Biomass-derived chlorosulfonated polyethylene

Abstract

To provide chlorosulfonated polyethylene with which it is possible to reduce an environmental load (emission of greenhouse gases) over its life cycle, by using plant-derived polyethylene as the raw material, instead of conventional polyethylene derived from fossil fuels.SOLUTION: There is provided chlorosulfonated polyethylene having a biomass content of 10 to 100% as measured in accordance with ASTM D 6866.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] In recent years, with the increasing demand for building a recycling-oriented society, the abandonment of petroleum raw materials in the material field has been desired, and the utilization of biomass has attracted attention. Similarly, in the rubber material field, the production of rubber materials using raw materials derived from biomass has attracted attention, and various studies have been conducted on this.

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

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

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Non-Patent Documents

[0006]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] The present invention focuses on polyethylene, which is a raw material for chlorosulfonated polyethylene, and by using plant-derived polyethylene as the raw material instead of polyethylene obtained from conventional fossil fuels, it provides chlorosulfonated polyethylene capable of reducing the environmental burden (greenhouse gas generation) in the life cycle.

Means for Solving the Problems

[0008] As a result of intensive studies to solve the above problems, the present inventor has completed the present invention. That is, the present invention relates to the following [1] to

[11] . [1] Chlorosulfonated polyethylene having a biomass content of 10 to 100% measured in accordance with ASTM D 6866. [2] The chlorosulfonated polyethylene according to [1], wherein the chlorine content is 10 to 50% by weight. [3] The chlorosulfonated polyethylene according to [1] or [2], wherein the sulfur content is 0.4 to 5% by weight. [4] The chlorosulfonated polyethylene according to any one of [1] to [3], wherein the glass transition temperature (Tg) measured by a differential scanning calorimeter (DSC) is -40 to 30°C. [5] The chlorosulfonated polyethylene according to any one of [1] to [4], wherein the Mooney viscosity (ML(1+4)100°C) is 10 to 150. [6] The chlorosulfonated polyethylene according to any one of [1] to [5], wherein the viscosity of a 25% by weight toluene solution is 100 to 10000 mPa·s. [7] The chlorosulfonated polyethylene according to any one of [1] to [6], wherein 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), is 2.0 to 4.2. [8] The chlorosulfonated polyethylene according to any one of [1] to [7], wherein the crystal melting point (Tm) measured by a differential scanning calorimeter (DSC) is 30 to 50°C, and the heat of fusion (ΔH) calculated from the peak area of the melting point is 0.01 to 1 g / J. The chlorosulfonated polyethylene described in any one of [1] to [8], having a yellowness index YI measured in accordance with ASTM D 1925 of 20 to 60. A method for producing a chlorosulfonated polyethylene according to any one of [1] to [9], comprising chlorosulfonating a polyethylene having a biomass content of 10 to 100% measured in accordance with ASTM D 6866. A composition comprising a chlorosulfonated polyethylene according to any one of [1] to [9] and a compounding agent.

Advantages of the Invention

[0009] The chlorosulfonated polyethylene according to the present invention has mechanical properties equivalent to those of chlorosulfonated polyethylene produced from raw materials obtained from conventional fossil fuels, can replace conventional chlorosulfonated polyethylene, and has a biomass content of 10 to 100% as measured by ASTM D 6866, so that the environmental load (greenhouse gas generation) in the life cycle can be reduced.

Embodiments for Carrying Out the Invention

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

[0011] The biomass-derived chlorosulfonated polyethylene according to one aspect of the present invention is a chlorosulfonated polyethylene having a biomass content of 10 to 100% measured in accordance with ASTM D 6866. Further, from the viewpoints of excellent processing stability and reduction of environmental load in the life cycle, chlorosulfonated polyethylene having a biomass content of 30% or more is preferable.

[0012] Biomass refers to any renewable natural raw material and its residue derived from plants or animals, including fungi, yeasts, algae, and bacteria, and the carbon of the olefin obtained from biomass contains a certain amount of C14 isotope derived from biomass (about 10 ―12 proportion).

[0013] Fossil fuels refer to substances such as petroleum, coal, natural gas, and shale gas, which are formed by the fossilization of the remains of animals and plants through processes such as sedimentation and pressurization over hundreds of millions of years. Since the carbon of olefins derived from fossil fuels has experienced a time period much longer than the half-life of 5730 years of C14 isotope, C14 isotope derived from biomass is not detected.

[0014] The biomass content refers to the proportion of naturally derived raw materials contained in a product. By measuring how much radioactive carbon C14, which is only contained in naturally derived substances, is contained in the product, the biomass content can be measured. In the present invention, the biomass content is determined by measuring the radioactive carbon C14 concentration of chlorosulfonated polyethylene by accelerator mass spectrometry (AMS method) based on 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 is, in contrast to those obtained from fossil fuels, an effective means to reduce the increase in atmospheric carbon dioxide concentration and efficiently limit the expansion of the greenhouse effect. In contrast to those obtained from fossil fuels, biomass-derived products have the additional property that they can be incinerated at the end of their life cycle, producing only carbon dioxide not derived from fossils, and the greater the biomass content, the greater the 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, since 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 biomass-derived chlorosulfonated polyethylene is preferably from 10 to 150, more preferably from 20 to 120, because it can achieve both particularly excellent mechanical properties and processability.

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

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

[0021] The crystal melting point (Tm) of biomass-derived chlorosulfonated polyethylene measured by differential scanning calorimetry (DSC) is from 30 to 50 °C, and the heat of fusion (ΔH) calculated from the peak area of the melting point is preferably from 0.01 to 1 g / J, because excellent mechanical properties and processing stability can be obtained.

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

[0023] When chlorosulfonated polyethylene is dissolved in an organic solvent and used for applications such as drawing cloth, coating, and adhesives, the viscosity of a 25 wt% toluene solution of biomass-derived chlorosulfonated polyethylene is preferably 100 to 10000 mPa·s, more preferably 300 to 3000 mPa·s, because it balances mechanical properties and handleability.

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

[0025] The structure of the main chain of the 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, ultra-low-density polyethylene, etc. It may be used alone or as a blend of two or more types of polyethylene. When used for applications such as drawing cloth, coating, and adhesives, low-density polyethylene is preferred because it provides excellent solubility in organic solvents.

[0026] The biomass-derived chlorosulfonated polyethylene can be synthesized by a conventionally known method. For example, a method of dissolving it in a chlorine-based solvent such as carbon tetrachloride, chloroform, or 1,1,2-trichloroethane and blowing chlorine gas in the presence of a radical initiator can be mentioned. The reaction temperature is not particularly limited, but it is 60 to 180°C, and the reaction pressure is not particularly limited, but normal pressure to 1.0 megapascals is appropriate.

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

[0028] As a method for producing biomass-derived chlorosulfonated polyethylene, which is one aspect of the present invention, there is no particular limitation. For example, a solution method in which polyethylene having a biomass content 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, a dissolution method in which polyethylene is dissolved and reacted without a solvent, etc. can be mentioned. Among these, the solution method, which enables uniform chlorosulfonation of polyethylene, is preferable.

[0029] The solvent used for chlorosulfonation in the solution method is not particularly limited, and examples include carbon tetrachloride, trichloroethane, tetrachloroethane, chloroform, chlorobenzene, etc. from the viewpoints of solubility and reactivity. Trichloroethane is preferable because it exhibits particularly good reactivity.

[0030] In the present invention, the chlorosulfonating agent for chlorosulfonating polyethylene is not particularly defined, and sulfur dioxide gas, chlorine, sulfuryl chloride, etc. may be used alone or in combination. Further, a catalyst or the like for accelerating the chlorosulfonating reaction may be used as necessary. Examples of the catalyst include azo compounds and organic peroxides. Examples of the azo compounds include α,α'-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc., and examples of the organic peroxides include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, t-butyl perbenzoate, etc. An azo compound is preferably used because of its high stability in handling, and α,α'-azobisisobutyronitrile is particularly preferably used because an appropriate chlorination and chlorosulfonation reaction proceed. Further, an amino compound such as pyridine or quinoline or a phosphate ester compound may be added as a promoter for accelerating the chlorosulfonating reaction as necessary.

[0031] The reaction temperature for chlorosulfonation is not particularly limited and can be appropriately selected according to the melting point of the raw material polyethylene, etc. Among them, considering the reactivity and handleability, 50 to 150 °C is preferable, and more preferably 60 to 130 °C. Further, the reaction pressure for chlorosulfonation is not particularly limited, and is, for example, 0 to 1.0 megapascals, and preferably 0 to 0.6 megapascals for appropriate chlorosulfonation to proceed.

[0032] After completion of the chlorosulfonation reaction, sulfur dioxide gas or hydrogen chloride remaining in the reaction solution is removed by introducing nitrogen. Further, there is no problem in removing sulfur dioxide gas or hydrogen chloride, etc. under reduced pressure.

[0033] Furthermore, additives such as antioxidants and stabilizers may be added either before or after the chlorosulfonation reaction. The types of additives are not particularly limited. For example, hindered phenolic 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 type resins can be mentioned. These may be used alone or in combination of two or more. The addition timing of the additives is not particularly limited, but considering the work simplicity and the efficiency of the additives, it is preferable to add them after the chlorosulfonation reaction and after removing the residual gas.

[0034] As a method for separating the polymer and the solvent from the chlorosulfonated product polymer solution, it is not particularly limited. For example, steam distillation, drum dryer, vented extruder, etc. can be used.

[0035] The composition which is one aspect of the present invention contains the above-mentioned chlorosulfonated polyethylene and compounding agents. The biomass-derived chlorosulfonated polyethylene in the present invention is mainly used as a vulcanizate. As a method for obtaining the vulcanizate of the biomass-derived chlorosulfonated polyethylene of the present invention, after compounding or kneading the biomass-derived chlorosulfonated polyethylene and various compounding agents with a roll or a Banbury mixer, etc., press vulcanization, steam vulcanization, high-frequency (UHF) vulcanization, or electron beam vulcanization, etc. is carried out. The vulcanization temperature is not particularly limited, but it is 130 to 200 °C, preferably 150 to 180 °C. Also, secondary vulcanization can be carried out if necessary. The conditions for secondary vulcanization are carried out in the range of 140 to 180 °C in a heating oven for 2 to 6 hours. Various compounding agents include vulcanizing agents, vulcanization accelerators, acid acceptors, plasticizers, reinforcing agents, fillers, processing aids, anti-aging agents, etc., and are used as necessary.

[0036] Examples of the vulcanizing agent include inorganic vulcanizing agents such as sulfur, and organic vulcanizing agents such as thiuram polysulfides, dithiocarbamates, oximes, nitroso compounds, and organic peroxides. Examples of the vulcanization accelerator include thioureas, guanidines, thiazoles, sulfenamides, thiurams, dithiocarbamates, and xanthates. Examples of the acid acceptor include magnesium oxide, zinc oxide, hydrotalcite, and lyserg. Examples of the plasticizer include mineral oil-based softeners, vegetable oil-based softeners, synthetic softeners, and synthetic plasticizers. Examples of the reinforcing material include carbon black and white carbon. Examples of the filler include calcium carbonates, basic magnesium carbonates, silicic acid, and silicates. Examples of the processing aid include fatty acids, fatty acid esters, fatty acid metal salts, and hydrocarbon-based waxes. Examples of the anti-aging agent include amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents, phosphorus-based anti-aging agents, and waxes.

[0037] The uses of biomass-derived chlorosulfonated polyethylene are not particularly limited and include various industrial parts such as automotive hoses, gas hoses, industrial hoses, wire coatings, draw cloths, packings, gaskets, rolls, or linings, rubber boats, life jackets, window breakers, escalator handrails, adhesives, and shoe soles.

Examples

[0038] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

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

[0040] (1) Raw rubber properties <Measurement of biomass content> In accordance with ASTM D6866, the radiocarbon C14 concentration of chlorosulfonated polyethylene was measured by accelerator mass spectrometry (AMS method), and the biomass content of chlorosulfonated polyethylene was calculated.

[0041] In ASTM D6866, the radiocarbon C14 concentration in the atmosphere in 1950 is used as a reference material, and the radiocarbon C14 concentration of the sample is measured. The ratio is defined as the biomass content. However, since the current radiocarbon C14 concentration in the atmosphere is increasing year by year, it is stipulated that a coefficient is multiplied by this value for correction. According to ASTM D6866-22, the current C14 concentration in the atmosphere 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. For the measurement of the chlorine content, about 20 mg of chlorosulfonated polyethylene was burned according to the oxygen flask combustion method, and 15 mL of a 1.7 wt% hydrazinium sulfate aqueous solution was used as the absorption solution and allowed to stand. After 40 minutes, the absorption solution was washed out with about 100 mL of pure water, and then the chloride ions were quantified by potentiometric titration with a 0.5 N silver nitrate aqueous solution using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., MC-3000, TS-3000), and the chlorine content was measured.

[0043] The sulfur content of biomass-derived chlorosulfonated polyethylene was measured by burning about 20 mg of chlorosulfonated polyethylene according to the oxygen flask combustion method, and about 10 mL of 3 wt% hydrogen peroxide solution was used as the absorption solution and allowed to stand. After 40 minutes, the absorption solution was washed out with about 40 mL of pure water, and then about 1 mL of acetic acid, about 100 mL of 2-propanol, and about 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] <Measurement of Molecular Weight> The molecular weight of a polymer solution obtained by dissolving 10 mg of biomass-derived chlorosulfonated polyethylene in 10 mL of THF was measured by GPC. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined in terms of polystyrene using standard polystyrene (manufactured by Tosoh Corporation). The measurement conditions are shown below.

[0045] · Model: (Product name) HLC8420GPC · Solvent: THF · Column temperature: 40 °C · Measurement concentration: 10 mg / 10 mL · Injection volume: 200 μL · Column: 2 pieces of TSKgel (registered trademark) G7000HXL (manufactured by Tosoh Corporation) → TSKgel (registered trademark) GMHXL (manufactured by Tosoh Corporation) <Measurement of glass transition temperature> Using a differential scanning calorimeter (DSC3500Sirius, manufactured by NETZSCH), under a nitrogen gas flow, the temperature was raised from -100 °C to 150 °C at a rate of 10 °C / min, and the starting point of the transition region in the measured DSC curve was defined as the glass transition temperature (Tg). Also, the top of the endothermic peak that appeared between 10 and 100 °C was defined as the melting point of the crystal (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 conversion, and its viscosity was measured with a B-type viscometer. The measurement was carried out after immersing the sample container in a constant temperature bath at 23 °C for 1 hour, then using a No. 3 rotor to measure at 30 rpm, and using the value after 60 seconds.

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

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

[0049] (2) Compound characteristics <Measurement of Mooney scorch> Chlorosulfonated polyethylene was kneaded according to JIS-K 6299, and the Mooney scorch ML(1) 125°C of the obtained compound was measured according to JIS-K 6300. Here, Vm is the minimum Mooney viscosity after the start of rotor rotation, and the scorch time t5 is an index of processing stability, which is the time when the Mooney viscosity increases by 5 from Vm.

[0050] <Rheometer vulcanization test> Using the RUBBER PROCESS ANALYZER RPA 2000 manufactured by ALPHA TECHNOLOGIES, measurements were carried out at 160°C for 45 minutes, and according to JIS K 6300, the minimum torque value (ML), the maximum torque value (MH), and the 90% vulcanization time (Tc90) were determined.

[0051] (3) Vulcanized rubber properties <Normal physical properties> Chlorosulfonated polyethylene was kneaded according to JIS-K 6299, and the obtained sample was vulcanized in a mold with a thickness of 2 mm. Then, the hardness (HS) was measured at 23°C using a durometer hardness tester in accordance with JIS-K 6253. The tensile strength (TB), elongation at break (EB), and 100% tensile stress (M100) were evaluated according to JIS-K 6251 under the conditions of a tensile speed of 500 mm / min and 23°C.

[0052] <Heat aging resistance> The vulcanized rubber of chlorosulfonated polyethylene was aged in a gear oven at 120°C for 72 hours in accordance with JIS K6257, and then the change in normal physical properties was evaluated.

[0053] Also, the details of the reagents used in the synthesis of chlorosulfonated polyethylene in the examples are as follows.

[0054] Raw material biopolyethylene 1: Grade name 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 3 ) Raw material petroleum - derived polyethylene 1: Petrothene (trademark) 228 - 1, manufactured by Tosoh Corporation, Melt mass - flow rate (JISK6922 - 1, temperature 190°C, load 2.16 kg) 1.5 g / 10 min, low - density polyethylene (density 0.924 g / cm 3 ) Raw material petroleum - derived polyethylene 2: Petrothene (trademark) 208, manufactured by Tosoh Corporation, Melt mass - flow rate (JISK6922 - 1, temperature 190°C, load 2.16 kg) 23 g / 10 min, low - density polyethylene (density 0.918 g / cm 3 ) Raw material petroleum - derived polyethylene 3: Nipolon Hard (registered trademark) 4030, manufactured by Tosoh Corporation, Melt mass - flow rate (JISK6922 - 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 Corporation Sulfuryl chloride: Manufactured by Sumitomo Seika Chemicals Co., Ltd. Pyridine: Manufactured by Fujifilm Wako Pure Chemical Corporation 2,2 - Bis(4 - glycidyloxyphenyl)propane: Manufactured by Tokyo Chemical Industry Co., Ltd. Also, the details of the compounding agents used in the examples are as follows.

[0055] Magnesium oxide (acid acceptor): Kyowa Mag #150 (manufactured by Kyowa Chemical Industry Co., Ltd.) Processing Aid 1: Spreader (registered trademark) R-300 (fatty acid ester) (manufactured by Kao Corporation) Processing Aid 2: Struktol WB-212 (manufactured by Ess & Ess Japan Co., Ltd.) Carbon (reinforcing agent): SRF Carbon Sheet (registered trademark) S (manufactured by Tokai Carbon Co., Ltd.) Plasticizer: Aliphatic dibasic acid ester DOZ (manufactured by Daihachi Chemical Industry Co., Ltd.) Vulcanizing agent for CSM: Dipentamethylenethiuram tetrasulfide (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Pentaerythritol (activator): Neutralizer (registered trademark) P (manufactured by Mitsubishi Chemical Corporation) Example 1 Under a nitrogen atmosphere, in a 40 L glass-lined autoclave, 605 g of raw material biopolyethylene 1, 1411 g of raw material biopolyethylene 2, and 10 L of 1,1,2-trichloroethane were dissolved at 110°C. To this polymer solution, 0.3 g of pyridine was added under the condition of 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 during the reaction was maintained at 0.2 MPa. After the dropwise addition was completed, the temperature of the reaction solution was lowered to 70°C, and nitrogen blowing was carried out for 2 hours under the condition of 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 to obtain biomass-derived chlorosulfonated polyethylene 1.

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

[0057]

Table 1

[0058] To 100 parts by weight of the obtained chlorosulfonated polyethylene, 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 kneader. Further, 2 parts by weight of a vulcanizing agent for CSM and 3 parts by weight of pentaerythritol were added using an open roll kneader to obtain chlorosulfonated polyethylene composition 1. For the obtained chlorosulfonated polyethylene composition 1, a Mooney scorch test and a rheometer vulcanization test of the unvulcanized rubber were carried out, and the results are shown in Table 2. Also, the obtained chlorosulfonated polyethylene composition 1 was press-vulcanized at 160 °C for 20 minutes to obtain a vulcanizate. A normal physical property test and a heat aging resistance test of the obtained vulcanizate were carried out. The results are shown in Table 2. From Table 2, it was comparable in terms of physical properties to chlorosulfonated polyethylene made from petroleum-derived polyethylene as a raw material.

[0059]

Table 2

[0060] Comparative Example 1 Petroleum-derived chlorosulfonated polyethylene 2 was obtained in the same manner as in Example 1 except that 907.2 g of petroleum-derived polyethylene 1 and 1108.8 g of petroleum-derived pre-polyethylene 2 were used as the raw materials for charging. The composition, Mooney viscosity, and raw rubber properties such as biomass content of the obtained chlorosulfonated polyethylene 2 were measured. The results are shown in Table 1. As shown in Table 1, the chlorine content was 29.9% by weight, the sulfur content was 1.3% by weight, the Mooney viscosity was 28, the biomass content was 0%, and the viscosity of a 25% by weight toluene solution was 2000 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] Regarding the obtained chlorosulfonated polyethylene composition 2, the Mooney scorch test and rheometer vulcanization test of the unvulcanized rubber were carried out, and the results are shown in Table 2. Also, the obtained chlorosulfonated polyethylene composition 2 was press-vulcanized at 160 °C for 20 minutes to obtain a vulcanizate. The normal physical properties and heat aging resistance test of the obtained vulcanizate were carried out. These results are shown in Table 2.

[0063] Example 2 Under a nitrogen atmosphere, in a 40 L glass-lined autoclave, 1008 g of raw material biopolyethylene 3 was dissolved in 10 L of 1,1,2-trichloroethane at 120 °C. To this polymer solution, 0.3 g of pyridine was added under the condition of 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 during the reaction was maintained at 0.2 MPa. After the dropping was completed, the temperature of the reaction solution was lowered to 70 °C, and nitrogen blowing was carried out for 2 hours under the condition of 70 °C. 18 g of 2,2-bis(4-glycidyloxyphenyl)propane was added to the reaction solution, and the solvent was removed with a drum dryer heated to 155 °C to obtain 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 wt%, the sulfur content was 0.9 wt%, the Mooney viscosity was 64, Mw / Mn was 3.5, the biomass degree was 98%, and the 10 wt% toluene solution viscosity was 300 mPa·s.

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

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

[0067] The properties of the raw rubber 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, 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] A 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. For the obtained chlorosulfonated polyethylene composition 4, a Mooney scorch test and a rheometer vulcanization test of the unvulcanized rubber were carried out, and the results are shown in Table 2. From Table 2, although Tc90 was almost equivalent to that of petroleum-derived chlorosulfonated polyethylene, t5 was longer than that of petroleum-derived chlorosulfonated polyethylene, and the processing stability was good. Further, the obtained chlorosulfonated polyethylene composition was press-vulcanized at 160 °C for 20 minutes to obtain a vulcanizate. A normal physical property and heat aging resistance test of the obtained vulcanizate were carried out. The results are shown in Table 2. From Table 2, the mechanical properties were equivalent to those of chlorosulfonated polyethylene made from petroleum-derived polyethylene as a raw material.

[0069] Comparative Example 2 A petroleum-derived chlorosulfonated polyethylene 5 was obtained in the same manner as in Example 2, except that the raw material bio-polyethylene 3 was changed to raw material petroleum-derived polyethylene 3.

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

Claims

1. Chlorosulfonated polyethylene with a biomass content of 10 to 100% as 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 10,000 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, by chlorosulfonating polyethylene with 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 Claims 1 to 9 and a compounding agent.

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