Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/25—Incorporating silicon atoms into the molecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
  • C08C19/00—Chemical modification of rubber
  • C08C19/26—Incorporating metal atoms into the molecule
• • 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
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
  • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
  • C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L15/00—Compositions of rubber derivatives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

• the conjugated diene-based graft polymer obtained has high transparency, heat resistance, and weather resistance, and have completed the present invention.
• aromatic vinyl compound that can form the monomer unit of the unmodified conjugated diene polymer (F') are the aromatics that can form the monomer unit of P contained in the active terminal polymer (I). It is the same as the specific example of the group vinyl compound.
• aromatic vinyl compounds styrene, ⁇ -methylstyrene, and 4-methylstyrene are preferable.
• the aromatic vinyl compound may be used alone or in combination of two or more.
• the weight average molecular weight (Mw) of the unmodified conjugated diene polymer (F') is preferably 1,000 or more and less than 1,000,000, and more preferably 2,000 or more and less than 500,000. , 3,000 or more and less than 100,000 are more preferable.
• Mw of the unmodified conjugated diene polymer (F') is within the above range, the process passability during production tends to be excellent and the economic efficiency tends to be good.
• radical polymerization initiator examples include persulfates such as ammonium persulfate and potassium persulfate, organic peroxides, hydrogen peroxide and the like.
• the temperature of solution polymerization is usually in the range of ⁇ 80 to 150 ° C., preferably in the range of 0 to 100 ° C., and more preferably in the range of 10 to 90 ° C.
• the polymerization mode may be either a batch type or a continuous type.
• silane compound (IV) examples include mercaptomethylenemethyldiethoxysilane, mercaptomethylenetriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethylmethoxydimethylsilane, and 2-.
• Examples of the organic solvent used in the above method generally include a hydrocarbon solvent and a halogenated hydrocarbon solvent.
• hydrocarbon solvents such as n-butane, n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene are preferable.
• the organic solvent may be used alone or in combination of two or more.
• carboxylic acid examples include formic acid, acetic acid, propionic acid, butyric acid, methoxyacetic acid, pentanoic acid, caproic acid, heptanic acid, octanoic acid, lactic acid, and glycolic acid.
• formic acid, acetic acid and lactic acid are preferable, and acetic acid is more preferable.
• the melt viscosity of the functional group-modified conjugated diene polymer (F) measured at 38 ° C. is preferably 0.1 to 2,000 Pa ⁇ s, more preferably 0.1 to 1500 Pa ⁇ s, and 0.1 to 1000 Pa ⁇ s. -S is more preferable.
• the melt viscosity of the functional group-modified conjugated diene polymer (F) is within the above range, the process passability during production tends to be excellent and the economic efficiency tends to be good.
• the melt viscosity of the conjugated diene-based graft polymer is a value measured by a Brookfield viscometer at 38 ° C.
• a conjugated diene-based graft polymer is produced by the reaction of two kinds of polymers as described above, one of the raw materials is a polymer having a silyl chloride group as a reactive functional group as described in Non-Patent Document 1.
• a halide is produced as a by-product. Due to this halide, the transparency, heat resistance, and weather resistance of the obtained conjugated diene-based graft polymer tend to decrease. Further, chlorosilanes used for synthesizing a polymer having a silyl chloride group as a reactive functional group are very reactive and highly harmful, and therefore have a problem in handleability.
• the inactivation step (A-2) is preferably performed before the recovery step (B) because it is considered that they are likely to cause a condensation reaction with each other.
• Alkyl lithiums such as sec-butyl lithium and t-butyl lithium; alkyl sodiums such as methyl sodium, ethyl sodium, n-propyl sodium, isopropyl sodium, n-butyl sodium, sec-butyl sodium and t-butyl sodium; methyl Alkyl potassiums such as potassium, ethyl potassium, n-propyl potassium, isopropyl potassium, n-butyl potassium, sec-butyl potassium, t-butyl potassium; methylmagnesium bromide, ethylmagnesium bromide, t-butylmagnesium bromide, t-butyl Alkyl magnesium halides such as magnesium chloride and sec-butylmagnesium iodide; dialkyl copper lithium such as dimethyl copper lithium, diethyl copper lithium, methyl ethyl copper lithium, methyl n-propyl copper lithium, ethyl n-butyl copper lithium
• Amount of Inactivating Reagent Used in Step (A-2) / Molar Ratio of Total Amount of Alkoxy Group and Hydroxyl Group Derived from Group V in Conjugated Diene Graft Polymer Obtained in Step (A-1) Is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 2.0 or more. Further, it is preferably 100 or less, more preferably 50 or less, and further preferably 20 or less.
• the amount of the inactivating reagent is small, the number of functional groups (c) that can be directly bonded to the branch point cannot be adjusted to a desired range, and when the amount of the inactivating reagent is large, it is economical. Sex tends to worsen.
• the inactivation reaction of the above step (A-2) is usually carried out in a temperature range of 0 to 100 ° C. for 0.1 to 50 hours.
• the inactivating reagent may be diluted and used, and the diluting solvent is not particularly limited as long as it is inactive with respect to the inactivating reagent and does not adversely affect the reaction.
• the diluting solvent is not particularly limited as long as it is inactive with respect to the inactivating reagent and does not adversely affect the reaction.
• Saturated aliphatic hydrocarbons such as decane, toluene, benzene and xylene or aromatic hydrocarbons can be mentioned.
• the conjugated diene-based graft polymer of the present invention has a main chain (a) composed of a polymer containing a conjugated diene unit.
• the main chain contained in the conjugated diene-based graft polymer of the present invention is the same as the main chain in the functional group-modified conjugated diene-based polymer (F), and is a total monomer containing a conjugated diene unit constituting the main chain. Refers to the entire part derived from the unit.
• conjugated diene as the conjugated diene unit constituting the polymer of the main chain (a), and other than the conjugated diene as the monomer unit constituting the polymer.
• other monomers for example, aromatic vinyl compounds
• preferred examples, preferred contents, weight average molecular weight (Mw), vinyl contents, preferred embodiments of Tg, etc. are described in the description of the unmodified conjugated diene polymer (for example, an unmodified conjugated diene polymer). It is the same as the explanation regarding F').
• the side chain (b) is bonded to the main chain (a) via one heteroatom having a valence of 3 or more, which is a branching point.
• N represents the valence of Z, and m and n are integers that independently satisfy the following equation (5); 0 ⁇ m ⁇ N-1, 0 ⁇ n ⁇ N-1 (5)
• P may be the same or different
• V may be the same or different
• R 3 may be the same.
• Z 1 may be the same or different.
• P (side chain (b)) needs to be bonded at at least one branch point (Z 1 ) contained in the conjugated diene-based graft polymer of the present invention.
• X is preferably in the range of 0.01 or more and 9.9 or less, and more preferably in the range of 0.02 or more and 9 or less.
• the number of side chains (b) and the number of functional groups (c) directly bonded to the branch point are determined by the activity in the step (A-1) when the conjugated diene graft polymer is produced by the above production method.
• the amount and reaction time of the reagent used to inactivate at least a part of (functional group V existing unreacted) and the type and amount of polar compound used as needed, it is desired. Can be adjusted to a range.
• the average number W of side chains (b) directly bonded to the branch point per molecule of the conjugated diene-based graft polymer is the conjugated diene-based graft polymer in the step (A-1) of the above-mentioned production method.
• the following formula is used using the amount (number of moles) of the active terminal polymer (I) serving as the side chain (b) per active terminal and the amount (number of moles) of the functional group-modified conjugated diene polymer (F). Obtained from (8).
• the molecular weight distribution (Mw / Mn) of the conjugated diene-based graft polymer of the present invention is preferably 1.0 to 20.0, more preferably 1.0 to 10.0, still more preferably 1.0 to 5.0. 1.0 to 2.0 is particularly preferable.
• Mw / Mn is within the above range, the variation in viscosity of the conjugated diene-based graft polymer is small, which is more preferable.
• Mn means a number average molecular weight
• Mn is a standard polystyrene-equivalent number average molecular weight obtained from GPC measurement.
• the conjugated diene-based graft polymer of the present invention preferably has a catalyst residue amount derived from the polymerization catalyst used for its production in the range of 0 to 200 ppm in terms of metal.
• a catalyst residue amount derived from the polymerization catalyst used for its production in the range of 0 to 200 ppm in terms of metal.
• the metal that serves as a reference for the amount of catalyst residue is an alkali such as lithium. Become metal.
• the amount of the catalyst residue is in the above range, the tack does not decrease during processing and the like, and the heat resistance of the conjugated diene-based graft polymer of the present invention is improved.
• the conjugated diene-based graft polymer of the present invention preferably has a halogen content of 1000 ppm or less.
• the reference halogen is chlorine.
• the halogen content is in the above range, transparency, heat resistance, and weather resistance tend to be good.
• the other polymer ( ⁇ ) is a curable polymer ( ⁇ 2)
• the polymer composition is sufficiently mixed with a mixer or the like, then melt-kneaded with a mixing roll, an extruder or the like, and then cooled and pulverized to prepare the polymer composition. Can be made.
• the other polymer ( ⁇ ) is a thermoplastic polymer ( ⁇ 1)
• the polymer composition is molded by, for example, extrusion molding, injection molding, hollow molding, compression molding, vacuum molding, calendar molding, or the like.
• a product can be manufactured.
• molded products, sheets, films and the like having various shapes can be obtained.
• a molded product in the form of a non-woven fabric or a fibrous material can be produced by a method such as a melt blow method or a spunbond method.
• adhesives such as (adhesives for assembling parts in transportation equipment such as aircraft); various paints such as anticorrosion / waterproof paints for water and sewage, anticorrosion paints for metals;
• coating primers such as coating primers for transportation equipment; various lining materials such as metal lining materials, concrete lining materials, tank lining materials; various repair materials such as crack repair materials for concrete; printed wiring boards, insulating boards ,
• electrical and electronic parts such as semiconductor encapsulants and packaging materials.
• Coupling rate of the conjugated diene-based graft polymer is calculated by the following formula using the sum of the peak areas of the unreacted polymer components obtained by the above GPC measurement and all the peak areas.
• (Coupling rate (%)) [ ⁇ ((Sum of all peak areas)-(Peak area of components derived from active terminal polymer (I)) ⁇ / (Sum of all peak areas)] ⁇ 100
• Step (4) Subsequently, 7.0 g of tetrahydrofuran and the functional group-modified conjugated diene polymer (F-1) obtained in step (2) were added to the solution containing the active terminal polymer (I-1) obtained in step (3). 1480 g of the diluted solution was added, and the coupling reaction was carried out at 50 ° C. for 2 hours. Then, 190 g of sec-butyllithium (10.5 mass% cyclohexane solution) was added and reacted for 6 hours to seal a part of the remaining alkoxy groups. Then, 21 g of methanol was added to stop the polymerization reaction to obtain a polymer solution.
• Step (5) Water was added to the obtained polymer solution, the mixture was stirred, and the polymer solution was washed with water. After the stirring was completed and it was confirmed that the polymer solution phase and the aqueous phase were separated, water was separated. After the washing was completed, the polymer solution was vacuum dried at 70 ° C. for 24 hours to obtain a conjugated diene-based graft polymer (G-1).
• the obtained functional group-modified conjugated diene polymer (F-15) revealed that the main chain (a) of the conjugated diene graft polymer (G-15) described later contains the weight average molecular weight, vinyl content, and styrene unit. The amount can be calculated.
• the obtained functional group-modified conjugated diene polymer (F-15) has a weight average molecular weight of 26,000, a vinyl content of 30 mol%, a styrene unit content of 0% by mass, and B atoms per molecule of the polymer. The average number was four.
• Step (3) A sufficiently dried 5 L autoclave is replaced with nitrogen, 700 g of cyclohexane and 78 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is set to 50 ° C. under stirring conditions. While controlling in this manner, 340 g of butadiene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-15).
• the weight average molecular weight, vinyl content, and styrene unit content of the side chain (b) of the conjugated diene-based graft polymer (G-15) described later can be determined. be able to.
• the weight average molecular weight of the obtained active terminal polymer (I-15) was 5,000, the vinyl content was 10 mol%, and the styrene unit content was 0% by mass.
• Step (3) A sufficiently dried 5 L autoclave is replaced with nitrogen, 700 g of cyclohexane and 78 g of sec-butyllithium (10.5 mass% cyclohexane solution) are charged, the temperature is raised to 50 ° C., and then the polymerization temperature is set to 50 ° C. under stirring conditions. While controlling in this manner, 340 g of butadiene was sequentially added and polymerized for 1 hour to obtain an active terminal polymer (I-18).
• the weight average molecular weight, vinyl content, and styrene unit content of the side chain (b) of the conjugated diene-based graft polymer (G-18) described later can be determined. be able to.
• the weight average molecular weight of the obtained active terminal polymer (I-18) was 5,000, the vinyl content was 10 mol%, and the styrene unit content was 0% by mass.
• the obtained functional group-modified conjugated diene polymer (F-19) has a weight average molecular weight of 100,000, a vinyl content of 30 mol%, a styrene unit content of 0% by mass, and Si atoms per polymer molecule. The average number was four. 1650 g of cyclohexane is added to the obtained functional group-modified conjugated diene polymer (F-19) to dilute it to a concentration of 30% by mass, and the functional group-modified conjugated diene polymer (F-19) used in the coupling reaction described later is used. ) was obtained.

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• 2020
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