petroleum-derived polyethylene 3: Nipolon Hard (registered trademark) 4030 manufactured by Tosoh Corporation. Melt mass flow rate (JIS K6922-1, temperature 190°C, load 2.16 kg): 4.8 g / 10 min. High-density polyethylene (density 0.964 g / cm ３ ) 1,1,2-Trichloroethane: manufactured by Tosoh Corporation α,α'-Azobisisobutyronitrile: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Sulfuryl chloride: manufactured by Sumitomo Seika Chemicals Co., Ltd. Pyridine: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 2,2-Bis(4-glycidyloxyphenyl)propane: manufactured by Tokyo Chemical Industry Co., Ltd. The details of the compounding ingredients used in the examples are as follows.

[0055] Magnesium oxide (acid acceptor): Kyowamag #150 (Kyowa Chemical Industry Co., Ltd.) Processing aid 1: Splendor (registered trademark) R-300 (fatty acid ester) (Kao Corporation) Processing aid 2: Struktol WB-212 (S&S Japan Co., Ltd.) Carbon (reinforcing agent): SRF Carbon Seast (registered trademark) S (Tokai Carbon Co., Ltd.) Plasticizer: Aliphatic dibasic acid ester DOZ (Daihachi Chemical Co., Ltd.) CSM vulcanizing agent: Dipentamethylene thiuram tetrasulfide (Ouchi Shinko Chemical Industry Co., Ltd.) Pentaerythritol (activator): Neuraizer (registered trademark) P (Mitsubishi Chemical Corporation) Example 1 Under a nitrogen atmosphere, 605 g of raw biopolyethylene 1 and 1,411 g of raw biopolyethylene 2 were dissolved in 10 L of 1,1,2-trichloroethane at 110°C in a 40 L glass-lined autoclave. To this polymer solution, 0.3 g of pyridine was added at 110°C, and a solution of 2.1 g of α,α'-azobisisobutyronitrile dissolved in 1 kg of 1,1,2-trichloroethane and 3.8 kg of sulfuryl chloride were added dropwise over 120 minutes. The pressure inside the reactor was maintained at 0.2 MPa during the reaction. After completion of the dropwise addition, the temperature of the reaction solution was lowered to 70°C, and nitrogen was blown into the reaction mixture for 2 hours at 70°C. 33 g of 2,2-bis(4-glycidyloxyphenyl)propane was added to the reaction solution, and the solvent was removed using a drum dryer heated to 155°C, yielding biomass-derived chlorosulfonated polyethylene 1.

[0056] The composition of the obtained chlorosulfonated polyethylene 1 and its raw rubber properties, such as Mooney viscosity and biomass content, were measured. The results are shown in Table 1. As shown in Table 1, the chlorine content was 29.7% by weight, the sulfur content was 1.4% by weight, the Mooney viscosity was 28, the biomass content was 99%, and the viscosity of a 25% by weight toluene solution was 1700 mPa s.

[0057]

[0058] To 100 parts by weight of the obtained chlorosulfonated polyethylene 1, 6 parts by weight of magnesium oxide, 1 part by weight of processing aid 1, 1 part by weight of processing aid 2, 30 parts by weight of carbon, and 15 parts by weight of plasticizer were added using an open roll mixer, and then 2 parts by weight of a CSM vulcanizing agent and 3 parts by weight of pentaerythritol were added using an open roll mixer to obtain chlorosulfonated polyethylene composition 1. The obtained chlorosulfonated polyethylene composition 1 was subjected to a Mooney scorch test and a rheometer vulcanization test of unvulcanized rubber, and the results are shown in Table 2. The obtained chlorosulfonated polyethylene composition 1 was also press-vulcanized at 160°C for 20 minutes to obtain a vulcanizate. The obtained vulcanizate was subjected to normal state physical properties and heat aging resistance tests. The results are shown in Table 2. As can be seen from Table 2, the physical properties were comparable to those of chlorosulfonated polyethylene made from petroleum-derived polyethylene.

[0059]

[0060] Comparative Example 1 Petroleum-derived chlorosulfonated polyethylene 2 was obtained in the same manner as in Example 1, except that the raw polyethylene charged was 907.2 g of petroleum-derived polyethylene 1 and 1,108.8 g of petroleum-derived polyethylene 2. The composition of the obtained chlorosulfonated polyethylene 2 and its raw rubber properties, such as Mooney viscosity and biomass content, were measured. The results are shown in Table 1. As shown in Table 1, the chlorine content was 29.9 wt%, the sulfur content was 1.3 wt%, the Mooney viscosity was 28, the biomass content was 0%, and the viscosity of a 25 wt% toluene solution was 2,000 mPa s.

[0061] Chlorosulfonated polyethylene composition 2 was obtained in the same manner as in Example 1, except that petroleum-derived chlorosulfonated polyethylene 2 was used instead of biomass-derived chlorosulfonated polyethylene 1.

[0062] The resulting chlorosulfonated polyethylene composition 2 was subjected to a Mooney scorch test of unvulcanized rubber and a rheometer vulcanization test, and the results are shown in Table 2. The resulting chlorosulfonated polyethylene composition 2 was also press-vulcanized at 160°C for 20 minutes to obtain a vulcanizate. The resulting vulcanizate was subjected to normal state physical properties and heat aging resistance tests. The results are shown in Table 2.

[0063] Example 2: Under a nitrogen atmosphere, 1008 g of raw biopolyethylene 3 was dissolved in 10 L of 1,1,2-trichloroethane at 120°C in a 40 L glass-lined autoclave. To this polymer solution, 0.3 g of pyridine was added at 110°C, and a solution of 2.1 g of α,α'-azobisisobutyronitrile dissolved in 1 kg of 1,1,2-trichloroethane and 3.8 kg of sulfuryl chloride were added dropwise over 70 minutes. The pressure inside the reactor was maintained at 0.2 MPa during the reaction. After the dropwise addition was completed, the temperature of the reaction solution was lowered to 70°C, and nitrogen was blown into the reaction mixture for 2 hours at 70°C. 18 g of 2,2-bis(4-glycidyloxyphenyl)propane was added to the reaction solution, and the solvent was removed using a drum dryer heated to 155°C, yielding biomass-derived chlorosulfonated polyethylene 3.

[0064] The raw rubber properties of the obtained chlorosulfonated polyethylene 3 were measured. The results are shown in Table 1. As shown in Table 1, the chlorine content was 35.8% by weight, the sulfur content was 0.9% by weight, the Mooney viscosity was 64, the Mw / Mn was 3.5, the biomass degree was 98%, and the viscosity of a 10% by weight toluene solution was 300 mPa s.

[0065] To 100 parts by weight of the obtained chlorosulfonated polyethylene 3, 10 parts by weight of magnesium oxide was added using an open roll kneader, and then 2 parts by weight of a CSM vulcanizing agent and 3 parts by weight of pentaerythritol were added using an open roll kneader to obtain chlorosulfonated polyethylene composition 3. The obtained chlorosulfonated polyethylene composition 3 was subjected to a Mooney scorch test and a rheometer vulcanization test of the unvulcanized rubber, and the results are shown in Table 2. As shown in Table 2, although Tc90 was almost equivalent to that of petroleum-derived chlorosulfonated polyethylene, t5 was longer than that of petroleum-derived chlorosulfonated polyethylene, indicating good processing stability. Furthermore, the obtained chlorosulfonated polyethylene composition was press-vulcanized at 160°C for 20 minutes to obtain a vulcanizate. The obtained vulcanizate was subjected to normal state physical properties and heat aging resistance tests. These results are shown in Table 2. As shown in Table 2, the mechanical properties were equivalent to those of chlorosulfonated polyethylene made from petroleum-derived polyethylene.

[0066] Example 3 Biomass-derived chlorosulfonated polyethylene 4 was obtained in the same manner as in Example 2, except that 806 g of biopolyethylene 3 and 202 g of petroleum-derived polyethylene 3 were charged as the raw polyethylene.

[0067] The raw rubber properties of the obtained chlorosulfonated polyethylene 4 were measured. The results are shown in Table 1. As shown in Table 1, the chlorine content was 35.2% by weight, the sulfur content was 0.9% by weight, the Mooney viscosity was 61, the Mw / Mn was 3.8, the biomass degree was 78%, and the viscosity of a 10% by weight toluene solution was 460 mPa s.

[0068] Chlorosulfonated polyethylene composition 4 was obtained in the same manner as in Example 2, except that chlorosulfonated polyethylene 4 was used instead of chlorosulfonated polyethylene 3. The resulting chlorosulfonated polyethylene composition 4 was subjected to a Mooney scorch test and a rheometer vulcanization test on the unvulcanized rubber, and the results are shown in Table 2. Table 2 indicates that, although Tc90 was nearly equivalent to that of petroleum-derived chlorosulfonated polyethylene, t5 was longer than that of petroleum-derived chlorosulfonated polyethylene, demonstrating good processing stability. Furthermore, the resulting chlorosulfonated polyethylene composition was press-vulcanized at 160°C for 20 minutes to obtain a vulcanizate. The resulting vulcanizate was subjected to normal state physical properties and heat aging resistance tests. These results are shown in Table 2. Table 2 indicates that the mechanical properties were equivalent to those of chlorosulfonated polyethylene made from petroleum-derived polyethylene.

[0069] Comparative Example 2 Petroleum-derived chlorosulfonated polyethylene 5 was obtained in the same manner as in Example 2, except that the raw material biopolyethylene 3 was replaced with raw material petroleum-derived polyethylene 3.

[0070] The raw rubber properties of the resulting chlorosulfonated polyethylene 5 were measured. The results are shown in Table 1. As shown in Table 1, the chlorine content was 35.6 wt%, the sulfur content was 1.1 wt%, the Mooney viscosity was 56, the Mw / Mn was 4.6, the biomass content was 0%, and the viscosity of a 10 wt% toluene solution was 640 mPa·s. Chlorosulfonated polyethylene composition 5 was obtained in the same manner as in Example 2, except that chlorosulfonated polyethylene 5 was used instead of biomass-derived chlorosulfonated polyethylene 3. The resulting chlorosulfonated polyethylene composition 5 was subjected to a Mooney scorch test and a rheometer vulcanization test of the unvulcanized rubber. The results are shown in Table 2. The resulting chlorosulfonated polyethylene composition was press-vulcanized at 160°C for 20 minutes to obtain a vulcanizate. The resulting vulcanizate was then subjected to a normal state physical property test and a heat aging resistance test. The results are shown in Table 2.

[0071] While the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

[0072] The entire contents of the specifications, claims and abstracts of Japanese Patent Application Nos. 2024-000795 and 2024-000796 filed on January 5, 2024 are hereby cited and incorporated as the disclosure of the specification of the present invention.

Claims

1. Chlorosulfonated polyethylene with a biomass content of 10 to 100% measured in accordance with ASTM D 6866.

2. The chlorosulfonated polyethylene according to claim 1, having a chlorine content of 10 to 50% by weight.

3. The chlorosulfonated polyethylene according to claim 1, having a sulfur content of 0.4 to 5% by weight.

4. The chlorosulfonated polyethylene according to claim 1, having a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) of -40 to 30°C.

5. The chlorosulfonated polyethylene according to claim 1, having a Mooney viscosity (ML(1+4) 100°C) of 10 to 150.

6. The chlorosulfonated polyethylene according to claim 1, having a 25% by weight toluene solution viscosity of 100 to 10000 mPa·s.

7. The chlorosulfonated polyethylene according to claim 1, having an Mw / Mn, which is the ratio of the number average molecular weight Mn to the weight average molecular weight Mw measured by gel permeation chromatography (GPC), of 2.0 to 4.

2.

8. The chlorosulfonated polyethylene according to claim 1, having a crystal melting point (Tm) measured by differential scanning calorimetry (DSC) of 30 to 50°C and a heat of fusion (ΔH) calculated from the peak area of the melting point of 0.01 to 1 g / J.

9. The chlorosulfonated polyethylene according to claim 1, having a yellowness index YI measured in accordance with ASTM D 1925 of 20 to 60.

10. A method for producing the chlorosulfonated polyethylene according to any one of claims 1 to 9, comprising chlorosulfonating polyethylene with a biomass content of 10 to 100% measured in accordance with ASTM D 6866.

11. A composition comprising the chlorosulfonated polyethylene according to any one of claims 1 to 9 and a compounding agent.

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