JP5481792B2 - Chlorosulfonated polyethylene, its production method and use - Google Patents

Description

  The present invention relates to a chlorosulfonated polyethylene having a characteristic molecular weight distribution, a method for producing the same, and use 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. It is used. 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 inside during a kneading operation with a closed kneader, that a part of the composition adheres to the die during extrusion, and that the settling rate is large.

  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 No. 3770701

  In order to solve the problems of the prior art, the object of the present invention is that the Banbury discharge property of the composition and the die cleaning property of the extruder are good, the set rate of the extruded vulcanizate is small, and the vulcanized product It is to provide a chlorosulfonated polyethylene having a large tensile stress.

  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 Z average molecular weight (Mz) / weight average molecular weight (Mw) is 6.0 or more, and the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 2.0-7. 0.0 chlorosulfonated polyethylene.

  The present invention is described in detail below.

  In the chlorosulfonated polyethylene of the present invention, the ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) is 6.0 or more, and the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 2. 0 to 7.0.

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 ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) is obtained by dividing the Z average molecular weight (Mz) by the weight average molecular weight (Mw), and the weight average molecular weight (Mw) / number average molecular weight. The ratio of (Mn) is obtained by dividing the weight average molecular weight (Mw) by the number average molecular weight (Mn).

  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 ratio of the Z average molecular weight (Mz) / weight average molecular weight (Mw) of the chlorosulfonated polyethylene of the present invention is 6.0 or more, and the composition has good Banbury discharge property and the extruded vulcanized product The rate is small. When the ratio of the Z average molecular weight (Mz) / weight average molecular weight (Mw) of the chlorosulfonated polyethylene is less than 6.0, the composition is hardly discharged naturally after Banbury kneading, and the composition remains in the apparatus.

  Furthermore, the ratio of the weight average molecular weight (Mw) / number average molecular weight (Mn) of the chlorosulfonated polyethylene of the present invention is 2.0 to 7.0, and the die cleaning property of the extruder of the composition is good and vulcanized. The tensile stress of the object is large. When the ratio of the weight average molecular weight (Mw) / number average molecular weight (Mn) of the chlorosulfonated polyethylene is less than 2.0, the composition is hardly discharged naturally after Banbury kneading, and the composition remains in the apparatus. When the ratio of the weight average molecular weight (Mw) / number average molecular weight (Mn) of chlorosulfonated polyethylene exceeds 7.0, the tensile strength of the vulcanizate is small.

  In the chlorosulfonated polyethylene of the present invention, the ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) is 5.0 or more, and the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 2. It is obtained from chlorination or chlorosulfonation using polyethylene of 0 to 10.0 as a raw material. If the molecular weight distribution of polyethylene is within the above range after blending, it is suitably used as a raw material for the chlorosulfonated polyethylene of the present invention.

  Since the molecular weight distribution of polyethylene as a raw material for the chlorosulfonated polyethylene of the present invention is an important factor for controlling the molecular weight and molecular weight distribution of chlorosulfonated polyethylene, the ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) Is 5.0 or more, and the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is required to be 2.0 to 10.0.

  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 where high heat resistance and oil resistance are required, and linear chains of less than 930 kg / m ³ are used in applications where high low-temperature characteristics are required. A 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 can be used for automobile hoses, gas hoses, industrial hoses, electric wire coverings, pulling cloths, packings, gaskets, rolls, linings, rubber boats, life jackets, window breakers, escalator handrails or adhesives. In order to sufficiently adapt to the use of chlorosulfonated polyethylene, 100 parts by weight of chlorosulfonated polyethylene was mixed with a compounding agent at the following compounding ratio, and the resulting chlorosulfonated polyethylene composition was measured by the following 100% tensile stress measurement method The 100% tensile stress is preferably 5.4 MPa or more.

<Combination ratio>
Magnesium oxide: 4 parts by weight, special ester wax (manufactured by Kao Corporation: Splendor (trademark) R-300): 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 100% 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 8 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 with a No. 3 dumbbell and pulled at 500 mm / min to measure 100% tensile stress.

  The vulcanized product using the chlorosulfonated polyethylene of the present invention has a lower settling rate than other chlorosulfonated polyethylene vulcanized products exhibiting the same Mooney viscosity when compounding, kneading and vulcanization are performed under the same conditions.

  The chlorosulfonated polyethylene of the present invention can be used for automobile hoses, gas hoses, industrial hoses, electric wire coverings, pulling cloths, packings, gaskets, rolls, linings, rubber boats, life jackets, window breakers, escalator handrails or adhesives. In order to sufficiently adapt to the use of chlorosulfonated polyethylene, 100 parts by weight of chlorosulfonated polyethylene was mixed with a compounding agent at the following compounding ratio to obtain a chlorosulfonated polyethylene composition measured by the following method for measuring the settling rate. The rate is preferably 5% or less.

<Combination ratio>
Magnesium oxide: 4 parts by weight, ester wax: 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
The mixture is kneaded at 63 rpm for 3 minutes in a closed kneader (OOC type 4.3 L Banbury mixer manufactured by Kobe Steel). Next, the composition was collected by a 12-inch open roll, and then 2 parts by weight of dipentamethylenetyramium tetrasulfide (manufactured by Ouchi Shinsei Chemical Co., Ltd .: Noxeller (trademark) TRA) and pentaerythritol were collected by an 8-inch open roll. 3 parts by weight (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Neulizer (trademark) P) is added and kneaded at 40 ° C. for 10 minutes. The composition conforms to ASTM-D-2230's garbage die extrusion test, the extrusion part is a 14 mmφ round bar, L / D = 8/1, rotation speed: 15 rpm, temperature: cylinder: 70 ° C., head: 70 ° C., Die: Extrude at 80 ° C. From the diameter (d) in the gravitational direction after 10 minutes of extrusion and the diameter (D) in the gravitational direction after vulcanizing the can for 20 minutes at 160 ° C., the settling rate is calculated using the following formula.

(D−D) / d × 100
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.

  The amount of sulfur in 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, and tensile stress. 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 good Banbury discharge property of the composition and die cleaning property of the extruder, the vulcanized product of the extruded product has a low settling rate, and the tensile property of the vulcanized product is large. Various industrial parts such as automobile hose, gas hose, industrial hose, wire covering, cloth, packing, gasket, roll or lining, rubber boat, life jacket, window breaker, escalator that can use conventional chlorosulfonated polyethylene It is suitably used for handrails or adhesives.

  As described above, the chlorosulfonated polyethylene of the present invention has good Banbury discharge property of the composition and die-cleaning property of the extruder, the set rate of the vulcanized product is small, and the tensile stress of the vulcanized product is low. It has a great effect.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these.

  Various physical properties were measured according to the following methods.

<Density>
The density of polyethylene used as a raw material for chlorosulfonated polyethylene was measured according to JIS-K-6790 (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), the number average molecular weight (Mn), and the Z average molecular weight (Mz) can be obtained by converting from a calibration curve of known polystyrene by a line segment method from a chromatogram.

<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.

<Banbury emissions>
The Banbury discharge property 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 at the following blending ratio, and kneaded for 3 minutes at 63 rpm with a closed kneader (OOC type 4.3 L Banbury mixer manufactured by Kobe Steel). After kneading, the dischargeability when the bottom of the Banbury was opened was evaluated in three stages: ◎: naturally discharged, ◯: mostly discharged naturally, but a small amount of deposits, and x: not discharged naturally.

<Die cleanability and settling rate of extruder>
Evaluation of the die cleaning property and the settling rate of the extruder 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 at the following blending ratio, and kneaded for 3 minutes at 63 rpm with a closed kneader (OOC type 4.3 L Banbury mixer manufactured by Kobe Steel). Next, the composition was collected by a 12-inch open roll, and then 2 parts by weight of dipentamethylenetyramium tetrasulfide (manufactured by Ouchi Shinsei Chemical Co., Ltd .: Noxeller (trademark) TRA) and pentaerythritol were collected by an 8-inch open roll. 3 parts by weight (manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: Neulizer (trademark) P) was added and kneaded at 40 ° C. for 10 minutes. The composition conforms to ASTM-D-2230's garbage die extrusion test, the extrusion part is a 14 mmφ round bar, L / D = 8/1, rotation speed: 15 rpm, temperature: cylinder: 70 ° C., head: 70 ° C., Die: Extruded at 80 ° C. The die cleaning property at the time of extrusion molding was evaluated in three stages: ◎: no deposit, ○: little deposit, x: deposit. The settling rate was calculated from the diameter (d) in the gravitational direction after 10 minutes of extrusion molding and the diameter (D) in the gravitational direction after vulcanizing the can at 160 ° C. for 20 minutes using the following equation.

(D−D) / d × 100
<Tensile properties and hardness>
The tensile properties and hardness of the chlorosulfonated polyethylene vulcanizate were evaluated by the following methods.

First, 100 parts by weight of chlorosulfonated polyethylene is mixed with a compounding agent at the following compounding ratio,
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) were 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 to measure 100% tensile stress, breaking strength, and breaking elongation. On the other hand, the hardness was measured with a type A durometer in accordance with JIS-K-6253.

(Combination)
Magnesium oxide (manufactured by Kyowa Chemical Industry Co., Ltd .: Kyowa Mag ™ 150)
4 parts by weight Special ester wax (Kao Corporation: Splendor (trademark) R-300)
2 parts by weight SRF carbon (manufactured by Tokai Carbon Co., Ltd .: Seast (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 Manufactured: Sansosizer (trademark) nDOP) 20 parts by weight <Synthesis example of polyethylene used in Examples>
The method for synthesizing the ethylene polymer used in the examples of the present invention is, for example, a method described in JP-A-2005-206777, that is, a method of polymerizing ethylene using a catalyst containing at least two types of metallocene compounds. Alternatively, ethylene and α-olefin are copolymerized.

  Preparation of clay mineral treated with organic compound used for synthesis of polyethylene used in Examples of the present invention, preparation of catalyst for production of ethylene polymer, production of ethylene polymer and solvent purification are all in an inert gas atmosphere Went under. 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 and diphenylmethylene (3-trimethylsilylcyclopentadienyl-9-fluorenyl) zirconium dichloride were synthesized and identified by known methods. A hexane solution (0.714M) of triisobutylaluminum manufactured by Tosoh Finechem Co., Ltd. was used.

Polyethylene synthesis example 1
(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.
(Preparation 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, and triisobutylaluminum Washed with heptane solution (0.03M). Further, a hexane solution (0.15 M) of triethylaluminum was added to obtain a catalyst precursor slurry (100 g / L). Diphenylmethylene (3-trimethylsilylcyclopentadienyl-9-fluorenyl) zirconium dichloride (1.89 g, 3.0 mmol) was added to the precursor slurry, and the mixture was stirred at 25 ° C. for 8 hours, and then an ethylene polymer production catalyst slurry (100 g / L). Got.
(Manufacture of ethylene polymer)
The ethylene polymer production catalyst prepared in the above (Preparation of ethylene polymer production catalyst) was continuously added to a polymerization vessel having an internal volume of 300 L at a rate of 105 kg / hour of hexane, 30 kg / hour of ethylene, 45 NL / hour of hydrogen, and Supplied. 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 unreacted gas, the slurry containing the ethylene polymer produced in the polymerization vessel was separated into ethylene polymer and hexane by a centrifugal separator, and the ethylene polymer was continuously dried.

  The ethylene polymer extracted every 4 hours was 115 kg, and the catalytic activity was 22900 g / g catalyst.

The density of the obtained ethylene polymer was 962 kg / m ³ and the MFR was 4.1 g / 10 min. Mw = 95,000 and Mw · Mn = 6.4.

Polyethylene synthesis example 2
In a polymerization vessel having an internal volume of 300 L, hexane at 135 kg / hour, ethylene at 30 kg / hour, 1-butene at 1 kg / hour, hydrogen at 13 NL / hour, and polyethylene synthesis example 1 (ethylene polymer production) The ethylene polymer production catalyst prepared in (Preparation of catalyst) was 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 unreacted gas, the slurry containing the ethylene copolymer produced in the polymerization vessel was separated into ethylene copolymer and hexane by a centrifugal separator, and the ethylene copolymer was continuously dried.

  The ethylene copolymer withdrawn every 4 hours was 118 kg, and the catalytic activity was 25500 g / g catalyst.

The density of the obtained ethylene copolymer was 943 kg / m ³ and the MFR was 2.0 g / 10 min. Moreover, it was Mw = 110,000 and Mw / Mn = 4.1.

Polyethylene synthesis example 3
An ethylene polymer was produced in the same manner as in polyethylene synthesis example 1 (production of ethylene polymer) except that hexane was continuously supplied at 135 kg / hour and hydrogen was continuously supplied at 95 NL / hour.

  The ethylene polymer withdrawn every 4 hours was 118 kg, and the catalytic activity was 17200 g / g catalyst.

The density of the obtained ethylene polymer was 961 kg / m ³ and the MFR was 5.2 g / 10 min. Mw = 88,000 and Mw / Mn = 5.5.

Polyethylene synthesis example 4
An ethylene polymer was produced in the same manner as in polyethylene synthesis example 1 (production of ethylene polymer) except that hexane was continuously supplied at 135 kg / hour and hydrogen was continuously supplied at 85 NL / hour.

  The ethylene polymer extracted every 4 hours was 114 kg, and the catalytic activity was 15400 g / g catalyst.

The density of the obtained ethylene polymer was 968 kg / m ³ and the MFR was 2.8 g / 10 min. Mw = 100,000 and Mw / Mn = 9.2.

<Synthesis example of polyethylene used in Comparative Example 1 and Comparative Example 2>
The method for producing an ethylene polymer used in Comparative Example 1 and Comparative Example 2 of the present invention is, for example, a method described in JP-A-7-224106, that is, a method of polymerizing ethylene using a metallocene catalyst or ethylene. And α-olefin are copolymerized.

  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.

Polyethylene synthesis example 5
(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, it dried at 60 degreeC and 10-3 torr for 24 hours, and modified | denatured hectorite with an average particle diameter of 4.5 micrometers was obtained by 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.
(Preparation 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, and triisobutylaluminum Washed with heptane solution (0.03M). Further, a hexane solution of triethylaluminum (0.15M) was added to obtain an ethylene polymer production catalyst slurry (100 g / L).
(Manufacture of ethylene copolymer)
Into a polymerization vessel having an internal volume of 300 L, hexane is 105 kg / hour, ethylene is 25 kg / hour, 1-butene is 0.4 kg / hour, hydrogen is 22 NL / hour, and the above (preparation of ethylene polymer production catalyst) The ethylene polymer production catalyst prepared in (1) was 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 unreacted gas, the slurry containing the ethylene copolymer produced in the polymerization vessel was separated into ethylene copolymer and hexane by a centrifugal separator, and the ethylene copolymer was continuously dried.

  The ethylene copolymer extracted every 4 hours was 100 kg, and the catalytic activity was 23300 g / g catalyst.

The density of the obtained ethylene copolymer was 950 kg / m ³ and the MFR was 14.8 g / 10 min. Mw = 55,000 and Mw / Mn = 2.7.

Polyethylene synthesis example 6
Except that ethylene was continuously supplied at 30 kg / hour, 1-butene at 0.1 kg / hour, and hydrogen at 35 NL / hour, ethylene was synthesized in the same manner as in Synthesis Example 5 (Production of ethylene polymer) of ethylene. A copolymer was produced.

  The ethylene copolymer extracted every 4 hours was 122 kg, and the catalytic activity was 22300 g / g catalyst.

The density of the obtained ethylene copolymer was 958 kg / m ³ , and the MFR was 14.4 g / 10 min. Mw = 54,000 and Mw / Mn = 2.8.

Example 1
Polyethylene synthesized in Synthesis Example 1, density: 962 kg / m ³ , melt flow rate (MFR): 4.1 g / 10 min, number average molecular weight (Mn): 1.5 × 10 ⁴ , weight average molecular weight (Mw) : 9.5 × 10 ⁴ , Z average molecular weight (Mz): 76 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 6.4, Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio: 3000 g of 8.0 g of polyethylene was charged in 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 the analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 34.8% by weight, a sulfur content: 1.04% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 43, and a number average molecular weight (Mn ): 5.6 × 10 ⁴ , weight average molecular weight (Mw): 27 × 10 ⁴ , Z average molecular weight (Mz): 247 × 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 9.3.

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

実施例２
ポリエチレンの合成例２で合成した、密度：９４３ｋｇ／ｍ^３、メルトフロレート（ＭＦＲ）：２．０ｇ／１０分、数平均分子量（Ｍｎ）：２．７×１０^４、重量平均分子量（Ｍｗ）：１１×１０^４、Ｚ平均分子量（Ｍｚ）：６２×１０^４、重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）の比 ： ４．１、Ｚ平均分子量（Ｍｚ）／重量平均分子量（Ｍｗ）の比：５．６のポリエチレン用いて実施例１と同様にクロロスルホン化ポリエチレンを合成した。

Example 2
Density: 943 kg / m ³ , melt flow rate (MFR): 2.0 g / 10 min, number average molecular weight (Mn): 2.7 × 10 ⁴ , weight average molecular weight (Mw) synthesized in Synthesis Example 2 of polyethylene : 11 × 10 ⁴ , Z average molecular weight (Mz): 62 × 10 ⁴ , weight average molecular weight (Mw) / number average molecular weight (Mn) ratio: 4.1, Z average molecular weight (Mz) / weight average molecular weight (Mw) ) Ratio: A chlorosulfonated polyethylene was synthesized in the same manner as in Example 1 using polyethylene of 5.6.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 35.1% by weight, a sulfur content: 1.01% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 39, and a number average molecular weight (Mn ): 9.4 × 10 ⁴ , weight average molecular weight (Mw): 33 × 10 ⁴ , Z average molecular weight (Mz): 199 × 10 ⁴ , weight average molecular weight (Mw) / number average molecular weight (Mn) ratio: 3 The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) was 6.0.

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

Example 3
Density: 961 kg / m ³ , melt flow rate (MFR): 5.2 g / 10 min, number average molecular weight (Mn): 1.6 × 10 ⁴ , weight average molecular weight (Mw) synthesized in Synthesis Example 3 of polyethylene : 8.8 × 10 ⁴ , Z average molecular weight (Mz): 62 × 10 ⁴ , Weight average molecular weight (Mw) / Number average molecular weight (Mn) ratio: 5.5, Z average molecular weight (Mz) / Weight average molecular weight (Mw) ratio: A chlorosulfonated polyethylene was synthesized in the same manner as in Example 1 using polyethylene of 7.0.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 35.2% by weight, a sulfur content: 1.00% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 37, and a number average molecular weight (Mn ): 6.1 × 10 ⁴ , weight average molecular weight (Mw): 25 × 10 ⁴ , Z average molecular weight (Mz): 201 × 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): 8.0.

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

Example 4
Density: 968 kg / m ³ , melt flow rate (MFR): 2.8 g / 10 min, number average molecular weight (Mn): 1.1 × 10 ⁴ , weight average molecular weight (Mw) synthesized in Synthesis Example 4 of polyethylene : 10 × 10 ⁴ , Z average molecular weight (Mz): 86 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 9.2, Z average molecular weight (Mz) / weight average molecular weight (Mw) ): A chlorosulfonated polyethylene was synthesized in the same manner as in Example 1 using polyethylene of 8.6.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 35.1% by weight, a sulfur content: 0.99% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 36, and a number average molecular weight (Mn ): 4.3 × 10 ⁴ , weight average molecular weight (Mw): 30 × 10 ⁴ , Z average molecular weight (Mz): 315 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 6 The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) was 10.5.

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

Comparative Example 1
Density: 950 kg / m ³ , melt flow rate (MFR): 14.8 g / 10 min, number average molecular weight (Mn): 2.0 × 10 ⁴ , weight average molecular weight (Mw) synthesized in Synthesis Example 5 of polyethylene : 5.5 × 10 ⁴ , Z average molecular weight (Mz): 11 × 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: Chlorosulfonated polyethylene was synthesized in the same manner as in Example 1 using polyethylene having a ratio of 2.0.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 35.2 wt%, a sulfur content: 0.99 wt%, a Mooney viscosity (ML (1 + 4) 100 ° C.): 47, and a number average molecular weight (Mn ): 6.9 × 10 ⁴ , weight average molecular weight (Mw): 16 × 10 ⁴ , Z average molecular weight (Mz): 31 × 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 1.9.

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

比較例２
ポリエチレンの合成例６で合成した、密度：９５８ｋｇ／ｍ^３、メルトフロレート（ＭＦＲ）：１４．４ｇ／１０分、数平均分子量（Ｍｎ）：１．９×１０^４、重量平均分子量（Ｍｗ）：５．４×１０^４、Ｚ平均分子量（Ｍｚ）：１１×１０^４、重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）の比 ： ２．８、Ｚ平均分子量（Ｍｚ）／重量平均分子量（Ｍｗ）の比：２．０のポリエチレンを用いて実施例１と同様にクロロスルホン化ポリエチレンを合成した。

Comparative Example 2
Density: 958 kg / m ³ , melt flow rate (MFR): 14.4 g / 10 min, number average molecular weight (Mn): 1.9 × 10 ⁴ , weight average molecular weight (Mw) synthesized in Synthesis Example 6 of polyethylene : 5.4 × 10 ⁴ , Z average molecular weight (Mz): 11 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 2.8, Z average molecular weight (Mz) / weight average molecular weight (Mw) ratio: Chlorosulfonated polyethylene was synthesized in the same manner as in Example 1 using 2.0 polyethylene.

As a result of analysis, the obtained chlorosulfonated polyethylene had a chlorine content of 34.9% by weight, a sulfur content of 0.96% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 47, and a number average molecular weight ( Mn): 6.9 × 10 ⁴ , weight average molecular weight (Mw): 17 × 10 ⁴ , Z average molecular weight (Mz): 30 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 2.4 Ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw): 1.8.

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

Comparative Example 3
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 , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 5.9, ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw): 4.0 Nisoron Hard (trademark) 4030 manufactured by Tosoh Corporation in polyethylene A, density: 960 kg / m ³ , melt flow rate (MFR): 14.2 g / 10 min, number average molecular weight (Mn): 1.2 × 10 ⁴ , weight Average molecular weight (Mw): 5.9 × 10 ⁴ , Z average molecular weight (Mz): 21 × 10 ⁴ , Weight average molecular weight (Mw) / Number average molecular weight (Mn) ratio: 4.9, Z average molecular weight (Mz) ) / Weight average molecular weight (Mw) ratio: When Nipolon Hard (trademark) 2000 manufactured by Tosoh Corporation in 3.6 is polyethylene B, a blend of polyethylene A: polyethylene B = 40: 60 in weight ratio [(number average molecular weight (Mn): 1.3 × 10 ⁴ , weight average molecular weight (Mw): 6.9 × 10 ⁴ , Z average molecular weight (Mz): 26 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 5.3, Z average The ratio of molecular weight (Mz) / weight average molecular weight (Mw): 3.8)] 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 34.9% by weight, a sulfur content: 1.04% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 41, and a number average molecular weight (Mn ): 5.0 × 10 ⁴ , weight average molecular weight (Mw): 16 × 10 ⁴ , Z average molecular weight (Mz): 45 × 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 2.7.

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

Comparative Example 4
Density: 958 kg / m ³ , melt flow rate (MFR): 2.7 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 Nipolon Hard (trademark) 5730 manufactured by 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 , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 5.9, Z average molecular weight (Mz) / Weight average molecular weight (Mw) ratio: 4. No. 0 Tosoh Co., Ltd. Nipolon Hard (trademark) 4030 is polyethylene B, polyethylene A: polyethylene B = 25:75 weight ratio [(number average molecular weight (Mn): 1.6 × 10 ⁴ , Weight average molecular weight (Mw): 9.6 × 10 ⁴ , Z average molecular weight (Mz): 41 × 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: 4.2)] 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 35.1% by weight, a sulfur content: 1.00% by weight, a Mooney viscosity (ML (1 + 4) 100 ° C.): 45, and a number average molecular weight (Mn ): 1.3 × 10 ⁴ , weight average molecular weight (Mw): 11 × 10 ⁴ , Z average molecular weight (Mz): 531 × 10 ⁴ , ratio of weight average molecular weight (Mw) / number average molecular weight (Mn): 8 1. Ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw): 5.0.

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

Claims (3)

The ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) is 6.0 or more, and the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 2.0 to 7.0. Characterized chlorosulfonated polyethylene. A polyethylene having a ratio of Z average molecular weight (Mz) / weight average molecular weight (Mw) of 5.0 or more and a ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) of 2.0 to 10.0. preparation of chlorosulfonated polyethylene of claim 1, characterized in that the chlorination and chlorosulfonation. Automotive hoses, characterized in that it is manufactured using a chlorosulfonated polyethylene of claim 1, gas hose, industrial hose or wire coating.