JP5115188B2 - Chlorosulfonated ethylene homopolymer, production method and use thereof - Google Patents

Description

  The present invention relates to a narrow molecular weight distribution chlorosulfonated polyethylene, a method for producing the same, and an application thereof.

  Chlorosulfonated polyethylene produced by chlorinating and chlorosulfonated polyethylene is excellent in weather resistance, ozone resistance, flame resistance, oil resistance, mechanical strength, lightness and the like. Therefore, for example, automotive hoses, gas hoses, industrial hoses, wire coverings, pulling cloths, packings, gaskets, rolls, linings and other industrial parts, rubber boats, life jackets, window breakers, escalator handrails and adhesives, etc. in use. Compared to the halogen-based elastomer chloroprene rubber, its heat resistance, weather resistance, and ozone resistance are excellent, and it is positioned as a special rubber with higher performance.

  Despite these excellent properties, chlorosulfonated polyethylene compositions are inferior in workability and processability. As an example, it is easy to stick to the roll during the kneading operation with an open roll or a calender roll, and a part of the composition adheres to the die in the extrusion process.

  For this reason, when processing chlorosulfonated polyethylene, processability is improved by adding processing aids such as various soaps, polyhydric alcohols, low molecular weight polyethylene, fatty acid esters and waxes (for example, patent documents). 1, Patent Document 2).

  However, there is a limit to the improvement of processability by such additives, and it is not preferable to use a large amount of additives because it causes a decrease in mechanical properties and poor adhesion.

  For this reason, improvement of workability | operativity and workability of chlorosulfonated polyethylene which does not impair mechanical physical properties is desired.

Japanese Patent No. 3619913 Japanese Patent Laid-Open No. 11-21382

  In order to solve the problems of the prior art, the object of the present invention is excellent in the roll workability of the composition and the die cleaning property of the extruder, the die swell during extrusion is small, and the tensile stress of the vulcanizate is low. It is to provide a large chlorosulfonated polyethylene.

  In order to solve the problems of the prior art, the present inventors have intensively studied paying attention to the molecular weight distribution of chlorosulfonated polyethylene, and as a result, completed the present invention. That is, in the present invention, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 3.5 or less, and the ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) is 2.7 or less. A chlorosulfonated polyethylene.

  The present invention is described in detail below.

  The chlorosulfonated polyethylene of the present invention has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 3.5 or less and a Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio of 2. 7 or less.

Here, the Z average molecular weight (Mz) is a kind of average molecular weight of a high molecular substance, and is an average molecular weight that sharply reflects the existence of a molecular species having a high molecular weight. “Molecules of molecular weight M _j contained in a polymer” When the number of N is N _j , the Z average molecular weight is an average molecular weight defined by Mz = ΣM _j ³ N _j / ΣM _j ² N _j and is obtained from a sedimentation equilibrium method or the like. ”(New Edition Polymer Dictionary) Pp. 236 to 237). The weight average molecular weight (Mw) is defined as Mw = ΣM _i ² N _i / ΣM _i N _i (New Edition Polymer Dictionary, page 417). The number average molecular weight (Mn) is defined as Mn = ΣM _i N _i / ΣN _i (New Edition Polymer Dictionary, page 417). The weight average molecular weight (Mw) / number average molecular weight (Mn) ratio is obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn), and the Z average molecular weight (Mz) / weight average molecular weight. The (Mw) ratio is obtained by dividing the Z average molecular weight (Mz) by the weight average molecular weight (Mw).

  The molecular weight of the chlorosulfonated polyethylene and the polyethylene used as the raw material in the present invention can be measured with a general GPC (gel permeation chromatography) apparatus.

  The weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of the chlorosulfonated polyethylene of the present invention is 3.5 or less, preferably 3.0 or less. Is good. When the ratio of the weight average molecular weight (Mw) / number average molecular weight (Mn) of the chlorosulfonated polyethylene exceeds 3.5, the chlorosulfonated polyethylene tends to stick to the roll, and the die cleaning property of the extruder also deteriorates.

  Furthermore, the ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) of the chlorosulfonated polyethylene of the present invention is 2.7 or less, preferably 2.4 or less, and the vulcanizate has a large tensile stress, And the die swell at the time of extrusion of a composition is small. When the ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) of chlorosulfonated polyethylene exceeds 2.7, the tensile stress of the vulcanizate decreases, and the die swell at the time of extrusion of the composition increases. .

  The chlorosulfonated polyethylene of the present invention has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 4.0 or less, and a Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio of 2. It is obtained from chlorination and chlorosulfonation using polyethylene of 7 or less as a raw material. Furthermore, a polyethylene having a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 3.0 or less and a Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio of 2.4 or less. It is more preferable to use a raw material in order to produce chlorosulfonated polyethylene having a larger tensile stress and a smaller die swell. When polyethylenes having different molecular weights and / or molecular weight distributions are blended, if the molecular weight distribution of the blend is within the above range, it is suitably used as a raw material for the chlorosulfonated polyethylene of the present invention.

  Polyethylene as a raw material is generally produced by low-density polyethylene by radical polymerization under high temperature and high pressure, and by high-density polyethylene by coordination anionic polymerization using a polymerization catalyst under relatively mild conditions. Linear low density polyethylene is produced by copolymerization of α-olefins such as 1-butene and 1-hexene. Low-density polyethylene contains radical initiators such as peroxides, and high-density polyethylene and linear low-density polyethylene contain Ziegler-Natta catalysts, which are composed of titanium chloride and organoaluminum compounds, and chromium compounds such as chromium oxide. Used as a catalyst. By using a metallocene catalyst, a polymer having a very uniform molecular weight and composition can be produced.

Regarding the density of polyethylene, high-density polyethylene of 930 kg / m ³ or more is preferably used in applications requiring high heat resistance and oil resistance, and direct use of less than 930 kg / m ³ in applications requiring high low-temperature characteristics. A chain low density polyethylene is preferably used.

  The method of obtaining the chlorosulfonated polyethylene of the present invention is a method of chlorinating and chlorosulfonated polyethylene. For example, polyethylene is inactive in halogenation reactions such as chloroform, trichloroethane, tetrachloroethane, monochlorobenzene, chlorofluorobenzene and the like. Examples thereof include a solution method in which the reaction is performed in a homogeneous system by dissolving in a solvent, a suspension method in which polyethylene is suspended in a solvent and a reaction, and a gas phase method in which the reaction is performed by suspending polyethylene in the gas phase. Among these, the solution method is preferable when considering the flexibility of rubber. Examples of the chlorinating agent and chlorosphoning agent used include chlorine and sulfurous acid gas, chlorine and sulfuryl chloride, and sulfuryl chloride alone.

  A general method for producing chlorosulfonated polyethylene by the solution method is shown below.

  After dissolving polyethylene in a solvent to make a uniform solution, the reaction is carried out by adding a radical generator and sulfuryl chloride to the reaction solution. The reaction temperature is not particularly limited, but is 30 ° C. to 180 ° C., and the reaction pressure is not particularly limited, but normal pressure to 1.0 megapascal is appropriate. During the reaction, the generated hydrogen chloride and sulfurous acid gas are continuously purged out of the reaction system. Examples of the radical generator include azo radical generators such as α, α′-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, and 2,2′-azobis (2,4-dimethylvaleronitrile), and benzoyl peroxide. And organic peroxide radical generators such as t-butyl peroxide and acetyl peroxide. Moreover, you may irradiate an ultraviolet-ray instead of using a radical generator. When the reaction is carried out using sulfuryl chloride, an amine compound such as pyridine, quinoline, dimethylaniline, nicotine, or piperidine is used as a co-catalyst as needed in order to add a chlorosphon group.

  The amount of polyethylene to be dissolved is not particularly limited, but is preferably 5 to 30% by weight in order to appropriately maintain the viscosity during the reaction. After completion of the reaction, hydrogen chloride and sulfurous acid gas dissolved in the solution are removed from the reaction system by blowing an inert gas such as nitrogen under reflux of the solvent. If necessary, an epoxy compound is added as a stabilizer. In the obtained chlorosulfonated polyethylene solution, the polymer and the solvent are separated by steam distillation, drum drying, extrusion drying or the like.

  When the vulcanized product using the chlorosulfonated polyethylene of the present invention is blended, kneaded and vulcanized under the same conditions, it has a higher tensile stress than other chlorosulfonated polyethylene vulcanized products exhibiting the same Mooney viscosity.

  The chlorosulfonated polyethylene of the present invention is used for various industrial parts such as automobile hoses, gas hoses, industrial hoses, wire coverings, draw cloths, packings, gaskets, rolls or linings, rubber boats, life jackets, window breakers, escalators. In order to sufficiently adapt to use in handrails and adhesives, etc., a chlorosulfonated polyethylene composition obtained by mixing a compounding agent with 100 parts by weight of chlorosulfonated polyethylene at the following blending ratio is subjected to the following 300% tension. The 300% tensile stress measured by the stress measurement method is preferably 22 MPa or more.

<Combination ratio>
Magnesium oxide: 4 parts by weight, special ester wax (manufactured by Kao Corporation: Splendor (trademark) R-300): 1 part by weight, specially selected special wax (manufactured by Ouchi Shinsei Chemical Co., Ltd .: Sannok (trademark) -N) : 2 parts by weight, SRF carbon: 40 parts by weight, activated calcium carbonate: 30 parts by weight, di-n-octyl phthalate: 20 parts by weight <Measurement method of 300% tensile stress>
After kneading for 3 minutes at 63 rpm in a closed kneader (OOC type 4.3L Banbury mixer, manufactured by Kobe Steel), dipentamethylene tiraum tetrasulfide (Ouchi Shinsei Chemical Co., Ltd .: 2 parts by weight of Noxeller (trademark) TRA) and 3 parts by weight of pentaerythritol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Neuiser (trademark) P) are added and kneaded at 40 ° C. for 10 minutes. Next, the composition is press-vulcanized for 30 minutes at a pressure of 15 MPa and a temperature of 160 ° C. using a 150 mm × 150 mm × 2 mm mold. In accordance with JIS-K-6251, the vulcanized rubber sheet is punched out with a No. 3 dumbbell and pulled at 500 mm / min to measure 300% tensile stress.

  The composition using the chlorosulfonated polyethylene of the present invention has a smaller die swell than other chlorosulfonated polyethylene compositions exhibiting the same Mooney viscosity when blending and kneading are performed under the same conditions.

  In order to maintain the shape of the chlorosulfonated polyethylene of the present invention in applications such as various industrial parts such as automobile hose, gas hose, industrial hose, wire coating, draw cloth, packing, gasket, roll or lining, A chlorosulfonated polyethylene composition obtained by mixing a compounding agent with 100 parts by weight of chlorosulfonated polyethylene at the following compounding ratio is 65% or less in die swell measured by the following method for measuring die swell. preferable.

<Combination ratio>
Magnesium oxide: 4 parts by weight, SRF carbon: 40 parts by weight, activated calcium carbonate: 30 parts by weight, di-n-octyl phthalate: 20 parts by weight <Die swell measurement method>
The mixture was kneaded at 63 rpm for 3 minutes in a closed kneader (OOC type 4.3L Banbury mixer manufactured by Kobe Steel). Next, the composition was compliant with ASTM-D-2230 Garbage Die Extrusion Test, extruder: 50 mmφ, L / D = 8/1, rotation speed: 30 rpm, temperature: cylinder; 70 ° C., head: 70 ° C., Die: Extrude at 80 ° C. and measure die swell.

  The amount of chlorine in the chlorosulfonated polyethylene of the present invention is not particularly limited, but is preferably 5.0 to 50.0% by weight in order to maintain cold resistance and bending fatigue.

  Further, the amount of sulfur of the chlorosulfonated polyethylene of the present invention is a scale indicating the amount of chlorosulfone groups acting as a crosslinking point, and is not particularly limited, but useful mechanical strength, sufficient tensile strength, tensile stress and In order to obtain elongation at break, 0.3 to 3.0% by weight is preferable.

  A vulcanizing agent, a vulcanization accelerator, an acid acceptor, a plasticizer, a reinforcing agent, a filler, a processing aid, an antiaging agent, and the like are added to the chlorosulfonated polyethylene of the present invention as necessary.

  Examples of the vulcanizing agent include inorganic vulcanizing agents such as magnesium oxide and lizage, maleimide compounds such as N, N′-m-phenylene dimaleimide, and organic oxides such as dicumyl peroxide. Examples of the vulcanization accelerator include thiuram compounds such as dipentamethylene thiuram tetrasulfide, tetramethyltylium disulfide, and tetraethyltylium disulfide, 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline, Examples include dibutyldithiocarbamic acid and 2-mercaptobenzimidazole. Examples of the acid acceptor include metal oxides such as magnesium oxide, resurge, calcium hydroxide, metal hydroxides, hydrotalcite, and the like. Examples of the plasticizer include di (2-ethylhexyl) phthalate, sebacic acid (di-2-ethylhexyl), tristritate tris (2-ethylhexyl), and the like. Examples of the reinforcing agent and filler include carbon black, white carbon, calcium carbonate, clay, and talc. Examples of the processing aid include low molecular weight polyethylene, metal soap, and stearic acid. Examples of the anti-aging agent include amine-based anti-aging agents and phenol-based anti-aging agents.

  These are blended and kneaded with a roll or Banbury mixer, and then press vulcanization, steam vulcanization, high frequency (UHF) vulcanization, electron beam vulcanization, or the like is performed.

  The chlorosulfonated polyethylene of the present invention has a good roll workability of the composition and a die cleaning property of the extruder, a small die swell at the time of extrusion, and a large tensile stress of the vulcanizate. Hose for automobiles, gas hoses, industrial hoses, wire coverings, pulling cloths, packings, gaskets, rolls or linings, etc., rubber boats, life jackets, window breakers, handrails and escalators It is suitably used for the agent. Particularly for hose applications, the die swell is small, which is more preferable. For example, automobile hoses and the like can be manufactured by molding rubber filled in a cylinder by extruding it from a die having various shapes with a piston and vulcanizing it at 120 ° C. to 200 ° C.

  As described above, the chlorosulfonated polyethylene of the present invention has good roll workability of the composition, excellent die cleaning property of the extruder, small die swell at the time of extrusion, and high tensile stress of the vulcanizate. There is an effect.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these. Unless otherwise specified, commercially available reagents were used.

  Various physical properties were measured according to the following methods.

<Density>
The density of polyethylene as a raw material for chlorosulfonated polyethylene was measured according to JIS-K-6760 (1995).

<Melt flow rate (MFR)>
The melt flow rate (MFR) of polyethylene as a raw material for chlorosulfonated polyethylene was measured under the conditions of 190 ° C. and a load of 21.18 N in accordance with JIS-K-6922-1.

<Molecular weight of high-density polyethylene>
The molecular weight of the high density polyethylene was measured by the gel permeation chromatography method under the following measurement conditions.

  Column: Tosoh Co., Ltd. GMHHhr-H (20) × 3, solvent: 1,2,4-trichlorobenzene (for HPLC) + bishydroxytoluene (0.05 wt%), flow rate: 1.0 mL / min, column Temperature: 140 ° C., sample concentration: 1.0 mg / ml, detector: HLC-8121GPC / HT manufactured by Tosoh Corporation, detection method: RI method, calibration curve: converted to polyethylene.

<Molecular weight of chlorosulfonated polyethylene>
The molecular weight of chlorosulfonated polyethylene was measured by the gel permeation chromatography method under the following measurement conditions.

Column: Two GMH6 manufactured by Tosoh Corporation, one XL connected, solvent: tetrahydrofuran, flow rate: 1.2 mL / min, pressure: 44-45 kg / cm ² , temperature: 38 ° C., sample concentration: 0.01 Weight%, detector: HLC-82201 GPC manufactured by Tosoh Corporation, detection method: RI method, calibration curve: polystyrene conversion.

<Weight average molecular weight (Mw), number average molecular weight (Mn) and Z average molecular weight (Mz)>
The weight average molecular weight (Mw), number average molecular weight (Mn), and Z average molecular weight (Mz) are the elution volumes at the elution peak using nine monodisperse samples with molecular weights of 2,500 to 6,200,000 as references. The molecular permeation chromatogram was converted into a molecular weight distribution curve by using a composition curve between the molecular weight and the molecular weight.

<Chlorine content, sulfur content>
The chlorine content and sulfur content of chlorosulfonated polyethylene were measured by the combustion flask method.

  In the measurement of the amount of chlorine, about 30 mg of chlorosulfonated polyethylene was first combusted according to the oxygen combustion method in a combustion flask containing 15 mL of a 1.7 wt% hydrazinium sulfate aqueous solution as an absorbing solution, and left for 30 minutes. Next, this absorbing solution was washed out with about 100 mL of pure water, and chloride ions were quantified by potentiometric titration with an aqueous silver nitrate solution having a concentration of 0.05N.

  On the other hand, in the measurement of the amount of sulfur, first, about 30 mg of chlorosulfonated polyethylene was burned according to the oxygen combustion method in a combustion flask containing 10 mL of 3% by weight hydrogen peroxide as an absorbing solution, and left for 30 minutes. Next, after washing out this absorbing solution with about 40 mL of pure water, 1 mL of acetic acid, about 100 mL of 2-propanol, and about 0.47 mL of Arsenazo III are added, and the amount of sulfur is determined by a photometric titration method using a barium acetate solution with a concentration of 0.01 N. It was measured.

<Mooney viscosity>
The Mooney viscosity of the chlorosulfonated polyethylene was measured according to JIS-K-6300-1, using a L-shaped rotor at 100 ° C. for 1 minute of preheating and 4 minutes after starting the rotor.

<Die swell and die cleanability>
Evaluation of the die swell and die cleaning property of the chlorosulfonated polyethylene composition was performed by the following method.

  First, a compounding agent was mixed with 100 parts by weight of chlorosulfonated polyethylene by the following formulation A, and kneaded at 63 rpm for 3 minutes with a closed kneader (OOC type 4.3 L Banbury mixer manufactured by Kobe Steel). Next, the composition was compliant with ASTM-D-2230 Garbage Die Extrusion Test, extruder: 50 mmφ, L / D = 8/1, rotation speed: 30 rpm, temperature: cylinder; 70 ° C., head: 70 ° C., Die: Extruded at 80 ° C. to evaluate die swell. The die cleaning property was evaluated in three stages: ◎: no deposit, ○: little deposit, ×: deposit.

<Roll workability>
The roll workability test of the chlorosulfonated polyethylene composition was evaluated by the following method.

  First, a compounding agent was mixed with 100 parts by weight of chlorosulfonated polyethylene by the following formulation A, and kneaded at 63 rpm for 3 minutes with a closed kneader (OOC type 4.3 L Banbury mixer manufactured by Kobe Steel). Next, 700 g of the composition was wound around a roll with a 10-inch open roll made by Toyo Seiki at a guide width of 22 cm, a roll gap of 2.4 mm, and a roll surface temperature of 62 ° C. for 3 minutes, and then cut out. The workability at this time was evaluated in three stages: ◎: very good without roll stickiness, ○: little roll stickiness, ×: roll stickiness.

<Tensile properties and hardness>
The tensile properties and hardness of the chlorosulfonated polyethylene vulcanizate were evaluated by the following methods.

  After 100 parts by weight of the chlorosulfonated polyethylene of the present invention is mixed with the following B compounding agent, and kneaded for 3 minutes at 63 rpm in a closed kneading machine (KOC type 4.3L Banbury mixer manufactured by Kobe Steel). 2 parts by weight of dipentamethylene tyrium tetrasulfide (Ouchi Shinsei Chemical Co., Ltd .: Noxeller (trademark) TRA) and pentaerythritol (Nippon Gosei Chemical Co., Ltd .: Neuiser (trademark) P) 3 in a 10-inch open roll A part by weight was added and kneaded at 40 ° C. for 10 minutes. Next, the composition was press-vulcanized for 30 minutes at a pressure of 15 MPa and a temperature of 160 ° C. using a 150 mm × 150 mm × 2 mm mold. In accordance with JIS-K-6251, the vulcanized rubber sheet was punched with a No. 3 dumbbell and pulled at 500 mm / min, and 300% tensile stress, breaking strength, and breaking elongation were measured. On the other hand, the hardness was measured with a type A durometer in accordance with JIS-K-6253.

(A blend)
Magnesium oxide (manufactured by Kyowa Chemical Industry Co., Ltd .: Kyowamag (trademark) 150)
4 parts by weight SRF carbon (manufactured by Tokai Carbon Co., Ltd .: Seest (trademark) S) 40 parts by weight activated calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd .: white glazed CC) 30 parts by weight di-n-octyl phthalate (Shin Nippon Rika Co., Ltd.) Manufactured: Sansosizer (trademark) nDOP) 20 parts by weight (B blend)
Magnesium oxide (manufactured by Kyowa Chemical Industry Co., Ltd .: Kyowamag (trademark) 150)
4 parts by weight Special ester wax (Kao Corporation: Splendor (trademark) R-300)
1 part by weight carefully selected special wax (manufactured by Ouchi Shinsei Chemical Co., Ltd .: Sunnock (trademark) -N)
2 parts by weight SRF carbon (manufactured by Tokai Carbon Co., Ltd .: Seest (trademark) S) 40 parts by weight activated calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd .: white glazed CC) 30 parts by weight di-n-octyl phthalate (Shin Nippon Rika Co., Ltd.) Manufactured by: Sunsocizer (trademark) nDOP) 20 parts by weight Example of polyethylene synthesis The method of synthesizing polyethylene used in the present invention is, for example, the method described in JP-A-7-224106, that is, using a metallocene catalyst to produce ethylene. The method of polymerizing is mention | raise | lifted.

  Preparation of the clay mineral processed with the organic compound used for the synthesis | combination of polyethylene, preparation of the catalyst for ethylene polymer manufacture, manufacture of ethylene polymer, and solvent refinement | purification were all performed in inert gas atmosphere. Preparation of clay mineral treated with organic compound, preparation of catalyst for ethylene polymer production, solvent used for production of ethylene polymer, etc. are all purified, dried and deoxygenated in advance by known methods Using. Bis (indenyl) zirconium dichloride was synthesized and identified by a known method. A hexane solution (0.714M) of triisobutylaluminum manufactured by Tosoh Finechem Co., Ltd. was used.

(Preparation of clay minerals treated with organic compounds)
After adding 3.0 L of ethanol and 250 mL of 37% concentrated hydrochloric acid to 3.0 L of water, 330 g (1.1 mol) of N, N-dimethyl-octadecylamine was added to the resulting solution and heated to 60 ° C. A hydrochloride solution was prepared. To this solution, 1.0 kg of hectorite was added. The suspension was stirred at 60 ° C. for 3 hours, the supernatant was removed, and then washed with 5 L of water at 60 ° C. Then, the modified hectorite with an average particle diameter of 4.5 micrometers was obtained by drying at 60 degreeC and 10 < ^-3 > torr for 24 hours, and grind | pulverizing with a jet mill. As a result of elemental analysis, the amount of ions per gram of modified hectorite was 0.85 mmol.

(Adjustment of ethylene polymer production catalyst)
Bis (indenyl) zirconium dichloride 7.85 g (20.0 mmol) was suspended in hexane 2.07 L, triisobutylaluminum hexane solution (0.714 M) 2.93 L was added, bis (indenyl) zirconium dichloride and tris A contact product of isobutylaluminum was obtained. To this contact product, 500 g of the modified hectorite prepared in [Preparation of Clay Mineral Treated with Organic Compound] was added, stirred at 60 ° C. for 3 hours, and then allowed to stand to remove the supernatant liquid. Washed with heptane solution (0.03M). Further, a hexane solution of triethylaluminum (0.15M) was added to form a catalyst slurry (100 g / L).

(Manufacture of polyethylene)
An ethylene polymer production catalyst prepared by adjusting the amount of hexane at 115 kg / hour, ethylene at 14 kg / hour, hydrogen at 6 NL / hour, and the above (adjustment of ethylene polymer production catalyst) in a first polymerization vessel having an internal volume of 300 L. Continuously fed. Further, triisobutylaluminum was continuously supplied so that the concentration in the liquid was 0.19 mmol / kg hexane. The polymerization temperature was controlled at 85 ° C. After removing the unreacted gas from the slurry containing the ethylene polymer produced in the polymerization vessel, it was transferred to a second polymerization vessel having an internal volume of 300 L using a liquid feed pump, and again hexane was 40 kg / hour and ethylene was 15 kg / hour. Then, hydrogen was continuously supplied at 6 NL / hour. The polymerization temperature was controlled at 85 ° C. After removing the unreacted gas, the slurry containing the ethylene polymer produced in the second polymerizer was separated into ethylene polymer and hexane by a centrifugal separator, and the ethylene polymer (polyethylene) was continuously dried. The ethylene polymer extracted every 4 hours was 130 kg, and the catalytic activity was 15000 g / g catalyst.

Example 1
Density: 950 kg / m ³ , melt flow rate (MFR): 4.2 g / 10 min, number average molecular weight (Mn): 2.8 × 10 ⁴ , weight average molecular weight (Mw): 7.5 × 10 ⁴ , Z average molecular weight (Mz): 14 × 10 ⁴ , Weight average molecular weight (Mw) / Number average molecular weight (Mn) ratio: 2.7, Z average molecular weight (Mz) / Weight average molecular weight ( Mw) Ratio: 1.9 g of polyethylene having a ratio of 1.9 was charged into a 30 L autoclave, and after purging with nitrogen, the polyethylene was dissolved at 120 ° C. under pressure. Next, 0.60 g of pyridine was added as a promoter. As a radical generator, a 1,1,2-trichloroethane solution of α, α′-azobisisobutyronitrile at a concentration of 2.5 g / L and 7000 g of sulfuryl chloride were added and reacted. During this time, the reaction temperature was maintained at 110 ° C. or higher and 113 ° C. or lower, and the reaction pressure was maintained at 0.24 MPa or higher and 0.27 MPa or lower (gauge pressure). After completion of the reaction, the pressure in the reaction system was reduced to normal pressure, and then nitrogen was blown under normal pressure to discharge hydrogen chloride and sulfurous acid gas remaining in the solution out of the system. The discharged hydrogen chloride and sulfurous acid gas were recovered with a sodium hydroxide scrubber. After adding 52 g of 2,2′-bis (4-glycidyloxyphenyl) propane as a stabilizer, the product was isolated in a drum dryer.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 36.1% by weight, a sulfur content: 1.03% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 98, and a number average molecular weight (Mn ): 8.8 × 10 ⁴ , weight average molecular weight (Mw): 24 × 10 ⁴ , Z average molecular weight (Mz): 52 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 2 The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) was 2.2.

  Table 1 shows the evaluation results of the chlorosulfonated polyethylene composition and the vulcanizate.

Example 2
Density: 941 kg / m ³ , melt flow rate (MFR): 3.0 g / 10 min, number average molecular weight (Mn): 2.2 × 10 ⁴ , weight average molecular weight (Mw): 8.1 × 10 ⁴ , Z Average molecular weight (Mz): 22 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 3.6, ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw): 2.7 A chlorosulfonated polyethylene was synthesized in the same manner as in Example 1 using the above polyethylene.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 36.0% by weight, a sulfur content: 1.04% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 100, and a number average molecular weight (Mn ): 7.8 × 10 ⁴ , weight average molecular weight (Mw): 27 × 10 ⁴ , Z average molecular weight (Mz): 69 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 3 The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) was 2.6.

  Table 1 shows the evaluation results of the chlorosulfonated polyethylene composition and the vulcanizate.

Example 3
Density: 939 kg / m ³ , melt flow rate (MFR): 2.7 g / 10 min, number average molecular weight (Mn): 2.4 × 10 ⁴ , weight average molecular weight (Mw): 9.4 × 10 ⁴ , Z Average molecular weight (Mz): 22 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 3.9, ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw): 2.3 A chlorosulfonated polyethylene was synthesized in the same manner as in Example 1 using polyethylene (manufactured by Asahi Kasei Corporation: Creolex (trademark) K4125).

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 36.1% by weight, a sulfur content: 1.01% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 102, and a number average molecular weight (Mn ): 8.0 × 10 ⁴ , weight average molecular weight (Mw): 28 × 10 ⁴ , Z average molecular weight (Mz): 68 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 3 The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) was 2.5.

  Table 1 shows the evaluation results of the chlorosulfonated polyethylene composition and the vulcanizate.

Example 4
Density: 939 kg / m ³ , melt flow rate (MFR): 2.7 g / 10 min, number average molecular weight (Mn): 2.4 × 10 ⁴ , weight average molecular weight (Mw): 9.4 × 10 ⁴ , Z Average molecular weight (Mz): 22 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 3.9, ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw): 2.3 Manufactured by Asahi Kasei Corporation: Creolex (trademark) K4125 in polyethylene A, density: 946 kg / m ³ , melt flow rate (MFR): 5.2 g / 10 min, number average molecular weight (Mn): 1.4 × 10 ⁴ , Weight average molecular weight (Mw): 7.2 × 10 ⁴ , Z average molecular weight (Mz): 16 × 10 ⁴ , weight average molecular weight (Mw) / number average molecular weight (Mn) ratio: 5.1, Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio: 2.2 Asahi Kasei Co., Ltd .: When Cleorex (trademark) K4750 is polyethylene B, polyethylene A: polyethylene B blended at a weight ratio of 55:45 [(number average molecular weight (Mn): 2.0) × 10 ⁴ , weight average molecular weight (Mw): 8.4 × 10 ⁴ , Z average molecular weight (Mz): 19 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 4.3, The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw): 2.3)] was used to synthesize chlorosulfonated polyethylene in the same manner as in Example 1.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 36.1% by weight, a sulfur content: 1.00% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 91, and a number average molecular weight (Mn ): 7.2 × 10 ⁴ , weight average molecular weight (Mw): 25 × 10 ⁴ , Z average molecular weight (Mz): 65 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 3 The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) was 2.6.

  Table 1 shows the evaluation results of the chlorosulfonated polyethylene composition and the vulcanizate.

Comparative Example 1
Density: 953 kg / m ³ , melt flow rate (MFR): 1.0 g / 10 min, number average molecular weight (Mn): 2.3 × 10 ⁴ , weight average molecular weight (Mw): 13 × 10 ⁴ , Z average molecular weight (Mz): 63 × 10 ⁴ , weight average molecular weight (Mw) / number average molecular weight (Mn) ratio: 5.6, Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio: 4.8 Tosoh Manufactured by Nipolon Hard (trademark) 5730, polyethylene A, density: 964 kg / m ³ , melt flow rate (MFR): 5.0 g / 10 min, number average molecular weight (Mn): 1.4 × 10 ⁴ , weight average Molecular weight (Mw): 8.4 × 10 ⁴ , Z average molecular weight (Mz): 34 × 10 ⁴ , Weight average molecular weight (Mw) / Number average molecular weight (Mn) ratio: 5.9, Z average molecular weight (Mz) / Weight average molecular weight (Mw) ratio: 4 0 of Tosoh Corporation: Nipolon Hard (TM) 4030 when polyethylene B and polyethylene A: Polyethylene B = 60: a blend at a weight ratio of 40 (number-average molecular weight (Mn): 1.9 × 10 ⁴ , Weight average molecular weight (Mw): 11 × 10 ⁴ , Z average molecular weight (Mz): 51 × 10 ⁴ , weight average molecular weight (Mw) / number average molecular weight (Mn) ratio: 5.8, Z average molecular weight (Mz) ) / Weight average molecular weight (Mw) ratio: 4.6)], and chlorosulfonated polyethylene was synthesized in the same manner as in Example 1.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 35.8 wt%, a sulfur content: 0.98 wt%, a Mooney viscosity (ML (1 + 4) 100 ° C.): 93, and a number average molecular weight (Mn ): 7.0 × 10 ⁴ , weight average molecular weight (Mw): 32 × 10 ⁴ , Z average molecular weight (Mz): 100 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 4 The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) was 3.2.

  Table 2 shows the evaluation results of the chlorosulfonated polyethylene composition and the vulcanizate.

Comparative Example 2
Density: 960 kg / m ³ , melt flow rate (MFR): 0.90 g / 10 min, number average molecular weight (Mn): 1.4 × 10 ⁴ , weight average molecular weight (Mw): 12 × 10 ⁴ , Z average molecular weight (Mz): 70 × 10 ⁴ , weight average molecular weight (Mw) / number average molecular weight (Mn) ratio: 8.6, Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio: 5.8 Manufactured by Nipolon Hard (trademark) 5110, polyethylene A, density: 953 kg / m ³ , melt flow rate (MFR): 1.0 g / 10 min, number average molecular weight (Mn): 2.3 × 10 ⁴ , weight average Molecular weight (Mw): 13 × 10 ⁴ , Z average molecular weight (Mz): 63 × 10 ⁴ , Weight average molecular weight (Mw) / Number average molecular weight (Mn) ratio: 5.6, Z average molecular weight (Mz) / weight Average molecular weight (Mw) ratio: 4. 8 manufactured by Tosoh Corporation: When Nipolon Hard (trademark) 5730 is polyethylene B, a blend of polyethylene A: polyethylene B at a weight ratio of 65:35 [(number average molecular weight (Mn): 1.7 × 10 ⁴ , Weight average molecular weight (Mw): 12 × 10 ⁴ , Z average molecular weight (Mz): 68 × 10 ⁴ , weight average molecular weight (Mw) / number average molecular weight (Mn) ratio: 7.2, Z average molecular weight (Mz) ) / Weight average molecular weight (Mw) ratio: 5.5)], and chlorosulfonated polyethylene was synthesized in the same manner as in Example 1. As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 35.9% by weight, a sulfur content: 1.01% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 98, and a number average molecular weight (Mn ): 6.8 × 10 ⁴ , weight average molecular weight (Mw): 33 × 10 ⁴ , Z average molecular weight (Mz): 110 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 4 The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) was 3.3.

  Table 2 shows the evaluation results of the chlorosulfonated polyethylene composition and the vulcanizate.

Comparative Example 3
Density: 951 kg / m ³ , melt flow rate (MFR): 2.5 g / 10 min, number average molecular weight (Mn): 2.6 × 10 ⁴ , weight average molecular weight (Mw): 9.4 × 10 ⁴ , Z Average molecular weight (Mz): 26 × 10 ⁴ , weight average molecular weight (Mw) / number average molecular weight (Mn) ratio: 3.6, Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio: 2.8 A chlorosulfonated polyethylene was synthesized in the same manner as in Example 1 using the above polyethylene.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 35.8 wt%, a sulfur content: 0.98 wt%, a Mooney viscosity (ML (1 + 4) 100 ° C.): 93, and a number average molecular weight (Mn ): 7.8 × 10 ⁴ , weight average molecular weight (Mw): 26 × 10 ⁴ , Z average molecular weight (Mz): 72 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 3 The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) was 2.8.

  Table 2 shows the evaluation results of the chlorosulfonated polyethylene composition and the vulcanizate.

Comparative Example 4
Density: 953 kg / m ³ , melt flow rate (MFR): 2.0 g / 10 min, number average molecular weight (Mn): 2.2 × 10 ⁴ , weight average molecular weight (Mw): 9.0 × 10 ⁴ , Z Average molecular weight (Mz): 23 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 4.1, ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw): 2.6 A chlorosulfonated polyethylene was synthesized in the same manner as in Example 1 using the above polyethylene.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 36.0% by weight, a sulfur content: 1.02% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 95, and a number average molecular weight (Mn ): 6.9 × 10 ⁴ , weight average molecular weight (Mw): 29 × 10 ⁴ , Z average molecular weight (Mz): 69 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 4 The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) was 2.4.

  Table 2 shows the evaluation results of the chlorosulfonated polyethylene composition and the vulcanizate.

Claims (6)

The ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) produced using a 1,1,2-trichloroethane solution is 3.5 or less, and Z average molecular weight (Mz) / weight average molecular weight (Mw ) a chlorosulfonated ethylene homopolymer ratio is 2.7 or less, chlorosulfonated obtained by mixing the formulation with the following composition ratio to the chlorosulfonic instead styrene homopolymer 100 parts by weight et styrene homopolymer composition, following the 300% tensile stress characteristics and to torque Rorosuruhon instead styrene homopolymers that the measured 300% tensile stress was measured by the method is not less than 22MPa in.
<Combination ratio>
Magnesium oxide: 4 parts by weight, special ester wax (manufactured by Kao Corporation: Splendor (trademark) R-300): 1 part by weight, specially selected special wax (manufactured by Ouchi Shinsei Chemical Co., Ltd .: Sannok (trademark) -N) : 2 parts by weight, SRF carbon: 40 parts by weight, activated calcium carbonate: 30 parts by weight, di-n-octyl phthalate: 20 parts by weight <Measurement method of 300% tensile stress>
After kneading for 3 minutes at 63 rpm in a closed kneader (OOC type 4.3L Banbury mixer, manufactured by Kobe Steel), dipentamethylene tiraum tetrasulfide (Ouchi Shinsei Chemical Co., Ltd .: 2 parts by weight of Noxeller (trademark) TRA) and 3 parts by weight of pentaerythritol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Neuiser (trademark) P) are added and kneaded at 40 ° C. for 10 minutes. Next, the composition is press-vulcanized for 30 minutes at a pressure of 15 MPa and a temperature of 160 ° C. using a 150 mm × 150 mm × 2 mm mold. In accordance with JIS-K-6251, the vulcanized rubber sheet is punched out with a No. 3 dumbbell and pulled at 500 mm / min to measure 300% tensile stress. The weight average molecular weight (Mw) / number average molecular weight (Mn) ratio produced using a 1,1,2-trichloroethane solution is 3.0 or less, and the Z average molecular weight (Mz) / weight average molecular weight (Mw ) Is a chlorosulfonated ethylene homopolymer having a ratio of 2.4 or less, and is obtained by mixing a compounding agent in the following compounding ratio with 100 parts by weight of the chlorosulfonated ethylene homopolymer. A chlorosulfonated ethylene homopolymer, wherein the homopolymer composition has a 300% tensile stress measured by the following 300% tensile stress measurement method of 22 MPa or more.
<Combination ratio>
  Magnesium oxide: 4 parts by weight, special ester wax (manufactured by Kao Corporation: Splendor (trademark) R-300): 1 part by weight, specially selected special wax (manufactured by Ouchi Shinsei Chemical Co., Ltd .: Sannok (trademark) -N) : 2 parts by weight, SRF carbon: 40 parts by weight, activated calcium carbonate: 30 parts by weight, di-n-octyl phthalate: 20 parts by weight
<Measurement method of 300% tensile stress>
  After kneading for 3 minutes at 63 rpm in a closed kneader (OOC type 4.3L Banbury mixer, manufactured by Kobe Steel), dipentamethylene tiraum tetrasulfide (Ouchi Shinsei Chemical Co., Ltd .: 2 parts by weight of Noxeller (trademark) TRA) and 3 parts by weight of pentaerythritol (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Neuiser (trademark) P) are added and kneaded at 40 ° C. for 10 minutes. Next, the composition is press-vulcanized for 30 minutes at a pressure of 15 MPa and a temperature of 160 ° C. using a 150 mm × 150 mm × 2 mm mold. In accordance with JIS-K-6251, the vulcanized rubber sheet is punched out with a No. 3 dumbbell and pulled at 500 mm / min to measure 300% tensile stress. Chlorosulfonic instead styrene homopolymer obtained by mixing formulations in the following mixing ratio to 100 parts by weight of chlorosulfonic replaced styrene homopolymer composition, the die swell was measured by the measuring method of the following die swell chlorosulfonated instead styrene homopolymer according to claim 1 or claim 2, characterized in that 65% or less.
<Combination ratio>
Magnesium oxide: 4 parts by weight, SRF carbon: 40 parts by weight, activated calcium carbonate: 30 parts by weight, di-n-octyl phthalate: 20 parts by weight <Die swell measurement method>
The mixture was kneaded at 63 rpm for 3 minutes in a closed kneader (OOC type 4.3L Banbury mixer manufactured by Kobe Steel). Next, the composition was compliant with ASTM-D-2230 Garbage Die Extrusion Test, extruder: 50 mmφ, L / D = 8/1, rotation speed: 30 rpm, temperature: cylinder; 70 ° C., head: 70 ° C., Die: Extrude at 80 ° C. and measure die swell. Chlorinated polyethylene having a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 4.0 or less and a Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio of 2.7 or less. method for producing a chlorosulfonated changing styrene homopolymer according to any one of claims 1 to claim 3, characterized in that the chlorosulfonated. Chlorination of polyethylene having a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 3.0 or less and a Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio of 2.4 or less. the method according to claim 2 or claim 3 chlorosulfonated instead styrene homopolymers wherein a is chlorosulfonated. Automotive hoses, characterized in that it is manufactured using chlorosulfonic instead styrene homopolymer according to one of claims 1 to claim 3, gas hose, industrial hoses, wire coatings, coated fabrics, Packing, gasket, roll, lining, rubber boat, life jacket, window breaker, escalator handrail or adhesive.