JP5990902B2 - Chlorosulfonated polyolefin and process for producing the same - Google Patents

Description

  The present invention relates to a chlorosulfonated polyolefin and a method for producing the same, and more particularly to a chlorosulfonated polyolefin excellent in cold resistance and light color and a method for producing the same.

  Chlorosulfonated polyolefin is manufactured by dissolving or suspending polyolefin in a solvent, chlorinated and chlorosulfonated, and has excellent heat resistance, weather resistance, ozone resistance, chemical resistance and light color. From various uses such as cover materials for various hoses, wire covering materials, packing, gaskets, rolls, and handrails for escalators. In addition, chlorosulfonated polyolefin is dissolved or dispersed in a solvent or water and used in a wide range of fields such as adhesives, coating agents, paints, and primers.

  However, one of the drawbacks of chlorosulfonated polyolefins is their poor cold resistance.

  Therefore, a process for producing chlorosulfonated polyolefin using an aromatic compound as a solvent to improve cold resistance (for example, see Reference 1), and a chlorosulfonated ethylene α-olefin copolymer composition having a specific structure. A method of adding a small amount of a plasticizer and / or a softening agent to a product (for example, see Patent Document 2) has been proposed.

  However, although the above method is effective in improving the cold resistance, the light color is not sufficient. Therefore, it has been desired to satisfy both of these characteristics.

JP 60-144306 A JP-A-9-179364

  The present invention has been made in view of the above problems, and an object thereof is to provide a chlorosulfonated polyolefin having excellent cold resistance and light color.

  As a result of intensive studies to solve the above-described problems, the present inventors have completed the present invention. That is, the present invention relates to a chlorosulfonated polyolefin containing 0.001 to 1.0% by weight or less of 1,1,2-trichloroethane and having a YI value of 15 or less, and a method for producing the same. It is.

  The present invention is described in detail below.

  The chlorosulfonated polyolefin of the present invention contains 0.001, 1.0% by weight of 1,1,2-trichloroethane. If the content exceeds 1.0% by weight, the storage stability is lowered, and if it is less than 0.001% by weight, the cold resistance is lowered. Among these, in order to ensure good cold resistance, 0.003 to 0.8% by weight is preferable, and 0.005 to 0.5% by weight is more preferable.

  The chlorosulfonated polyolefin of the present invention has a YI value of 15 or less. When the YI value is 15 or less, the light color is excellent. When the YI value exceeds 15, the light color is inferior. This YI value is measured using a spectral color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., SE-2000) under the conditions of normal temperature, reflection mode, measurement wavelength of 380 to 780 nm, and C / 2 light source. Is.

  The amount of chlorine in the chlorosulfonated polyolefin of the present invention is not particularly limited, but is preferably 10.0 to 50.0% by weight, more preferably 20.0 to 45.0% by weight in consideration of cold resistance and mechanical properties. Further, the amount of sulfur of the chlorosulfonated polyolefin of the present invention is not particularly limited, but is preferably 0.3 to 3.0% by weight, more preferably 0.5 to 2.0% by weight in consideration of crosslinkability and mechanical properties. preferable.

  The chlorosulfonated polyolefin of the present invention is not particularly limited as long as it is a chlorosulfonated polyolefin obtained by chlorinating and chlorosulfonated a raw material polyolefin. For example, chlorosulfonated polyethylene, chlorosulfonated ethylene-α -Olefin copolymer, chlorosulfonated α-olefin polymer, chlorosulfonated α-olefin copolymer, chlorosulfonated ethylene-vinyl acetate copolymer and the like. Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene. Examples of the raw material polyolefin include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE). These may be used alone or in combination. Can be used. Of these, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE) are preferable in order to achieve both cold resistance and light color. In addition, the polyolefin as a raw material may be copolymerized with other polymerizable components in addition to the above components. Examples of other polymerizable components include 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6. -Chain non-conjugated dienes such as octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene- Non-conjugated dienes such as cyclic non-conjugated dienes such as 2-norbornene and 6-chloromethyl-5-isopropenyl-2-norbornene.

  The solvent used for chlorination and chlorosulfonation of the raw material polyolefin is 1,1,2-trichloroethane. Good cold resistance cannot be obtained unless 1,1,2-trichloroethane is used. In addition, 1,1,2-trichloroethane and other solvents can be used in combination. Examples of other solvents include chlorination reactions such as carbon tetrachloride, chloroform, dichloroethane, 1,1,1-trichloroethane, tetrachloroethane, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodifluoromethane, and trichlorofluoromethane. And an inert solvent. The amount to be used as the solvent is not particularly limited, but an amount in which the raw material polyolefin is 5 to 50% by weight is preferable.

  The reaction process for chlorination and chlorosulfonation uses a radical initiator as a catalyst and chlorine gas and sulfurous acid gas, chlorine gas and sulfuryl chloride, sulfurous acid gas and sulfuryl chloride, sulfuryl chloride alone, or chlorine gas, sulfurous acid gas and sulfuryl chloride. And reacting with a polyolefin dissolved or suspended in a solvent. When sulfuryl chloride is added, an amino compound such as pyridine or quinoline as a co-catalyst is added as necessary. The reaction temperature is not particularly limited as long as the chlorination reaction and the chlorosulfonation reaction proceed. For example, the reaction temperature is 40 to 150 ° C., and an appropriate chlorination reaction proceeds, preferably 60 to 130. ° C. The reaction pressure is not particularly limited as long as the chlorination and chlorosulfonation reactions proceed. For example, the reaction pressure is 0 to 1.0 megapascal, and preferably 0 because the appropriate chlorination and chlorosulfonation reactions proceed. ~ 0.7 megapascals.

  The radical initiator used is not particularly limited as long as the chlorination reaction proceeds, and examples thereof include azo compounds and organic oxides. Examples of the azo compound include α, α′-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and organic oxides. Examples thereof include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, and t-butyl perbenzoate. An azo compound is preferred because of its high stability in handling, and α, α'-azobisisobutyronitrile is particularly preferred since moderate chlorination and chlorosulfonation reactions proceed.

  In the reaction step of chlorination and chlorosulfonation of the present invention, a chlorinating agent (chlorine gas and sulfurous acid gas, chlorine gas and sulfuryl chloride, sulfurous acid gas and sulfuryl chloride, sulfuryl chloride alone, or chlorine gas, sulfurous acid gas and sulfuryl chloride) ) And a radical initiator are added by adding a chlorinating agent before adding the radical initiator, and stopping the addition of the chlorinating agent after stopping the radical initiator addition at the end of the process. If this order of addition is not performed, the light color is inferior.

  An antioxidant may be added before or during the reaction step for chlorination and chlorosulfonation in the present invention. The antioxidant is not particularly limited, and examples thereof include a phenolic antioxidant, an amine antioxidant, a sulfur antioxidant, and a phosphorus antioxidant. Examples of phenolic antioxidants include poly-2,2,4-trimethyl-1,2-dihydroquinoline, 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol), 2,6. -Di-t-butyl-p-cresol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and the like, and as the amine antioxidant, N-isopropyl-N′-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, and the like. Examples of the sulfur-based antioxidant include dilauryl. -3,3'-thiodipropionate and the like, and phosphorus antioxidants include, for example, tris (2,4-di-t-butylphenyl) phos Aito, and the like. The amount of these antioxidants to be added is not particularly limited, but 0.005 to 0.1 parts by weight with respect to 100 parts by weight of the raw material polyolefin is also used in order to suppress the effect of light color and reaction process. Preferably, 0.01-0.05 weight part is further more preferable.

  After completion of the chlorination and chlorosulfonation reactions, hydrogen chloride and / or sulfurous acid gas remaining in the reaction solution is removed by introducing nitrogen. Moreover, there is no problem even if chlorine hydrogen and / or sulfurous acid gas is removed under reduced pressure. After the removal of hydrogen chloride and / or sulfurous acid gas, an epoxy compound may be added as a stabilizer as necessary. Although it does not specifically limit as an epoxy compound, For example, unsaturated epoxidized soybean oil which epoxidized the vegetable oil which has a natural unsaturated group, epoxidized linseed oil, oleic acid, tall oil fatty acid, soybean oil fatty acid, etc. Aliphatic epoxy compounds such as epoxidized fatty acid esters obtained by epoxidizing fatty acids, cyclohexene oxide, α-pinene oxide, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, bisphenol A and polyvalent Glycidyl ethers such as bisphenol A glycidyl ether, ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether, etc. condensed with alcohol and epichlorohydrin Ter-type epoxy compound, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, s-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, phenol polyethylene oxide glycidyl ether The monoepoxy compounds such as are exemplified, and these can be used alone or in combination of two or more.

  Steam distillation, drum dryers, and vented extruders are known as methods for separating the product polymer from the solvent, and both are separated by these methods.

  The chlorosulfonated polyolefin of the present invention is blended and kneaded using a compounding agent in the same manner as conventional rubbers or resins, and used as a vulcanized or unvulcanized product of a chlorosulfonated polyolefin composition. Although it does not specifically limit as a compounding agent to be used, The acid acceptor, plasticizer, filler, reinforcing agent, anti-aging agent, lubricant, processing aid, vulcanization which are used for the conventional chlorosulfonated polyolefin are used. An agent or the like can be used.

  For end use, like existing chlorosulfonated polyolefin, automotive hose, gas hose, industrial hose, escalator handrail, electric wire, leisure boat, roofing, pound liner, roll, belt, boots, packing, seat, draw cloth, Adhesives, paints, sealants and the like can be mentioned.

  The chlorosulfonated polyolefin of the present invention has properties excellent in cold resistance and light color.

  EXAMPLES Next, although this invention is demonstrated concretely based on an Example, this invention does not receive any restriction | limiting by these Examples.

  In addition, the value used in these Examples was obtained based on the following measuring methods.

<Chlorine content, sulfur content>
The sulfur content of the chlorosulfonated polyolefin was measured by an oxygen combustion flask method according to JIS K6233 (1998 edition). The amount of chlorine was determined by burning the sample in a combustion flask, absorbing it in pure water as hydrochloric acid, and measuring the amount of chlorine with an automatic titrator using a 0.05 mol / L aqueous silver nitrate solution.

<Amount of 1,1,2-trichloroethane>
The amount of 1,1,2-trichloroethane in the chlorosulfonated polyolefin was measured by gas chromatography (column: DB-5, manufactured by Agilent).

<Evaluation of cold resistance>
The cold resistance of the chlorosulfonated polyolefin is determined by the chlorosulfonated polyolefin composition obtained by vulcanizing the obtained chlorosulfonated polyolefin with the composition shown in Table 1 and kneading the mixture at 150 ° C. for 15 minutes. Was measured by a Gehmann torsion test in accordance with JIS K6261 (2008 edition). T2 and T10 indicate temperatures at which the specific modulus corresponds to two times and ten times the modulus at 23 ± 2 ° C. If the values of T2 and T10 are large, it can be determined that the cold resistance is poor.

＜色調評価＞
クロロスルホン化ポリオレフィンの色調は、分光色差計（日本電色工業（株）製、ＳＥ−２０００）にて測定し、得られたＹＩ値にて評価した。ＹＩ値が１５以下になると明色性に優れる。

<Color tone evaluation>
The color tone of the chlorosulfonated polyolefin was measured with a spectral colorimeter (manufactured by Nippon Denshoku Industries Co., Ltd., SE-2000), and the obtained YI value was evaluated. When the YI value is 15 or less, the light color is excellent.

Example 1
After adding 15 kg of 1,1,2-trichloroethane, 2.25 kg of low density polyethylene having an MFR of 6.63, and 0.25 g of pyridine as a co-catalyst for the chlorosulfonation reaction to a 20 liter glass-lined autoclave, Steam was passed through the reactor jacket to uniformly dissolve the polyethylene at 110 ° C. During this time, nitrogen gas was introduced into the reactor at a flow rate of 10 liters / minute to remove air mixed in the reactor. As a radical initiator, 8.0 g of α, α′-azobisisobutyronitrile was dissolved in 2.0 kg of 1,1,2-trichloroethane. While continuously adding this solution to the reactor, 3.5 kg of sulfuryl chloride was added to the reactor from another inlet, and when the reaction was conducted, 22.0 cc / min of sulfuryl chloride, α, α -Azobisisobutyronitrile solution is continuously added at a flow rate of 5 cc / min, but sulfuryl chloride is added 2 minutes ahead of the addition of α, α'-azobisisobutyronitrile, and the reaction is completed. Occasionally, the addition of α, α'-azobisisobutyronitrile was stopped, and after 2 minutes, the addition of sulfuryl chloride was stopped. This took about 5 hours, but the pressure in the reaction vessel was kept at 0.2 megapascal. 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. Thereafter, the product was isolated with a drum dryer to obtain a chlorosulfonated polyolefin.

  Analysis revealed that the resulting chlorosulfonated polyolefin contained 30.6% by weight chlorine and 1.65% by weight sulfur. The amount of 1,1,2-trichloroethane was 0.001% by weight. The obtained chlorosulfonated polyolefin was used for cold resistance evaluation and color tone evaluation. These results are shown in Table 2. The results were excellent in cold resistance and color tone.

実施例２
酸化防止剤としてペンタエリスリトールテトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］を０．４５ｇ仕込んだ以外は実施例１と同様にしてクロロスルホン化ポリオレフィンを得た。

Example 2
A chlorosulfonated polyolefin was obtained in the same manner as in Example 1 except that 0.45 g of pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] was added as an antioxidant. .

  Analysis revealed that the resulting chlorosulfonated polyolefin contained 31.5 wt% chlorine and 1.69 wt% sulfur. The amount of 1,1,2-trichloroethane was 0.1% by weight. The obtained chlorosulfonated polyolefin was used for cold resistance evaluation and color tone evaluation. These results are also shown in Table 2. The results were excellent in cold resistance and color tone.

Example 3
Chlorosulfonated polyolefin in the same manner as in Example 1, except that the raw polyethylene was low density polyethylene having an MFR of 66.8 and 0.3 g of 2,6-di-t-butyl-p-cresol was added as an antioxidant. Got.

  Analysis revealed that the resulting chlorosulfonated polyolefin contained 31.9 wt% chlorine and 1.74 wt% sulfur. The amount of 1,1,2-trichloroethane was 0.06% by weight. The obtained chlorosulfonated polyolefin was used for cold resistance evaluation and color tone evaluation. These results are also shown in Table 2. The results were excellent in cold resistance and color tone.

Example 4
A chlorosulfonated polyolefin was obtained in the same manner as in Example 1 except that the raw material polyolefin was changed to a high-density polyethylene having an MFR of 3.8.

  Analysis revealed that the resulting chlorosulfonated polyolefin contained 31.0 wt% chlorine and 1.62 wt% sulfur. The amount of 1,1,2-trichloroethane was 0.05% by weight. The obtained chlorosulfonated polyolefin was used for cold resistance evaluation and color tone evaluation. These results are also shown in Table 2. The results were excellent in cold resistance and color tone.

Example 5
After adding 15 kg of 1,1,2-trichloroethane, 2.25 kg of low density polyethylene having an MFR of 15.3, and 0.25 g of pyridine as a co-catalyst for the chlorosulfonation reaction to a 20 liter glass-lined autoclave, Steam was passed through the reactor jacket to uniformly dissolve the polyethylene at 110 ° C. During this time, nitrogen gas was introduced into the reactor at a flow rate of 10 liters / minute to remove air mixed in the reactor.

  In the chlorination reaction, chlorine gas is first introduced into the reactor at a rate of 3 L / min, and after 10 minutes, 8.0 g of α, α′-azobisisobutyronitrile as a radical initiator is 1,1,1,2 -The addition of a solution dissolved in 2.0 kg of trichloroethane was started, the chlorination reaction was carried out for 3 hours, the addition of α, α'-azobisisobutyronitrile was stopped, 10 minutes later, the chlorine gas was stopped, and then When chlorosulfonation reaction is carried out by adding 2.0 kg of sulfuryl chloride to the reactor through another inlet, 22.0 cc / min of sulfuryl chloride and 5 cc of α, α′-azobisisobutyronitrile solution Is added continuously at a flow rate of 10 min / min., But sulfuryl chloride is added 10 min ahead, and at the end of the reaction, the addition of α, α'-azobisisobutyronitrile solution is stopped and 10 min after chlorination. The The addition of rufuryl was stopped. 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. Thereafter, the product was isolated with a drum dryer to obtain a chlorosulfonated polyolefin.

  Analysis revealed that the resulting chlorosulfonated polyolefin contained 30.1% by weight chlorine and 1.4% by weight sulfur. The amount of 1,1,2-trichloroethane was 0.03% by weight. The obtained chlorosulfonated polyolefin was used for cold resistance evaluation and color tone evaluation. These results are also shown in Table 2. The results were excellent in cold resistance and color tone.

Comparative Example 1
A chlorosulfonated polyolefin was obtained in the same manner as in Example 1 except that the solvent was changed to carbon tetrachloride.

  Analysis revealed that the resulting chlorosulfonated polyolefin contained 32.1 wt% chlorine and 1.72 wt% sulfur. The amount of 1,1,2-trichloroethane was 0.0 parts by weight. Using the resulting chlorosulfonated polyolefin, cold resistance evaluation and color difference meter measurement were performed. These results are also shown in Table 2. The color tone was excellent but the cold resistance was poor.

Comparative Example 2
A chlorosulfonated polyolefin was obtained in the same manner as in Example 4 except that the solvent was changed to carbon tetrachloride.

  Analysis revealed that the resulting chlorosulfonated polyolefin contained 31.5 wt% chlorine and 1.60 wt% sulfur. The amount of 1,1,2-trichloroethane was 0.0 parts by weight. Using the resulting chlorosulfonated polyolefin, cold resistance evaluation and color difference meter measurement were performed. These results are also shown in Table 2. The color tone was excellent, but the cold resistance was poor.

Comparative Example 3
When performing the reaction, add α, α'-azobisisobutyronitrile solution, add sulfuryl chloride 5 minutes later, and add α, α'-azobisisobutyronitrile 5 minutes after the addition of sulfuryl chloride. A chlorosulfonated polyolefin was obtained in the same manner as in Example 1 except that the change was made to stop the process.

  As a result of analysis, the obtained chlorosulfonated polyolefin was found to contain 31.3% by weight of chlorine and 1.2% by weight of sulfur. The amount of 1,1,2-trichloroethane was 0.01% by weight. The obtained chlorosulfonated polyolefin was used for cold resistance evaluation and color tone evaluation. These results are also shown in Table 2. The result was inferior in color tone.

  The chlorosulfonated polyolefin of the present invention has good cold resistance and is excellent in light color, so it is blended and kneaded in the same manner as conventional rubber or resin, and used as a vulcanized product or an unvulcanized product. Used in a wide range of areas.

Claims (4)

A chlorosulfonated polyolefin comprising 0.001 to 1.0% by weight of 1,1,2-trichloroethane and having a YI value of 15 or less. A method for producing a chlorosulfonated polyolefin in which 1,1,2-trichloroethane is used as a solvent to chlorinate and chlorosulfonate a polyolefin, the radical initiator being added after the addition of the chlorinating agent, The method for producing a chlorosulfonated polyolefin according to claim 1, wherein the addition is completed. The method for producing a chlorosulfonated polyolefin according to claim 2, wherein an antioxidant is added in the steps of chlorination and chlorosulfonate. 4. The material according to claim 2, wherein at least one selected from the group consisting of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and very low density polyethylene (VLDPE) is used as a raw material. Of producing chlorosulfonated polyolefin.