Chlorosulfonated polyethylene from biomass sources

Abstract

Provided is a chlorosulfonated polyethylene, which uses polyethylene from plants instead of polyethylene obtained from fossil fuels in the past as a raw material, thereby enabling reduction of environmental load (greenhouse gas generation) in a life cycle. The bio-based content of the chlorosulfonated polyethylene is 10 to 100% as measured according to ASTM D 6866.

Description

Technical Field

[0001] This invention relates to biomass chlorosulfonated polyethylene derived from plant-based raw materials. More specifically, this invention relates to a chlorosulfonated polyethylene comprising specific components. Background Technology

[0002] In recent years, with the growing calls for building a circular society, the utilization of biomass has gained attention in the materials field, with the aim of reducing reliance on petroleum-based feedstocks. Similarly, the manufacture of rubber materials using biomass-derived raw materials has attracted attention, leading to a wide range of research in this area.

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

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

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2014-024915

[0008] Non-patent literature

[0009] Non-Patent Document 1: NOK Corporation Press Release, March 25, 2022 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] This invention focuses on polyethylene as a raw material for chlorosulfonated polyethylene. By using plant-derived polyethylene instead of polyethylene derived from conventional fossil fuels as its raw material, chlorosulfonated polyethylene is provided that can reduce the environmental impact (greenhouse gas production) throughout its life cycle.

[0012] Problem Solving Methods

[0013] In order to solve the above problems, the inventors conducted in-depth research and completed the present invention. That is, the present invention relates to the following [1]~

[11] .

[0014] [1] A chlorosulfonated polyethylene having a bio-based content of 10 to 100% as determined by ASTM D 6866.

[0015] [2] According to the chlorosulfonated polyethylene described in [1], wherein,

[0016] The chlorine content is 10-50% by weight.

[0017] [3] The chlorosulfonated polyethylene according to [1] or [2], wherein,

[0018] The sulfur content is 0.4-5% by weight.

[0019] [4] Chlorosulfonated polyethylene according to any one of [1] to [3], wherein,

[0020] The glass transition temperature (Tg) measured using differential scanning calorimetry (DSC) is -40 to 30 °C.

[0021] [5] Chlorosulfonated polyethylene according to any one of [1] to [4], wherein,

[0022] The Mooney viscosity (ML(1+4) 100℃) is 10~150.

[0023] [6] The chlorosulfonated polyethylene according to any one of [1] to [5] has a viscosity of 100 to 10000 mPa·s for a 25% by weight toluene solution.

[0024] [7] Chlorosulfonated polyethylene according to any one of [1] to [6], wherein,

[0025] The ratio of number-average molecular weight Mn to weight-average molecular weight Mw, as determined by gel permeation chromatography (GPC), is 2.0 to 4.2.

[0026] [8] Chlorosulfonated polyethylene according to any one of [1] to [7], wherein,

[0027] The melting point (Tm) of the crystallization, determined by differential scanning calorimetry (DSC), is 30~50℃, and the heat of fusion (ΔH) calculated from the peak area of ​​this melting point is 0.01~1g / J.

[0028] [9] Chlorosulfonated polyethylene according to any one of [1] to [8], wherein,

[0029] The yellowness index YI, as determined by ASTM D 1925, is 20-60.

[0030]

[10] A method for manufacturing chlorosulfonated polyethylene according to any one of [1] to [9], comprising:

[0031] Polyethylene with a bio-based content of 10-100% as determined by ASTM D 6866 is chlorosulfonated.

[0032]

[11] A composition comprising chlorosulfonated polyethylene and a compounding agent as described in any one of [1] to [9].

[0033] The effects of the invention

[0034] The chlorosulfonated polyethylene of this invention has the same mechanical properties as chlorosulfonated polyethylene made from conventional fossil fuels, and can replace conventional chlorosulfonated polyethylene. The bio-based content is 10-100% as measured by ASTM D 6866, thus reducing the environmental impact (greenhouse gas production) over its life cycle. Detailed Implementation

[0035] The present invention will now be described in detail.

[0036] One aspect of the biomass-derived chlorosulfonated polyethylene of the present invention is chlorosulfonated polyethylene with a bio-based content of 10% to 100% as determined by ASTM D 6866. Furthermore, from the viewpoint of excellent processing stability and reduced environmental impact over its life cycle, chlorosulfonated polyethylene with a bio-based content of 30% or more is preferred.

[0037] Biomass refers to all renewable natural raw materials and their residues, including fungi, yeasts, algae, and bacteria, derived from plants or animals. The carbon in olefins obtained from biomass contains a certain amount of C14 isotopes derived from biomass (10⁻¹⁰). -12 (Left and right ratio).

[0038] Fossil fuels are substances formed from the fossilization of the remains of plants and animals such as petroleum, coal, natural gas, and shale gas over hundreds of millions of years through accumulation and compression. The carbon in olefins from fossil fuels has a much longer lifespan than the 5730-year half-life of the C14 isotope, so C14 isotopes from biomass cannot be detected.

[0039] Bio-based content refers to the proportion of naturally derived ingredients in a product. It can be determined by measuring the content of radioactive carbon C14 in substances found only in naturally derived materials. In this invention, the bio-based content can be calculated as follows: based on ASTM D 6866, the concentration of radioactive carbon C14 in chlorosulfonated polyethylene is determined using accelerator mass spectrometry (AMS), and its proportion to carbon from fossil fuels that does not contain radioactive carbon C14 is calculated.

[0040] Compared to materials derived from fossil fuels, the use of biomass byproducts is an effective means of reducing atmospheric carbon dioxide concentrations and efficiently limiting the greenhouse effect. Biomass byproducts have the added advantage of being incinerated at the end of their life cycle, producing only non-fossil carbon dioxide, and this effect is more pronounced with higher biomass content.

[0041] From the viewpoint of obtaining excellent softness and mechanical properties, 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.

[0042] From the viewpoint of obtaining sulfides with a suitable sulfur density, the sulfur content of 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.

[0043] From the viewpoint of balancing exceptionally good mechanical and processability properties, the Mooney viscosity (ML(1+4)100°C) of biomass-derived chlorosulfonated polyethylene is preferably 10 to 150, more preferably 20 to 120.

[0044] From the viewpoint of obtaining excellent softness and mechanical properties, the glass transition temperature (Tg) of biomass-derived chlorosulfonated polyethylene, as determined 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.

[0045] To obtain excellent mechanical and processability properties, the weight-average molecular weight of biomass-derived chlorosulfonated polyethylene is preferably 5,000 to 600,000, more preferably 10,000 to 500,000. Furthermore, to obtain excellent mechanical and processing stability, the ratio of number-average molecular weight (Mn) to weight-average molecular weight (Mw) is preferably 2.0 to 4.2, more preferably 3.0 to 4.0. It should be noted that the number-average molecular weight and weight-average molecular weight refer to the measured values ​​(converted to polystyrene values) based on gel permeation chromatography (hereinafter sometimes simply referred to as GPC).

[0046] The crystallization melting point (Tm) of biomass-derived chlorosulfonated polyethylene, determined by differential scanning calorimetry (DSC), is 30~50℃. From the viewpoint of obtaining excellent mechanical properties and processing stability, the heat of fusion (ΔH) calculated from the peak area of ​​this melting point is preferably 0.01~1 g / J.

[0047] From the viewpoint of imparting a yellow color to chlorosulfonated polyethylene, the yellowness index YI of biomass-derived chlorosulfonated polyethylene, as determined according to ASTM D 1925, is preferably 20 to 60.

[0048] When chlorosulfonated polyethylene is dissolved in an organic solvent for use as an impregnating agent (for fabric preparation), coating agent, adhesive, etc., from the viewpoint of balancing mechanical properties and operability, the viscosity of a 25% by weight toluene solution of biomass-derived chlorosulfonated polyethylene is preferably 100 to 10000 mPa·s, more preferably 300 to 3000 mPa·s.

[0049] The polyethylene used as a raw material for chlorosulfonated polyethylene derived from biomass is polyethylene with a bio-based content of 10% to 100% as determined by ASTM D 6866. It can be used alone or as a mixture of two or more types of polyethylene. Alternatively, if the bio-based content of the mixture is in the range of 10% to 100%, petroleum-derived polyethylene can also be used as the polyethylene in the mixture.

[0050] The main chain structure of polyethylene used as a raw material for chlorosulfonated polyethylene from biomass is not particularly limited, and examples include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene. Two or more types of polyethylene can be used as raw materials, either alone or in combination. When used for applications such as impregnation, coating, and adhesives, low-density polyethylene is preferred from the viewpoint of achieving excellent solubility in organic solvents.

[0051] The synthesis of chlorosulfonated polyethylene from biomass sources can be carried out using conventionally known methods. For example, a method involving dissolving the polyethylene in chlorine-based solvents such as carbon tetrachloride, chloroform, or 1,1,2-trichloroethane, and then blowing in chlorine gas in the presence of a free radical initiator, can be cited. There are no particular limitations on the reaction temperature, which is suitable for the range of 60–180 °C, and there are no particular limitations on the reaction pressure, which is suitable for atmospheric pressure to 1.0 MPa.

[0052] After the chlorination reaction is complete, residual chlorine and byproduct hydrogen chloride are removed from the reaction system by blowing in inert gases such as nitrogen under reflux of the solvent. The resulting chlorosulfonated polyethylene can then be separated from the solvent by methods such as steam distillation, drum drying, or extrusion drying, as needed.

[0053] The method for manufacturing chlorosulfonated polyethylene from biomass sources, as one aspect of the present invention, is not particularly limited. Examples include: a solution method in which polyethylene with a bio-based content of 10-100% as determined by ASTM D 6866 is uniformly dissolved in an inactive solvent and reacted; a suspension method in which polyethylene is suspended in a solvent and reacted; and a melt method in which polyethylene is melted under solvent-free conditions and reacted. Among these, the solution method, which uniformly chlorosulfonates the polyethylene, is preferred.

[0054] There are no particular limitations on the solvent used for chlorosulfonation in the solution process. From the viewpoint of solubility and reactivity, carbon tetrachloride, trichloroethane, tetrachloroethane, chloroform, chlorobenzene, etc. can be cited. From the viewpoint of particularly good reactivity, trichloroethane is preferred.

[0055] In this invention, the chlorosulfonating agent used for chlorosulfonating polyethylene is not particularly limited, and sulfur dioxide, chlorine, and sulfuryl chloride can be used alone or in combination. Additionally, catalysts that promote the chlorosulfonation reaction can be used as needed. Examples of catalysts include azo compounds and organic oxides. Examples of azo compounds include α,α'-azobisisobutyronitrile, azodicyclohexylformitrile, and 2,2'-azobis(2,4-dimethylpentanonitrile); examples of organic oxides include benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, and tert-butyl perbenzoate. From the perspective of high processing stability, azo compounds are preferred, and from the perspective of performing moderate chlorination and chlorosulfonation reactions, α,α'-azobisisobutyronitrile is particularly preferred. Furthermore, as a co-catalyst to promote the chlorosulfonation reaction as needed, amino compounds such as pyridine and quinoline, and phosphate ester compounds can be added.

[0056] The reaction temperature during chlorosulfonation is not particularly limited and can be appropriately selected based on the melting point of the raw material polyethylene, etc. However, considering reactivity and processability, 50~150°C is preferred, and 60~130°C is more preferred. Furthermore, the reaction pressure during chlorosulfonation is not particularly limited, for example, 0~1.0 MPa, but 0~0.6 MPa is preferred for achieving adequate chlorosulfonation.

[0057] After the chlorosulfonation reaction is complete, residual sulfur dioxide or hydrogen chloride in the reaction solution is removed by introducing nitrogen gas. Furthermore, removing sulfur dioxide or hydrogen chloride under reduced pressure is also not a problem.

[0058] In addition, antioxidants, stabilizers, and other additives can be added before or after the chlorosulfonation reaction. There are no particular limitations on the types of additives; examples include hindered phenolic antioxidants such as 4-tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, and triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], epoxidized polybutadiene, and epoxides such as bisphenol A resin. These can be used alone or in combination of two or more. There are no particular limitations on the timing of addition; however, considering ease of operation and additive efficiency, it is preferable to add the additive after the chlorosulfonation reaction and after the removal of residual gases.

[0059] There are no particular limitations on the method for separating the polymer and solvent from the polymer solution produced by chlorosulfonation; for example, steam distillation, drum dryer, extruder with vents, etc., can be used.

[0060] One embodiment of the composition of the present invention comprises the above-mentioned chlorosulfonated polyethylene and a compounding agent. The biomass-derived chlorosulfonated polyethylene of the present invention is primarily used in the form of a sulfide. As a method for obtaining the sulfide of the biomass-derived chlorosulfonated polyethylene of the present invention, the biomass-derived chlorosulfonated polyethylene and various compounding agents are compounded or mixed using a roller mill or Banbury mixer, followed by pressure vulcanization, steam vulcanization, high-frequency (UHF) vulcanization, or electron beam vulcanization. The vulcanization temperature is not particularly limited, but is 130-200°C, preferably 150-180°C. Alternatively, secondary vulcanization may be performed as needed. Secondary vulcanization is carried out in a heated oven at 140-180°C for 2-6 hours. Examples of various compounding agents include vulcanizing agents, vulcanization accelerators, acid scavengers, plasticizers, reinforcing agents, fillers, processing aids, and anti-aging agents, which can be used as needed.

[0061] Examples of vulcanizing agents include: inorganic vulcanizing agents such as sulfur, thiuram polysulfides, dithiocarbamates, oximes, nitrosamines, and organic peroxides. Examples of vulcanization accelerators include: thioureas, guanidines, thiazoles, sulfenamides, thiurams, dithiocarbamates, and xanthates. Examples of acid scavengers include: magnesium oxide, zinc oxide, hydrotalcite, and lead monoxide. 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 silica. Examples of fillers include: calcium carbonate, basic magnesium carbonate, silicic acid, and silicates. Examples of processing aids include: fatty acids, fatty acid esters, fatty acid metal salts, and hydrocarbon waxes. Examples of anti-aging agents include: amine-based anti-aging agents, phenol-based anti-aging agents, sulfur-based anti-aging agents, phosphorus-based anti-aging agents, and waxes.

[0062] There are no particular limitations on the uses of biomass-derived chlorosulfonated polyethylene. It can be used in various industrial parts such as automotive hoses, gas hoses, industrial hoses, wire sheathing, impregnation, padding, gaskets, rollers or liners, rubber boats, life jackets, windproof jackets, escalator handrails, adhesives and shoe soles.

[0063] Example

[0064] The present invention will be described in more detail below through embodiments, but the present invention is not limited to these embodiments.

[0065] It should be noted that the values ​​used in these embodiments were obtained according to the following measurement methods.

[0066] (1) Characteristics of raw rubber

[0067] <Determination of Bio-based Content>

[0068] According to ASTM D6866, the radioactive carbon C14 concentration of chlorosulfonated polyethylene was determined by accelerator mass spectrometry (AMS method), and the bio-based content of chlorosulfonated polyethylene was calculated.

[0069] ASTM D6866 specifies that the concentration of radioactive carbon C14 in the atmosphere in 1950 should be determined for both standard materials and samples, and the ratio should be used as the bio-based content. However, the concentration of radioactive carbon C14 in the atmosphere has been increasing year by year, therefore, it is specified that this value be multiplied by a factor for correction. Calculations were performed according to ASTM D6866-22, setting the current atmospheric C14 concentration at 100.0 pMC.

[0070] <Determination of Chlorine and Sulfur Content>

[0071] The chlorine content of biomass-derived chlorosulfonated polyethylene was determined using the combustion flask method. The determination was performed as follows: approximately 20 mg of chlorosulfonated polyethylene was burned using the oxygen flask combustion method, with 15 mL of a 1.7% (w / w) hydrazine sulfate aqueous solution as the absorbent and allowed to stand. After 40 minutes, the absorbent was rinsed with approximately 100 mL of pure water. The chlorine content was then determined by potentiometric titration using an automatic titration apparatus (Hiranuma Sangyo Co., Ltd., MC-3000, TS-3000) with a 0.5N silver nitrate aqueous solution.

[0072] The sulfur content of chlorosulfonated polyethylene derived from biomass was determined as follows: Approximately 20 mg of chlorosulfonated polyethylene was burned using the oxygen flask combustion method, with approximately 10 mL of 3% hydrogen peroxide water as the absorption solution, and allowed to stand. After 40 minutes, the absorption solution was washed 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 sulfur content was determined by spectrophotometric titration of sulfate ions in this solution using a 0.01 N barium acetate solution.

[0073] <Determination of molecular weight>

[0074] The molecular weight was determined by GPC of a polymer solution obtained by dissolving 10 mg of biomass-derived chlorosulfonated polyethylene in 10 mL of THF. It should be noted that the number-average molecular weight (Mn) and weight-average molecular weight (Mw) were calculated using standard polystyrene (Tosoh Corporation) and converted from polystyrene. The determination conditions are shown below.

[0075] Model: (Product Name) HLC8420GPC

[0076] Solvent: THF

[0077] Column temperature: 40℃

[0078] ·Measurement concentration: 10 mg / 10 mL

[0079] ·Injection volume: 200 μL

[0080] ·Chromatographic column: 2 pieces of TSKgel (registered trademark) G7000HXL (manufactured by Tosoh Corporation) → TSKgel (registered trademark) GMHXL (manufactured by Tosoh Corporation)

[0081] <Measurement of glass transition temperature>

[0082] Using a differential scanning calorimeter (manufactured by NETZSCH, DSC3500Sirius), with nitrogen gas flow, the starting point of the transition region in the DSC curve measured by heating from -100 °C to 150 °C at a rate of 10 °C / minute was taken as the glass transition temperature (Tg). In addition, the peak value of the endothermic peak appearing within 10 - 100 °C was taken as the melting point (Tm) of crystallization, and the heat of fusion (ΔH) was calculated from the peak area.

[0083] <Measurement of solution viscosity>

[0084] Chlorosulfonated polyethylene was dissolved in toluene to make its concentration 10% or 25% in terms of weight conversion, and its viscosity was measured using a B-type viscometer. After immersing the sample container in a constant temperature bath at 23 °C for 1 hour, measurement was carried out at 30 rpm using a No. 3 rotor, and the value after 60 seconds was used.

[0085] <Measurement of Mooney viscosity>

[0086] According to JIS K 6300, measurement was carried out using an L-type rotor under the conditions of preheating for 1 minute, rotor rotation time of 4 minutes, and 100 °C.

[0087] <Measurement of yellowness index YI>

[0088] Using a color difference meter (manufactured by KONICA MINOLTA, CR-5), according to ASTM D1925, the yellowness index YI of chlorosulfonated polyethylene was measured.

[0089] (2) Composite properties

[0090] <Measurement of Mooney Scorch>

[0091] Chlorosulfonated polyethylene was kneaded according to JIS-K 6299, and the Mooney Scorch ML(1)125 °C of the obtained composite was measured according to JIS-K 6300. It should be noted that 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 Vm rises by 5 Mooney viscosities.

[0092] <Rheometer Vulcanization Test>

[0093] The minimum torque value (ML), maximum torque value (MH), and 90% vulcanization time (Tc90) were determined by using a Rubber Process Analyzer RPA 2000 manufactured by ALPHA TECHNOLOGIES at 160°C for 45 minutes, in accordance with JIS K 6300.

[0094] (3) Properties of vulcanized rubber

[0095] <Normal Physical Properties>

[0096] Chlorosulfonated polyethylene was compounded according to JIS-K 6299, and the resulting samples were vulcanized using a 2 mm thick mold. Furthermore, the hardness (HS) was measured using a Durometer at 23°C according to JIS-K 6253. Tensile strength (TB), elongation at break (EB), and 100% tensile stress (M100) were evaluated according to JIS-K 6251 at a tensile speed of 500 mm / min and 23°C.

[0097] <Heat Aging Resistance>

[0098] According to JIS K6257, the changes in normal physical properties of chlorosulfonated polyethylene vulcanized rubber were evaluated after aging at 120°C for 72 hours in a gear oven.

[0099] In addition, the reagents used in the synthesis of chlorosulfonated polyethylene in the examples are described below.

[0100] Raw material: Bio-based polyethylene 1: Grade SPB208, Braskem, melt flow rate (ASTM D1238, temperature 190℃, load 2.16kg) 22g / 10min, low-density polyethylene (density 0.923g / cm³). 3 )

[0101] Raw material: Bio-based polyethylene 2: Grade SEB853, Braskem, melt flow rate (ASTM D1238, temperature 190℃, load 2.16kg): 2.7g / 10min, low-density polyethylene (density 0.923g / cm³). 3 )

[0102] Raw material: Bio-based polyethylene 3: Grade SHC7260, Braskem, melt flow rate (ASTM D1238, temperature 190℃, load 2.16kg): 7.2g / 10min, high-density polyethylene (density 0.959g / cm³).3 )

[0103] Raw material: Petroleum-derived polyethylene 1: Petrothene (trademark) 228-1, manufactured by Tosoh Corporation. Melt flow rate (JIS K6922-1, temperature 190℃, load 2.16kg): 1.5g / 10min. Low-density polyethylene (density 0.924g / cm³). 3 )

[0104] Raw material: Petroleum-derived polyethylene 2: Petrothene (trademark) 208, manufactured by Tosoh Corporation. Melt flow rate (JIS K6922-1, temperature 190℃, load 2.16kg) 23g / 10min. Low-density polyethylene (density 0.918g / cm³). 3 )

[0105] Raw material: Petroleum-derived polyethylene 3: NipolonHard (registered trademark) 4030, manufactured by Tosoh Corporation. Melt flow rate (JISK6922-1, temperature 190℃, load 2.16kg): 4.8g / 10min. High-density polyethylene (density 0.964g / cm³). 3 )

[0106] 1,1,2-Trichloroethane: Manufactured by Tosoh Corporation

[0107] α,α'-Azobisisobutyronitrile: Manufactured by Fuji Film and Koei Tecmo Pharmaceutical Co., Ltd.

[0108] Sulfuryl chloride: manufactured by Sumitomo Seika Co., Ltd.

[0109] Pyridine: Manufactured by Fuji Film and Koei Tecmo Chemical Co., Ltd.

[0110] 2,2-Bis(4-glycidyl etheroxyphenyl)propane: Manufactured by Tokyo Chemical Industry Co., Ltd.

[0111] In addition, the complexing agents used in the examples are described below.

[0112] Magnesium oxide (acid absorber): Kyowamag#150 (manufactured by Kyowa Chemical Industry Co., Ltd.)

[0113] Processing aid 1: Splender (registered trademark) R-300 (fatty acid ester) (manufactured by Kao Corporation)

[0114] Processing aid 2: Struktol WB-212 (manufactured by Sands Japan Co., Ltd.)

[0115] Carbon (reinforcing agent): SRF Carbon Seast (registered trademark) (manufactured by Tokai Carbon Co., Ltd.)

[0116] Plasticizer: Aliphatic diester DOZ (manufactured by Daihachi Chemical Co., Ltd.)

[0117] CSM vulcanizing agent: Dipentamethylene thiuram tetrasulfide (manufactured by Ouchi Shinsei Chemical Co., Ltd.)

[0118] Pentaerythritol (activator): Neutizer (registered trademark) P (manufactured by Mitsubishi Chemical Co., Ltd.)

[0119] Example 1

[0120] Under a nitrogen atmosphere, 605 g of bio-based polyethylene 1 and 1411 g of bio-based polyethylene 2 were dissolved in 10 L of 1,1,2-trichloroethane at 110 °C in a 40 L enamel-lined high-pressure reactor. At 110 °C, 0.3 g of pyridine was added to the polymer solution, followed by dropwise addition over 120 minutes of a solution containing 2.1 g of α,α'-azobisisobutyronitrile and 3.8 kg of thioyl chloride dissolved in 1 kg of 1,1,2-trichloroethane. The pressure inside the reactor was maintained at 0.2 MPa. After the addition was complete, the temperature of the reaction solution was lowered to 70 °C, and nitrogen was introduced at 70 °C for 2 hours. 33 g of 2,2-bis(4-glycidyloxyphenyl)propane was added to the reaction solution, and the solvent was removed using a rotary dryer heated to 155 °C to obtain biomass-derived chlorosulfonated polyethylene 1.

[0121] The composition, Mooney viscosity, bio-based content, and other raw rubber properties of the obtained chlorosulfonated polyethylene 1 were determined. 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 bio-based content was 99%, and the viscosity of the 25 wt% toluene solution was 1700 mPa·s.

[0122]

[0123] Using an open-faced mixer, 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 to 100 parts by weight of chlorosulfonated polyethylene 1. Then, 2 parts by weight of CSM vulcanizing agent and 3 parts by weight of pentaerythritol were added using the open-faced mixer to obtain chlorosulfonated polyethylene composition 1. Mooney Scorch test and rheometer vulcanization test were performed on the obtained chlorosulfonated polyethylene composition 1, and the results are shown in Table 2. In addition, the obtained chlorosulfonated polyethylene composition 1 was subjected to pressure vulcanization at 160°C for 20 minutes to obtain a sulfide. The normal physical properties and heat aging resistance tests of the obtained sulfide were performed. The results are shown in Table 2. As shown in Table 2, the physical properties are not inferior to those of chlorosulfonated polyethylene made from petroleum-derived polyethylene.

[0124]

[0125] Comparative Example 1

[0126] The added raw materials were set as 907.2 g of petroleum-derived polyethylene 1 and 1108.8 g of petroleum-derived polyethylene 2. Otherwise, petroleum-derived chlorosulfonated polyethylene 2 was obtained in the same manner as in Example 1. The composition, Mooney viscosity, bio-based content, and other raw rubber properties of the obtained chlorosulfonated polyethylene 2 were determined. 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 bio-based content was 0%, and the viscosity of a 25 wt% toluene solution was 2000 mPa·s.

[0127] Chlorosulfonated polyethylene 2 of petroleum origin was used instead of chlorosulfonated polyethylene 1 of biomass origin. Otherwise, chlorosulfonated polyethylene composition 2 was obtained in the same manner as in Example 1.

[0128] For the obtained chlorosulfonated polyethylene composition 2, Mooney Scorch test and rheometer vulcanization test of unvulcanized rubber were performed, and the results are shown in Table 2. In addition, the obtained chlorosulfonated polyethylene composition 2 was subjected to pressure vulcanization at 160°C for 20 minutes to obtain a vulcanizate. The normal physical properties and heat aging resistance tests of the obtained vulcanizate were performed. The results are shown in Table 2.

[0129] Example 2

[0130] Under a nitrogen atmosphere, 1008 g of bio-based polyethylene 3 was dissolved in 10 L of 1,1,2-trichloroethane in a 40 L enamel-lined high-pressure reactor at 120 °C. At 110 °C, 0.3 g of pyridine was added to the polymer solution, followed by the dropwise addition of a solution containing 2.1 g of α,α'-azobisisobutyronitrile and 3.8 kg of thiocyanate chloride dissolved in 1 kg of 1,1,2-trichloroethane over 70 minutes. The pressure inside the reactor was maintained at 0.2 MPa. After the addition was complete, the temperature of the reaction solution was lowered to 70 °C, and nitrogen flow was applied 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 rotary dryer heated to 155 °C to obtain biomass-derived chlorosulfonated polyethylene 3.

[0131] The raw rubber properties of the obtained chlorosulfonated polyethylene 3 were determined. 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, the Mw / Mn ratio was 3.5, the bio-based content was 98%, and the viscosity of 10 wt% toluene solution was 300 mPa·s.

[0132] Magnesium oxide (MgO) was added to 100 parts by weight of chlorosulfonated polyethylene (CSM) 3 using an open-faced mixer. Then, 2 parts by weight of CSM vulcanizing agent and 3 parts by weight of pentaerythritol were added using the same open-faced mixer to obtain chlorosulfonated polyethylene composition 3. Mooney Scorch test and rheometer vulcanization test were performed on the unvulcanized rubber of the obtained chlorosulfonated polyethylene composition 3. The results are shown in Table 2. Table 2 shows that although the Tc90 is almost the same as that of petroleum-derived chlorosulfonated polyethylene, the t5 is longer, indicating good processing stability. Furthermore, the obtained chlorosulfonated polyethylene composition was subjected to pressure vulcanization at 160°C for 20 minutes to obtain a sulfide. The normal physical properties and heat aging resistance tests of the obtained sulfide were performed. The results are shown in Table 2. Table 2 shows that the mechanical properties of this product are at the same level as those of chlorosulfonated polyethylene derived from petroleum.

[0133] Example 3

[0134] The added raw material polyethylene was set as 806g of bio-based polyethylene 3 and 202g of raw material polyethylene 3 derived from petroleum. Otherwise, biomass-derived chlorosulfonated polyethylene 4 was obtained in the same manner as in Example 2.

[0135] The raw rubber properties of the obtained chlorosulfonated polyethylene 4 were determined. The results are shown in Table 1. As shown in Table 1, the chlorine content is 35.2 wt%, the sulfur content is 0.9 wt%, the Mooney viscosity is 61, the Mw / Mn ratio is 3.8, the bio-based content is 78%, and the viscosity of 10 wt% toluene solution is 460 mPa·s.

[0136] Chlorosulfonated polyethylene 4 was used instead of chlorosulfonated polyethylene 3, and otherwise, chlorosulfonated polyethylene composition 4 was obtained in the same manner as in Example 2. Mooney-Scorch test and rheometer vulcanization test were performed on the obtained chlorosulfonated polyethylene composition 4, and the results are shown in Table 2. As shown in Table 2, although Tc90 is almost the same as that of petroleum-derived chlorosulfonated polyethylene, t5 is longer than that of petroleum-derived chlorosulfonated polyethylene, indicating good processing stability. Furthermore, the obtained chlorosulfonated polyethylene composition was subjected to pressure vulcanization at 160°C for 20 minutes to obtain a sulfide. The normal physical properties and heat aging resistance tests of the obtained sulfide were performed. The results are shown in Table 2. As shown in Table 2, the mechanical properties are at the same level as those of chlorosulfonated polyethylene made from petroleum-derived polyethylene.

[0137] Comparative Example 2

[0138] The raw material bio-based polyethylene 3 was set as polyethylene 3 derived from petroleum. Otherwise, petroleum-derived chlorosulfonated polyethylene 5 was obtained in the same manner as in Example 2.

[0139] The raw rubber properties of the obtained chlorosulfonated polyethylene 5 were determined. 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 ratio was 4.6, the bio-based content was 0%, and the viscosity of a 10 wt% toluene solution was 640 mPa·s. Chlorosulfonated polyethylene 5 was used instead of chlorosulfonated polyethylene 3 from biomass sources, and chlorosulfonated polyethylene composition 5 was obtained in the same manner as in Example 2. Mooney Scorch test and rheometer vulcanization test were performed on the obtained chlorosulfonated polyethylene composition 5, and the results are shown in Table 2. In addition, the obtained chlorosulfonated polyethylene composition was subjected to pressure vulcanization at 160°C for 20 minutes to obtain a sulfide. The normal physical properties and heat aging resistance tests of the obtained sulfide were performed. The results are shown in Table 2.

[0140] The present invention has been described in detail and with reference to specific embodiments, but it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the essence and scope of the present invention.

[0141] It should be noted that the entire contents of the description, claims and abstract of Japanese Patent Application Nos. 2024-000795 and 2024-000796, filed on January 5, 2024, are incorporated herein by reference as disclosure of the present invention.

Claims

1. A chlorosulfonated polyethylene having a bio-based content of 10-100% as determined according to ASTM D 6866.

2. The chlorosulfonated polyethylene according to claim 1, wherein, The chlorine content is 10-50% by weight.

3. The chlorosulfonated polyethylene according to claim 1, wherein, The sulfur content is 0.4-5% by weight.

4. The chlorosulfonated polyethylene according to claim 1, wherein, The glass transition temperature (Tg) measured using differential scanning calorimetry (DSC) is -40 to 30 °C.

5. The chlorosulfonated polyethylene according to claim 1, wherein, The Mooney viscosity (ML(1+4) 100℃) is 10~150.

6. The chlorosulfonated polyethylene according to claim 1, wherein the viscosity of its 25% by weight toluene solution is 100~10000 mPa·s.

7. The chlorosulfonated polyethylene according to claim 1, wherein, The ratio of number-average molecular weight Mn to weight-average molecular weight Mw, as determined by gel permeation chromatography (GPC), is 2.0 to 4.

2.

8. The chlorosulfonated polyethylene according to claim 1, wherein, The melting point (Tm) of the crystallization, determined by differential scanning calorimetry (DSC), is 30~50℃, and the heat of fusion (ΔH) calculated from the peak area of ​​this melting point is 0.01~1g / J.

9. The chlorosulfonated polyethylene according to claim 1, wherein, The yellowness index YI, as determined by ASTM D 1925, is 20-60.

10. A method for manufacturing chlorosulfonated polyethylene according to any one of claims 1 to 9, comprising: Polyethylene with a bio-based content of 10-100% as determined by ASTM D 6866 is chlorosulfonated.

11. A composition comprising chlorosulfonated polyethylene and a compounding agent as described in any one of claims 1 to 9.

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