Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
  • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
  • C08F255/023—On to modified polymers, e.g. chlorinated polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
  • C08F8/38—Sulfohalogenation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters

Definitions

• the present invention relates to a vulcanized composition of a modified halogenated polyolefin composition. More specifically, the present invention relates to a graft copolymer in which a copolymer of acrylonitrile and an acrylic compound is bonded to a halogenated polyolefin, and a bond to a halogenated polyolefin. The present invention relates to a vulcanized composition of a composition containing a copolymer of acrylonitrile and an acrylic compound.
• the inventor has intensively studied to solve the above problems, and as a result, has completed the present invention.
• a modified halogenated polyolefin composition containing a graft copolymer in which a copolymer of acrylonitrile and an acrylic compound is bonded to a halogenated polyolefin, and a copolymer of acrylonitrile and an acrylic compound not bonded to the halogenated polyolefin A vulcanized composition obtained by vulcanizing a product.
• the vulcanized composition according to [1] or [2], wherein [4] The total content of the copolymer of acrylonitrile and the acrylic compound not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the copolymer of the acrylonitrile and the acrylic compound in the graft copolymer is The vulcanized composition according to any one of [1] to [3], which is in the range of 20% to 75% by weight.
• the weight ratio of the components derived from the acrylonitrile and the acrylic compound contained in the copolymer of acrylonitrile and the acrylic compound not bonded to the halogenated polyolefin and the graft copolymer is in the range of 3/97 to 70/30.
• the vulcanized composition according to any one of [1] to [4], wherein [6] The vulcanized composition according to any one of [1] to [5], wherein the acrylic compound is 2-methoxyethyl acrylate.
• the weight ratio of the epoxy group-containing copolymer in the graft copolymer to the epoxy group-containing copolymer not bonded to the halogenated polyolefin is in the range of 3/97 to 70/30.
• the modified halogenated polyolefin composition of the second embodiment of the present invention is obtained by co-grafting an unsaturated monomer containing acrylonitrile, an epoxy group-containing compound and an acrylic compound to the halogenated polyolefin. Can do.
• the graft copolymer can be obtained by fractionation from the resulting modified halogenated polyolefin composition.
• the solvents include aromatic organic solvents such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodi Chlorinated organic solvents such as fluorobenzene, carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, tetrachloroethane, trichlorofluoroethane, etc. These may be used alone or in combination of two or more, but it is preferable to use only a chlorinated organic solvent that is inert to the chlorination reaction.
• aromatic organic solvents such as benzene, toluene, xylene, monochlorobenzene, dichlorobenzene, fluorobenzene, dichlorodi Chlorinated organic solvents such as fluoro
• an amino compound such as pyridine or quinoline is added as a co-catalyst as necessary.
• the amount of chlorine in the halogenated polyolefin used in the production of the modified halogenated polyolefin composition is not particularly limited, but it is preferably in the range of 15.0 to 45.0% by weight in consideration of oil resistance and mechanical properties, and further low temperature properties. In view of the above, it is preferably in the range of 20.0 wt% to 40.0 wt%.
• the amount of sulfur when the halogenated polyolefin is chlorosulfonated polyethylene obtained by chlorinating and chlorosulfonated polyolefin is not particularly limited, but is preferably in the range of 0.1 to 3.0% by weight.
• the acrylic compound co-grafted to the halogenated polyolefin is not limited as long as it is a compound containing an acryloyl group or a methacryloyl group.
• alkyl vinyl ketone compounds such as methyl vinyl ketone
• alkyl vinyl ether compounds such as vinyl ethyl ether
• allyl ether compounds such as allyl methyl ether
• vinyl aromatic compounds such as styrene, ⁇ -methyl styrene, chlorostyrene, vinyl toluene, vinyl naphthalene, etc.
• the weight ratio (graft selectivity) of the copolymer of acrylonitrile and acrylic compound in the graft copolymer and the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin,
• the weight ratio is preferably in the range of 3/97 to 70/30.
• an epoxy group-containing compound and an acrylic compound an epoxy group-containing copolymer bonded to the halogenated polyolefin in the graft copolymer and an epoxy group-containing copolymer not bonded to the halogenated polyolefin.
• the weight ratio (graft selectivity) between the epoxy group-containing copolymer in the graft copolymer and the epoxy group-containing copolymer that is not bonded to the halogenated polyolefin is not particularly limited, but the resulting modified halogenated polyolefin In order to achieve both the mechanical properties and oil resistance of the composition, the weight ratio is preferably in the range of 3/97 to 70/30.
• a copolymer of acrylonitrile and an acrylic compound that is not bonded to a halogenated polyolefin and a copolymer of acrylonitrile and an acrylic compound in a graft copolymer are used.
• the total content of the polymer is preferably in the range of 20% by weight to 75% by weight in order to achieve both excellent physical properties and oil resistance while maintaining the properties as the halogenated polyolefin composition. More preferably, it is in the range of 40% to 65% by weight.
• the remaining components are components derived from the halogenated polyolefin in the graft copolymer.
• the polymerization ratio of components derived from acrylonitrile and the acrylic compound contained in the coalescence is preferably in the range of 3/97 to 70/30, more preferably in the range of 10/90 to 70/30, and 15/85 to 60/40. It is preferable to be in the range.
• the weight ratio of acrylonitrile in the copolymer is 3% or more, the tensile strength of the resulting modified halogenated polyolefin vulcanizate is maintained.
• the weight ratio of acrylonitrile is 70% or less, the viscosity of the resulting modified halogenated polyolefin composition does not increase and the moldability is good.
• the weight ratio of acrylonitrile is preferably as low as possible without impairing the oil resistance, and is in the range of 3/97 to 50/50.
• the acrylonitrile contained in the epoxy group-containing copolymer in the graft copolymer and the epoxy group-containing copolymer not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition of the second embodiment of the present invention is preferably in the range of 3/97 to 70/30, more preferably in the range of 10/90 to 70/30, particularly in the range of 15/85 to 60/40. Is preferred. When the weight ratio of acrylonitrile in the copolymer is 3% or more, the tensile strength of the resulting modified halogenated polyolefin vulcanizate is maintained.
• the weight ratio of acrylonitrile is 70% or less, the viscosity of the resulting modified halogenated polyolefin composition does not increase and the moldability is good.
• the weight ratio of acrylonitrile is preferably as low as possible without impairing the oil resistance, and is in the range of 3/97 to 50/50.
• the content of the epoxy group-containing compound-derived component in the modified halogenated polyolefin composition of the second embodiment of the present invention is preferably in the range of 1% by weight to 12% by weight.
• the epoxy group-containing compound is an epoxy group-containing acrylic compound
• the epoxy group-containing copolymer not bonded to the halogenated polyolefin in the modified halogenated polyolefin composition and the epoxy group in the graft copolymer It is preferable to add an acrylic compound that does not contain an epoxy group in such a range that the weight ratio of the component derived from acrylonitrile and the acrylic compound contained in the containing copolymer is 10/90 to 70/30.
• the epoxy group-containing compound acts as a crosslinking point in the modified halogenated polyolefin composition, and if the weight ratio of the epoxy group-containing compound in the modified halogenated polyolefin composition is 1% by weight or more, A sufficient crosslinked structure can be formed, and the resulting modified halogenated polyolefin vulcanizate is excellent in oil resistance and tensile strength.
• the weight ratio of the component derived from the epoxy group-containing compound in the modified halogenated polyolefin composition is 12% by weight or less, the resulting modified halogenated polyolefin vulcanizate is hardened by forming an excessive cross-linked structure. The problem that the elongation at break is reduced does not occur without increasing the thickness.
• the weight ratio of the epoxy group-containing compound in the modified halogenated polyolefin composition is preferably in the range of 2 to 10% by weight.
• a copolymer containing acrylonitrile, an epoxy group-containing compound and an acrylic compound that are not bonded to the halogenated polyolefin is bonded to the halogenated polyolefin. Some are not bonded to halogenated polyolefins.
• the method for adding the unsaturated monomer and the radical initiator described above is not particularly limited, and is a method in which the unsaturated monomer and / or the radical initiator are added together at the initial stage of the co-grafting reaction. Examples thereof include a method of adding at the initial stage of the grafting reaction and continuously injecting the remaining unsaturated monomers and / or radical initiators, and a method of continuously injecting all unsaturated monomers and / or radical initiators.
• a molecular weight modifier may be added during the co-grafting reaction.
• the molecular weight regulator include diisopropyl xanthogen disulfide, diethyl xanthogen disulfide, diethyl thiuram disulfide, 2,2′-dithiopropionic acid, 3,3′-dithiopropionic acid, 4,4′-dithiodibranic acid, 2,2 ′.
• Disulfides such as dithiobisbenzoic acid, n-dodecyl mercaptan, octyl mercaptan, t-butyl mercaptan, thioglycolic acid, thiomalic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosalicylic acid, 3-mercaptobenzoic acid, Mercaptans such as thiomaleic anhydride, dithiomaleic acid, thioglutaric acid, cysteine, homocysteine, 6-mercaptotetrazoleacetic acid, 3-mercapto-1-propanesulfonic acid, diphenylethylene p- chloro diphenylethylene, p- cyano-diphenyl ethylene, alpha-methyl styrene dimer, benzyl dithio benzoate, organic tellurium compounds, sulfur and the like, can be used alone or in combination.
• the antioxidant is not particularly limited, and is generally used as an antioxidant for polymers.
• reaction temperature and reaction pressure of the co-grafting reaction are not particularly limited, but the reaction temperature is preferably 50 to 150 ° C. and the reaction pressure is preferably 0 to 1.0 MPa.
• the desired modified halogenated polyolefin composition is obtained by precipitation with an insoluble solvent such as methanol, concentration and drying using a drum dryer, an extruder with a vent, or the like.
• the graft copolymer is fractionated by adding the solution after completion of the reaction to a solvent in which the graft copolymer such as acetone is insoluble and the epoxy group-containing copolymer is soluble, and this is dried.
• a solvent in which the graft copolymer such as acetone is insoluble and the epoxy group-containing copolymer is soluble is dried.
• the vulcanized composition of the modified halogenated polyolefin composition of the present invention has both good flame retardancy, physical properties and oil resistance, especially various hoses, various seal materials, packing, etc. that require oil resistance. Can be used.
• the total content of the epoxy group-containing copolymer not bonded to the halogenated polyolefin and the epoxy group-containing copolymer in the graft copolymer in the modified halogenated polyolefin composition is the halogenated raw material. It calculated from the weight of the reacted unsaturated monomer calculated
• the modified halogenated polyolefin composition the total content of the copolymer of acrylonitrile and acrylic compound not bonded to the halogenated polyolefin and the copolymer of acrylonitrile and acrylic compound in the graft copolymer is The weight was calculated from the weight of the halogenated polyolefin as a raw material, the amount of unsaturated monomers (acrylonitrile and acrylic compound) charged, and the weight of reacted unsaturated monomers determined from the conversion rate of each unsaturated monomer.
• Acetone extract weight [A] Acetone extraction residue weight [B] 3
• the chlorine content in the acetone extract and the acetone extract residue is measured.
• the sulfur content is measured by first using an acetone extract of the raw halogenated polyolefin or modified halogenated polyolefin composition in a combustion flask containing 10.0 ml of 3.0% by weight hydrogen peroxide as an absorbent. 30.0 mg of acetone extraction residue was burned according to the oxygen combustion method and allowed to stand for 30 minutes. Next, this absorbing solution was washed out with about 40.0 ml of pure water, and then 1 ml of acetic acid, 100.0 ml of 2-propyl alcohol, and 0.47 ml of arsenazo III were added. This was determined by quantifying sulfate ion by a photometric titration method with a 0.01N concentration barium acetate solution.
• Example 1 After adding 21.6 kg of 1,1,2-trichloroethane, density of 960 kg / cm 3 , and melt flow rate (MFR) of 5.0 g / 10 min to 3 kg of 40 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 10.0 liters / minute to remove air in the reactor. As a radical generator, a solution of 5.0 g of ⁇ , ⁇ -azobisisobutyronitrile dissolved in 1.0 liter of 1,1,2-trichloroethane at a flow rate of 4.0 ml / min, 6.5 kg of chloride.
• MFR melt flow rate
• the obtained chlorosulfonated polyethylene contained 35.3% by weight of chlorine and 0.22% by weight of sulfur.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-n-butyl acrylate copolymer content of 31.7% by weight, and the acrylonitrile / n-butyl acrylate acrylonitrile / n-butyl acrylate ratio. was 26/74.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
• Example 2 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1, except that the amount of the unsaturated monomer charged was changed to 59.7 g of acrylonitrile and 48.1 g of n-butyl acrylate.
• the resulting modified halogenated polyolefin composition has an acrylonitrile-n-butyl acrylate copolymer content of 27.4% by weight, and the acrylonitrile / n-butyl acrylate copolymer has an acrylonitrile / n-butyl acrylate ratio.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
• Example 3 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 39.8 g of acrylonitrile and 75.1 g of ethyl acrylate.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 28.0% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 31/69. It was.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 26.1% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 59/41. It was.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
• Example 5 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 39.8 g of acrylonitrile and 97.6 g of 2-methoxyethyl acrylate.
• Example 6 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 59.7 g of acrylonitrile and 48.8 g of 2-methoxyethyl acrylate.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 24.4% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 45/55.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
• Example 7 Modified halogenated polyolefin composition in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 180 g, and the unsaturated monomer was changed to 53.4 g of acrylonitrile and 100.8 g of ethyl acrylate. Got.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 29.9% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 32/68. It was.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
• Example 8 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 103.9 g of acrylonitrile and 196.1 g of ethyl acrylate.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 54.0% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 33/67. It was.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 2.
• Example 9 Modified halogenated polyolefin composition in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 180 g, and the unsaturated monomer was changed to 79.4 g of acrylonitrile and 74.9 g of ethyl acrylate. Got.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-ethyl acrylate copolymer content of 28.5% by weight, and the acrylonitrile-ethyl acrylate copolymer had an acrylonitrile / ethyl acrylate ratio of 53/47. It was.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
• Example 10 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 154.4 g of acrylonitrile and 145.6 g of ethyl acrylate.
• Example 11 Modified halogenation in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 200 g, and the unsaturated monomer was changed to 49.7 g of acrylonitrile and 121.8 g of 2-methoxyethyl acrylate. A polyolefin composition was obtained.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 55.4% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 30/70.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
• Example 13 Modified halogenation in the same manner as in Example 1 except that the amount of chlorosulfonated polyethylene charged in the co-graft reaction was changed to 180 g, and the unsaturated monomer was changed to 69.3 g of acrylonitrile and 85.0 g of 2-methoxyethyl acrylate. A polyolefin composition was obtained.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 50.2% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 49/51.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 3.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 42.8% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 40/60.
• the physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 3.
• Example 16 Co-grafting reaction was carried out using the chlorosulfonated polyethylene described in Example 15 as the halogenated polyolefin.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 32.1% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 49/51.
• the physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 4.
• Example 17 Co-grafting reaction was carried out using the chlorosulfonated polyethylene described in Example 15 as the halogenated polyolefin.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 45.1% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl acrylate copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 39/61.
• the physical properties were evaluated according to the formulation of formulation 2. The evaluation results are shown in Table 4.
• Example 18 Co-grafting reaction was carried out using the chlorosulfonated polyethylene described in Example 15 as the halogenated polyolefin.
• Example 19 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the unsaturated monomer was changed to 100.0 g of acrylonitrile, 268.4 g of 2-methoxyethyl acrylate, and 10.9 g of glycidyl methacrylate.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 56.6% by weight, and acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer.
• the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate ratio was 31/64/5.
• the physical properties were evaluated according to the formulation of formulation 3. The evaluation results are shown in Table 4.
• Example 20 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the amount of the unsaturated monomer charged was changed to 39.8 g of acrylonitrile, 11.0 g of glycidyl methacrylate, and 96.1 g of n-butyl acrylate. It was.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-n-butyl acrylate copolymer (epoxy group-containing copolymer) content of 32.5% by weight, and acrylonitrile-glycidyl methacrylate-acrylic.
• the acrylonitrile / n-butyl acrylate ratio of the acid n-butyl copolymer was 29/71.
• the physical properties were evaluated according to the formulation of formulation 4. The evaluation results are shown in Table 4.
• Example 21 A modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that the amount of the unsaturated monomer charged was changed to 103.9 g of acrylonitrile, 11.0 g of glycidyl methacrylate, and 196.1 g of ethyl acrylate.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-ethyl acrylate copolymer content of 54.4% by weight and an acrylonitrile / acrylic acid acrylonitrile-glycidyl methacrylate-ethyl acrylate copolymer.
• the ethyl ratio was 35/65.
• the physical properties were evaluated according to the formulation of formulation 4. The evaluation results are shown in Table 4.
• Example 22 A modified halogenated polyolefin composition was obtained in the same manner as in Example 20 except that the unsaturated monomer was changed to 100.0 g of acrylonitrile, 11.0 g of glycidyl methacrylate, and 268.4 g of 2-methoxyethyl acrylate.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 56.3% by weight, and the acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer.
• the combined acrylonitrile / 2-methoxyethyl acrylate ratio was 33/67.
• the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 58.8% by weight, and acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer.
• the combined acrylonitrile / 2-methoxyethyl acrylate ratio was 31/69.
• the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 63.4% by weight, and an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer.
• the combined acrylonitrile / 2-methoxyethyl acrylate ratio was 29/71.
• the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer content of 55.1% by weight, and the acrylonitrile-glycidyl methacrylate-2-methoxyethyl acrylate copolymer.
• the combined acrylonitrile / 2-methoxyethyl acrylate ratio was 32/68.
• the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
• Example 26 Using TOSO-CSM TS-830 (manufactured by Tosoh Corporation) as the halogenated polyolefin, the unsaturated monomer was changed to 100.7 g of acrylonitrile, 317.3 g of 2-methoxyethyl acrylate, and 22.2 g of glycidyl methacrylate.
• a modified halogenated polyolefin composition was obtained in the same manner as in Example 1 except that.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 61.0% by weight, and acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer.
• the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate ratio was 28/63/9.
• the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
• Example 27 A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 56.0 g of acrylonitrile, 314.6 g of 2-methoxyethyl acrylate, and 21.9 g of glycidyl methacrylate.
• Example 28 A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 36.4 g of acrylonitrile, 282.2 g of 2-methoxyethyl acrylate, and 21.5 g of glycidyl methacrylate.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 61.9% by weight, and an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer.
• the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate ratio was 12/81/9.
• the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
• Example 29 A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 20.8 g of acrylonitrile, 298.6 g of 2-methoxyethyl acrylate, and 21.5 g of glycidyl methacrylate.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 65.5% by weight, and acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer.
• the ratio of the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate was 6/87/7.
• the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 5.
• Example 30 A modified halogenated polyolefin composition was obtained in the same manner as in Example 26 except that the unsaturated monomer was changed to 16.7 g of acrylonitrile, 328.6 g of 2-methoxyethyl acrylate, and 20.1 g of glycidyl methacrylate.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer content of 67.7% by weight, and the acrylonitrile-2-methoxyethyl acrylate-glycidyl methacrylate copolymer
• the ratio of the combined acrylonitrile / 2-methoxyethyl acrylate / glycidyl methacrylate was 4/90/6.
• the physical properties were evaluated according to the formulation of formulation 5. The evaluation results are shown in Table 6.
• the resulting modified halogenated polyolefin composition had an acrylonitrile polymer content of 15.2% by weight.
• the physical properties were evaluated according to the formulation of formulation 1. The evaluation results are shown in Table 6.
• the Mooney viscosity of the blend is high and has problems with moldability.
• Comparative Example 3 A modified halogenated polyolefin composition was obtained in the same manner as in Comparative Example 1 except that the graft reaction was changed to 100 g of chlorosulfonated polyethylene, 106.1 g of acrylonitrile, and 5.9 g of radical initiator.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 56.9% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 32/68.
• the obtained modified halogenated polyolefin composition had a low viscosity and was difficult to knead for physical property evaluation, so physical property evaluation could not be performed.
• the resulting modified halogenated polyolefin composition had an acrylonitrile-2-methoxyethyl acrylate copolymer content of 55.8% by weight, and the acrylonitrile-acrylic acid 2-methoxyethyl copolymer acrylonitrile / acrylic acid 2- The methoxyethyl ratio was 30/70. Although kneading was carried out with the formulation of Formula 4 and Formula 5, the physical property evaluation was difficult because the crosslinking reaction did not proceed.

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• 2016
  • 2016-11-16 WO PCT/JP2016/083966 patent/WO2017086347A1/ja active Application Filing
  • 2016-11-16 CN CN201680067357.9A patent/CN108291073A/zh active Pending
  • 2016-11-16 DE DE112016005267.7T patent/DE112016005267T5/de not_active Withdrawn

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