WO2017033749A1 - Procédé de production de polymère à base de polyisobutylène à terminaison (méth)acryloyle - Google Patents

Procédé de production de polymère à base de polyisobutylène à terminaison (méth)acryloyle Download PDF

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WO2017033749A1
WO2017033749A1 PCT/JP2016/073556 JP2016073556W WO2017033749A1 WO 2017033749 A1 WO2017033749 A1 WO 2017033749A1 JP 2016073556 W JP2016073556 W JP 2016073556W WO 2017033749 A1 WO2017033749 A1 WO 2017033749A1
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acryloyl
meth
terminated polyisobutylene
polyisobutylene polymer
producing
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PCT/JP2016/073556
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Japanese (ja)
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孝洋 大石
昌史 時實
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株式会社カネカ
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    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/08—Butenes
    • C08F10/10—Isobutene
    • 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

Definitions

  • the present invention relates to a method for producing a (meth) acryloyl-terminated polyisobutylene polymer. More specifically, the present invention relates to a production method capable of obtaining a (meth) acryloyl-terminated polyisobutylene-based polymer that is stable and good in transparency.
  • Active energy ray curing technology is more solvent-free, energy-saving, and space-saving in the curing process than heat curing technology.
  • active energy ray curing improves the productivity because the reaction can be completed in a short time.
  • this active energy ray curing technique is used in applications such as inks, paints, adhesives, sealants, precision parts for electric / electronic applications, and shaped articles.
  • the main characteristics required for the resin in the above fields include durability, heat resistance, weather resistance, water resistance, water gas permeability, etc., and examples of resins having such characteristics include Examples include polyisobutylene polymers having a photocrosslinkable group at the end of isobutylene.
  • Patent Document 1 discloses a process using a hydroxyl-terminated polyisobutylene polymer as a raw material
  • Patent Document 2 discloses a chlorine-terminated polyisobutylene polymer, an endcap agent having a (meth) acryloyl group and a carbon-carbon double bond
  • Patent Document 3 describes a production method based on the reaction between the chlorine-terminated polyisobutylene polymer and an end cap agent having a (meth) acryloyl group and a phenoxy group.
  • Patent Documents 2 and 3 are a one-step reaction between a polyisobutylene terminal obtained by using a chlorine-based initiator and a Lewis acid catalyst and an end-capping agent, and a (meth) acryloyl-terminated polyisobutylene system is simply used A polymer can be obtained.
  • an object of the present invention is to provide a simple method that can be employed in an actual production process, as well as a method for producing a (meth) acryloyl-terminated polyisobutylene polymer having excellent transparency. is there.
  • the present inventors have studied to find out the reason why a highly transparent and colorless (meth) acryloyl-terminated polyisobutylene polymer cannot be stably obtained.
  • I found out If the Lewis acid catalyst itself and the catalyst residue after deactivation of the catalyst remain in the polymer, it will cause many adverse effects such as corrosion, odor, coloring, turbidity, and functional group reaction inhibition. Don't be. However, it is not easy to remove the Lewis acid catalyst sufficiently.
  • the Lewis acid catalyst is coordinated to the terminal (meth) acryloyl group to form a complex. Therefore, the complete decomposition and removal is more than the usual removal of the Lewis acid catalyst. It turned out to be difficult.
  • the Lewis acid catalyst is deactivated by bringing the (meth) acryloyl-terminated polyisobutylene polymer solution containing the Lewis acid catalyst into contact with warm water at 30 to 80 ° C. Further, the Lewis acid catalyst can be efficiently removed by washing with an alkaline aqueous solution, the (meth) acryloyl-terminated polyisobutylene polymer is efficiently purified, and the (meth) acryloyl-terminated polyisobutylene polymer having excellent transparency is obtained.
  • the inventors have found that coalescence can be obtained, and have completed the present invention.
  • the first of the present invention is a method for producing a (meth) acryloyl-terminated polyisobutylene polymer, Living cationic polymerization process using Lewis acid catalyst, A terminal functionalization reaction step using a Lewis acid catalyst, Deactivating the Lewis acid catalyst with water at 30 ° C. to 80 ° C .; Washing with an alkaline aqueous solution, A process for producing a (meth) acryloyl-terminated polyisobutylene-based polymer.
  • the (meth) acryloyl-terminated polyisobutylene polymer has the following general formula (1):
  • R 1 represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group.
  • A represents a polyisobutylene polymer.
  • R 2 represents 2 to 6 carbon atoms.
  • R 3 and R 4 each represents hydrogen, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group.
  • 5 represents hydrogen or a methyl group, and n represents a natural number.
  • R 2 is —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 CH 2 —,
  • the (meth) acryloyl-terminated polyisobutylene-based heavy according to the second aspect of the present invention which is a divalent hydrocarbon group selected from the group consisting of —CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 — This is a manufacturing method of coalescence.
  • a fourth aspect of the present invention is the process for producing a (meth) acryloyl-terminated polyisobutylene polymer according to any one of the second or third aspects of the present invention, wherein R 3 and R 4 are hydrogen, It is.
  • a fifth aspect of the present invention is the process for producing a (meth) acryloyl-terminated polyisobutylene polymer according to any one of the second to fourth aspects of the present invention, wherein R 5 is hydrogen.
  • a sixth aspect of the present invention is the process for producing a (meth) acryloyl-terminated polyisobutylene polymer according to any one of the first to fifth aspects of the present invention, wherein the Lewis acid catalyst is titanium tetrachloride. is there.
  • a polymerization initiator is used in the living cationic polymerization step, and the amount of the Lewis acid catalyst used is 3 to 20 times mol of the polymerization initiator. 6.
  • a polymerization initiator is used in the living cationic polymerization step, and the polymerization initiator is (1-chloro-1-methylethyl) benzene, 1,3-bis (1-chloro-1- Methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene, 1,3-bis (1-chloro-1-methylethyl) -5- (tert-butyl) benzene, 1,3
  • the (meth) acryloyl-terminated poly according to any one of the first to seventh aspects of the present invention, which is at least one compound selected from 1,5-tris (1-chloro-1-methylethyl) benzene A method for producing an isobutylene polymer.
  • the amount of alkali contained in the aqueous alkali solution is 1.05 to 5 times mol of the amount capable of neutralizing an acid such as hydrochloric acid generated from the used Lewis acid catalyst (preferably titanium tetrachloride).
  • the method for producing a (meth) acryloyl-terminated polyisobutylene polymer according to any one of the first to eighth aspects of the present invention, wherein
  • the alkali used in the step of washing with the alkaline aqueous solution is any one of sodium hydroxide, lithium hydroxide, and potassium hydroxide.
  • the eleventh aspect of the present invention is the (meth) acryloyl-terminated polyisobutylene system according to any one of the first to tenth aspects of the present invention, wherein the temperature of the step of washing with an alkaline aqueous solution is in the range of 30 to 80 ° C. It is a manufacturing method of a polymer.
  • the solvent used in the living cationic polymerization step and the terminal functionalization reaction step is a mixed solvent of a monohalogenated hydrocarbon having 3 to 8 carbon atoms and an aliphatic and / or aromatic hydrocarbon.
  • the fourteenth aspect of the present invention is a method for purifying a (meth) acryloyl-terminated polyisobutylene polymer according to any one of the first to thirteenth aspects of the present invention.
  • the Lewis acid catalyst residue can be efficiently removed as compared with the conventional method. Even if a slight turbidity remains, the turbidity can be easily removed by filtration. As a result, the Lewis acid catalyst can be efficiently removed as compared with the prior art, and a (meth) acryloyl-terminated polyisobutylene-based polymer having stable and good transparency can be obtained.
  • the present invention is a method for producing a (meth) acryloyl-terminated polyisobutylene polymer, a living cationic polymerization step using a Lewis acid catalyst, A terminal functionalization reaction step using a Lewis acid catalyst, Deactivating the Lewis acid catalyst with water at 30 ° C. to 80 ° C .; Washing with an alkaline aqueous solution, Is a method for producing a (meth) acryloyl-terminated polyisobutylene polymer.
  • the polyisobutylene polymer in the present invention is not particularly limited as long as it contains isobutylene, but is preferably a polymer composed mainly of isobutylene. Specifically, it is obtained by living cationic polymerization of isobutylene monomer together with an initiator and, if necessary, an electron donor in the presence of a Lewis acid catalyst.
  • the polyisobutylene polymer obtained by living cationic polymerization can be converted to a (meth) acryloyl-terminated polyisobutylene polymer by terminal functionalization after the polymerization reaction by reaction with an appropriate end cap agent.
  • the (meth) acryloyl-terminated polyisobutylene polymer the following general formula (1);
  • R 1 represents a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group.
  • A represents a polyisobutylene polymer.
  • R 2 represents a divalent saturated hydrocarbon group having 2 to 6 carbon atoms and does not contain a hetero atom.
  • R 3 and R 4 each represent hydrogen, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group.
  • R 5 represents hydrogen or a methyl group.
  • n represents a natural number.
  • R 1 in the formula (1) is a monovalent or polyvalent aromatic hydrocarbon group, or a monovalent or polyvalent aliphatic hydrocarbon group.
  • aromatic hydrocarbon group include cumyl group, m-dicumyl group, p-dicumyl group, 5-tert-butyl-1,3-dicumyl group, 5-methyl-1,3-dicumyl group, 1 And alkyl-substituted benzenes having a free valence (also referred to as a bond, hereinafter the same) such as, 3,5-tricumyl group and the like (see the following formula).
  • aliphatic hydrocarbon group examples include CH 3 (CH 3 ) 2 CCH 2 (CH 3 ) 2 C—, — (CH 3 ) 2 CCH 2 (CH 3 ) 2 CCH 2 (CH 3 ).
  • cumyl group, m-dicumyl group, p-dicumyl group, 5-tert-butyl-1,3-dicumyl group, 1,3,5-tricumyl group, CH 3 (CH 3 ) 2 CCH 2 ( CH 3 ) 2 C—, — (CH 3 ) 2 CCH 2 (CH 3 ) 2 CCH 2 (CH 3 ) 2 C— are preferred from the viewpoint of availability, and among them, cumyl group, m-dicumyl group, p-dicumyl Of these, a 5-tert-butyl-1,3-dicumyl group and a 1,3,5-tricumyl group are more preferred.
  • a in the formula (1) is a polyisobutylene polymer, but as the monomer constituting the polyisobutylene polymer, other than the primary use of isobutylene, other cationic polymerizable monomers may be copolymerized.
  • examples of such monomers include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silane.
  • the ratio of the other monomer in the isobutylene polymer is preferably 50% by mass or less, more preferably 30% by mass or less, and still more preferably 10% by mass or less.
  • R 2 in the formula (1) is a divalent saturated hydrocarbon group having 2 to 6 carbon atoms and does not contain a hetero atom.
  • R 2 in the formula (1) is preferred.
  • R 3 and R 4 in the formula (1) are each hydrogen, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or an alkoxy group.
  • R 5 in the formula (1) is hydrogen or a methyl group. Hydrogen is more preferable from the viewpoints of availability and reactivity.
  • N in the formula (1) is a natural number, but is preferably 2 or 3 in order to achieve sufficient strength, durability, gel fraction, and the like when obtaining a crosslinkable polymer by a crosslinking reaction. .
  • the molecular weight of the (meth) acryloyl-terminated polyisobutylene polymer in the present invention is not particularly limited, but the number average molecular weight determined by SEC (Size Exclusion Chromatography) is 200 to 500, in terms of fluidity and physical properties after curing. Is preferably 1,000, more preferably 1,000 to 500,000, and still more preferably 5,000 to 500,000.
  • the molecular weight distribution (value represented by (mass average molecular weight Mw) / (number average molecular weight Mn)) of the (meth) acryloyl-terminated polyisobutylene polymer is 1. It is preferably 8 or less, more preferably 1.5 or less, and even more preferably 1.3 or less.
  • the lower limit of the molecular weight distribution may be about 1.1.
  • the (meth) acryloyl-terminated polyisobutylene polymer includes (1) a living cationic polymerization step using a Lewis acid catalyst, (2) a terminal functionalization reaction step using a Lewis acid catalyst, (3) The Lewis acid catalyst is produced through a step of deactivating with 30 ° C. to 80 ° C. water and (4) a step of washing with an aqueous alkali solution.
  • a living cationic polymerization step using a Lewis acid catalyst (2) a terminal functionalization reaction step using a Lewis acid catalyst, (3)
  • the Lewis acid catalyst is produced through a step of deactivating with 30 ° C. to 80 ° C. water and (4) a step of washing with an aqueous alkali solution.
  • the (meth) acryloyl-terminated polyisobutylene polymer of the present invention is a living cationic polymerization using a Lewis acid.
  • the polyisobutylene polymer obtained by the above can be obtained by terminal functionalization. Specifically, as described above, an isobutylene monomer is obtained by living cationic polymerization in the presence of a Lewis acid catalyst together with an initiator and, if necessary, an electron donor (polymerization step 1).
  • the polyisobutylene polymer obtained by living cationic polymerization is terminally functionalized after the polymerization reaction by reaction with an appropriate end cap agent in the presence of a Lewis acid catalyst, so that a (meth) acryloyl-terminated polyisobutylene polymer is obtained.
  • a Lewis acid catalyst e.g., J. Org. P. Kennedy et al.'S book (Carbational Polymerization. John Wiery & Sons. 1982) and K.
  • the description of the synthesis reaction is summarized in the book of Matyjazewski et al. (Cationic Polymerizations. Marcel Dekker. 1996).
  • isobutylene and other cationic polymerizable monomers capable of copolymerization with isobutylene may be used.
  • the other cationic polymerizable monomers include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes.
  • Polymerization initiator As a method for efficiently performing the initiation reaction of cationic polymerization, an inifer method has been developed in which a compound having a chlorine atom bonded to a tertiary carbon or a chlorine compound having an aromatic at the ⁇ -position is used as a polymerization initiator. (US Pat. No. 4,276,394), this method can also be applied to the present invention.
  • the polymerization initiator used in the inifer method may be any one that exhibits its function.
  • (1-chloro-1-methylethyl) benzene (hereinafter also referred to as cumyl chloride), 1,4-bis (1-chloro-1-methylethyl) benzene (hereinafter referred to as p-dichloro).
  • 1,3-bis (1-chloro-1-methylethyl) benzene (hereinafter also referred to as m-dichloromilk chloride), 1,3,5-tris (1-chloro-1-methylethyl) ) Benzene (hereinafter also referred to as 1,3,5-trimethyl milk chloride), 1,3-bis (1-chloro-1-methylethyl) -5- (tert-butyl) benzene (hereinafter referred to as 5-tert-butyl) 1,3-dicyclyl chloride), 1,3-bis (1-chloro-1-methylethyl) -5-methylbenzene (hereinafter, 5-methyl-1,3-dicumulyl chloride) And also referred to), and the like.
  • Examples of the aliphatic compound include CH 3 (CH 3 ) 2 CCH 2 (CH 3 ) 2 CCl and Cl (CH 3 ) 2 CCH 2 (CH 3 ) 2 CCH 2 (CH 3 ) 2 CCl.
  • (1-chloro-1-methylethyl) benzene 1,3-bis (1-chloro-1-methylethyl) benzene, 1,4-bis (1-chloro-1-methylethyl) benzene, At least one selected from 1,3-bis (1-chloro-1-methylethyl) -5- (tert-butyl) benzene and 1,3,5-tris (1-chloro-1-methylethyl) benzene It is a compound of this.
  • the Lewis acid catalyst used in the production of the (meth) acryloyl-terminated polyisobutylene polymer is not particularly limited as long as it has cationic polymerization ability.
  • TiCl 4 , AlCl 3 , BCl 3 , ZnCl 2 , SnCl 4 , ethylaluminum chloride, SnBr 4 and the like can be mentioned.
  • These Lewis acid catalysts may be used alone or in combination of two or more.
  • TiCl 4 is particularly preferable in terms of ease of handling, high polymerization activity, economy, and the like.
  • TiCl 4 can be said to be a preferred Lewis acid catalyst because it is also suitable as a Friedel-Crafts reaction catalyst for terminal acryloylation.
  • the Lewis acid catalyst may be used in an amount sufficient for the polymerization and functionalization to proceed, but in order to proceed the polymerization and functionalization with good yield, the total amount used (polymerization step 1 and terminal functionalization).
  • the total amount used in Step 2) is, for example, 2 to 40 times mol, preferably 3 to 20 times mol, more preferably 4 to 10 times mol of the polymerization initiator.
  • an electron donor When carrying out the polymerization, an electron donor may be further present if necessary. This electron donor is thought to have the effect of stabilizing the growing carbon cation during cationic polymerization, and the addition of an electron donor produces a polymer with a narrow molecular weight distribution and a controlled structure. Can do. As the above-mentioned electron donor, it is usually assumed that the number of donors defined as a parameter representing the strength as an electron donor (electron donor) of various compounds is 15 to 60.
  • the electron donor is usually used in an amount of 0.01 to 50 times mol, preferably in a range of 0.1 to 30 times mol, preferably in a range of 0.2 to 10 times mol with respect to the polymerization initiator. Is more preferably used.
  • the (meth) acryloyl-terminated polyisobutylene polymer of the present invention is, for example, the following general formula (2) after living cationic polymerization of an isobutylene monomer in the presence of a Lewis acid catalyst.
  • end cap agent of the formula (2) examples include 2-phenoxyethyl acrylate, 3-phenoxypropyl acrylate, 4-phenoxybutyl acrylate, 5-phenoxypentyl acrylate, 6-phenoxyhexyl acrylate, Examples include 2-phenoxyethyl methacrylate, 3-phenoxypropyl methacrylate, 4-phenoxybutyl methacrylate, 5-phenoxypentyl methacrylate, 6-phenoxyhexyl methacrylate, and the like.
  • a Lewis acid catalyst is generally preferably used, and the same Lewis acid catalyst as that used for polymerization may be used, or different ones may be used. May be. Details of the Lewis acid catalyst will be described later.
  • the living cationic polymerization and the terminal functionalization reaction are performed in a temperature range of ⁇ 100 to 0 ° C.
  • a particularly preferable temperature range is ⁇ 90 to ⁇ 30 ° C. in order to achieve both energy cost, stability of polymerization, and reactivity of Friedel-Crafts reaction.
  • the temperature refers to the temperature of the reaction solution, for example.
  • Living cationic polymerization and terminal functionalization can be achieved by combining monohalogenated hydrocarbons having 3 to 8 carbon atoms with aliphatic and / or aromatic hydrocarbons in order to achieve both polymerization stability and reactivity of Friedel-Crafts reaction. It is preferable to carry out in a mixed solvent.
  • monohalogenated hydrocarbon having 3 to 8 carbon atoms include monohalogenated alkanes such as n-propyl chloride, n-butyl chloride and n-pentyl chloride, and monohalogenated arenes such as chlorobenzene.
  • aliphatic hydrocarbon examples include pentane, hexane, heptane, octane, nonane, decane, 2-methylpropane, 2-methylbutane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
  • aromatic hydrocarbon examples thereof include benzene, toluene, xylene, ethylbenzene, butylbenzene and the like.
  • the amount of the mixed solvent used is determined so that the concentration of the polymer is 1 to 50% by mass, preferably 5 to 35% by mass, in consideration of the viscosity of the polymer solution obtained and ease of heat removal.
  • the isobutylene polymer may be once isolated and then reacted with the isobutylene polymer.
  • the end cap agent may be added to the polymerization system and allowed to react.
  • the end cap agent is added preferably when the conversion of isobutylene monomer measured by gas chromatography reaches 50% or more, and when it reaches 80% or more. More preferably, it is more preferably 95% or more.
  • Step of deactivating Lewis acid catalyst with water at 30 ° C. to 80 ° C. Step of washing with aqueous alkali solution
  • the deactivation of Lewis acid catalyst is performed using hot water at 30 ° C. to 80 ° C. This is carried out by stirring the reaction solution containing the system polymer for a certain period of time.
  • the temperature of deactivation by warm water is 30 ° C. or higher as described above from the viewpoint of promoting deactivation and from the viewpoint of oil / water separation after deactivation. And Preferably it is 40 degreeC or more. On the other hand, if the temperature is too high, the energy cost is increased.
  • the deactivation time is more preferably 30 minutes or more, and still more preferably 60 minutes or more.
  • the amount of the warm water is not particularly limited as long as it can be sufficiently stirred and deactivated.
  • the volume ratio of the organic phase to the aqueous phase is set to the organic phase.
  • an appropriate salt may be added to the hot water used for deactivation for the improvement.
  • the salt is not particularly limited as long as it can improve oil-water separation, and examples thereof include sodium sulfate, sodium chloride, calcium chloride, and the like. Corrosiveness and economic efficiency when industrial production is assumed. In view of comprehensive availability, sodium sulfate is preferably used.
  • Washing with an alkaline aqueous solution may be carried out after oil / water separation and drainage, after adding water and alkali, or by adding additional alkali or alkaline aqueous solution without draining. Also good.
  • a method of continuously washing with an alkaline aqueous solution without draining is preferable from the viewpoint of shortening the time cycle and increasing productivity.
  • the alkali to be used is particularly limited as long as it can neutralize the acid generated from the deactivated Lewis acid catalyst and effectively decompose and remove the complexed Lewis acid coordinated with the (meth) acryloyl terminal.
  • Alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, potassium hydroxide, are illustrated, for example. These may be used alone or in combination of two or more. Sodium hydroxide is particularly preferable from the viewpoint of cost and availability.
  • the amount of alkali contained in the aqueous alkali solution is not particularly limited as long as it is an amount that can neutralize the acid generated from the Lewis acid used, but from the viewpoint of efficient catalyst removal, the generated acid is not limited.
  • the amount is preferably 1.05 to 5 times mol, more preferably 1.1 to 3 times mol.
  • the amount of the aqueous alkali solution is not particularly limited as long as it can be sufficiently stirred and can be efficiently washed.
  • the volume ratio of the organic phase to the aqueous phase must be organic.
  • the washing temperature (liquid temperature at the time of washing, which corresponds to the internal temperature in the examples described later) is not particularly limited, it is advantageous from the viewpoint of equipment and energy cost to carry out at the same temperature as deactivation. , Preferably 30 to 80 ° C. Moreover, it is preferable that it is 30 degreeC or more also from a viewpoint of the oil-water separability improvement in stationary separation after washing
  • the terminal portion of the polyisobutylene polymer of the present invention is unexpectedly stable against alkali, even if alkali is used and the washing temperature is increased as described above, the terminal functional It can be secured without losing the group.
  • the cleaning time is not particularly limited, but is preferably about 10 to 240 minutes, more preferably 10 to 180 minutes, and particularly preferably 10 to 120 minutes in order to obtain a sufficient cleaning effect.
  • the oil / water can be left and separated and drained. What is necessary is just to select the frequency
  • the alkali cleaning is repeatedly performed by performing a static separation of oil and water for each cleaning, and adding a new aqueous alkali solution after draining.
  • washing with water may be performed. Washing with water may be repeated until the pH of the wastewater returns to around neutral (for example, about 5 to 8), and the conditions are not particularly limited, but usually the same temperature as washing with an alkaline aqueous solution, It is carried out with the ratio of oil to water and washing time, and the number of times is about 1 to 3 times. If oil / water separation after washing with water is poor, an appropriate salt may be dissolved in water used for washing with water.
  • the salt is not particularly limited as long as it can improve oil-water separation, and examples thereof include sodium sulfate, sodium chloride, calcium chloride, and the like. Corrosiveness and economic efficiency when industrial production is assumed. In view of comprehensive availability, sodium sulfate is preferably used.
  • the filtration method include a vacuum filtration method using Nutsche and the like, a pressure filtration method such as a filter press method, and the like.
  • a vacuum filtration method using Nutsche and the like When the amount of insoluble components is small and the filterability is good, simple filtration with a cartridge filter, bag filter or the like is simple.
  • cake filtration using a filter aid is also suitable. Although it does not specifically limit as a kind of filter aid, Diatomaceous earth can be used suitably. Moreover, an adsorbent can also be used together as needed. Although it does not specifically limit as a kind of adsorbent, Activated carbon and a silicate can be used suitably.
  • a polymerization inhibitor may be added as necessary during purification after polymerization or during storage.
  • polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether (ie MEHQ), p-tert-butylcatechol, 4-methoxy-naphthol, 2,6-di-t-butyl-4-methylphenol, 2,2 '-Methylenebis (4-ethyl-6-t-butylphenol), 2,6-di-t-butyl-N, N-dimethylamino-p-cresol, 2,4-dimethyl-6-t-butylphenol, 4- phenolic compounds such as t-butylcatechol, 4,4′-thio-bis (3-methyl-6-t-butylphenol), 4,4′-butylidene-bis (3-methyl-6-t-butylphenol), 4-hydroxy-2,2,6,6, -tetramethylpipe
  • the amount of the polymerization inhibitor used is desirably 1 to 5000 ppm by mass, preferably 50 to 3000 ppm by mass, based on the (meth) acryloyl-terminated polyisobutylene polymer, from the viewpoint of sufficiently exhibiting the polymerization inhibitory effect.
  • Example 1 Polymerization and terminal functionalization reaction
  • 20 mL of n-hexane (dried with molecular sieves) and 182 mL of butyl chloride (dried with molecular sieves) were added and stirred at -70 while stirring in a nitrogen atmosphere. Cooled to ° C. Subsequently, 72 mL (0.76 mol) of isobutylene), 0.84 g (0.0036 mol) of p-dicumyl chloride and 0.14 g (0.0013 mol) of lutidine were added.
  • the APHA of the present invention here refers to the Hazen color number obtained by the Hazen color number test defined in ISO 6721-2: 2004 as a method for evaluating the degree of coloring of chemical products and the like.
  • the Hazen color number test was conducted with an SC-P spectrocolorimeter (manufactured by Suga Test Instruments Co., Ltd.).
  • the spectral colorimeter is hereinafter referred to as a “color difference meter”.
  • the organic phase (200 mL) was subjected to pressure filtration (filter cloth; 16 cc / cm 2 / sec, nitrogen pressure; 0.04 MPa, filter aid; Radiolite 100S (manufactured by Showa Chemical Industry) (0.5 g), activated carbon; TAIKO A (made by Phutamura Chemical) (3.5 g), total addition concentration of filter aid and activated carbon; 20 g / L) gave a colorless and transparent solution. 0.076 g of MEHQ was added, the solvent was distilled off under reduced pressure, and the resulting polymer was vacuum dried at 120 ° C. for 4 hours to obtain a colorless and transparent acryloyl-terminated polyisobutylene polymer.
  • transduced into the terminal of the obtained acryloyl terminal polyisobutylene polymer was calculated
  • required as follows. First, the molecular weight of the polymer was calculated by the GPC measurement, and the number average molecular weight Mn was determined. Next, 1 H NMR measurement was performed, and the area of the peak attributed to two methyl groups in the polyisobutylene skeleton near 1.3 ppm was calculated using the value of the number average molecular weight Mn (the peak near 1.3 ppm). ) ((Number average molecular weight Mn) /56.11) ⁇ 6H.
  • Example 2 Polymerization and terminal functionalization reaction
  • Polymerization / terminal functionalization reaction was carried out in the same manner as in Example 1.
  • Distilled water (208 mL) and 24% sodium hydroxide aqueous solution (42 g) were added, and the mixture was further stirred at an internal temperature of 50 ° C. for 30 minutes for alkali cleaning. Stirring was stopped, stationary separation was performed for 30 minutes, and the aqueous phase was discharged. The pH of the effluent was> 14.
  • Distilled water (208 mL) and 5% aqueous sodium sulfate solution (27 g) were added, and the mixture was stirred for 30 minutes after the internal temperature reached 50 ° C. Stirring was stopped, stationary separation was performed for 30 minutes, and the aqueous phase was discharged. The pH of the wastewater was around 10.
  • Example 3 Polymerization and terminal functionalization reaction
  • Polymerization / terminal functionalization reaction was carried out in the same manner as in Example 1.
  • Deactivation and alkali cleaning were performed in the same manner as in Example 1 except that the amount of distilled water used at the time of alkali cleaning carried out after deactivation and at the time of water washing after alkali cleaning was changed to 173 ml.
  • the obtained organic phase was almost colorless and transparent.
  • APHA was measured with a color difference meter, it was 150.
  • Example 4 Polymerization and terminal functionalization reaction
  • Polymerization / terminal functionalization reaction was carried out in the same manner as in Example 1.
  • Deactivation and alkali cleaning were performed in the same manner as in Example 1 except that the amount of distilled water used at the time of alkali cleaning performed after deactivation and at the time of water washing after alkali cleaning was changed to 150 ml.
  • the obtained organic phase was almost colorless and transparent.
  • APHA was measured with a color difference meter, it was 150.
  • Example 5 Polymerization and terminal functionalization reaction
  • Polymerization / terminal functionalization reaction was carried out in the same manner as in Example 1.
  • Deactivation and alkali cleaning were performed in the same manner as in Example 1 except that the deactivation time was 90 minutes. The obtained organic phase was almost colorless and transparent. When APHA was measured with a color difference meter, it was 150.
  • Example 6 Polymerization and terminal functionalization reaction
  • Polymerization / terminal functionalization reaction was carried out in the same manner as in Example 1.
  • Deactivation and alkali cleaning were performed in the same manner as in Example 1 except that the deactivation time was 60 minutes. The obtained organic phase was almost colorless and transparent. When APHA was measured with a color difference meter, it was 160.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'objet de la présente invention est de fournir un procédé qui est destiné à produire un polymère à base de polyisobutylène à terminaison (méth)acryloyle présentant une excellente transparence et qui est un procédé simple pouvant être appliqué à des procédés de production réels. Ledit procédé de production de polymère à base de polyisobutylène à terminaison (méth)acryloyle est caractérisé en ce qu'il comprend : une étape de polymérisation cationique vivante dans laquelle est utilisé un catalyseur acide de Lewis ; une étape de formation d'un groupe fonctionnel terminal dans laquelle est utilisé un catalyseur acide de Lewis ; une étape dans laquelle sont désactivés lesdits catalyseurs acides de Lewis avec de l'eau à une température de 30 à 80 °C ; et une étape dans laquelle le mélange réactionnel est lavé avec une solution alcaline aqueuse.
PCT/JP2016/073556 2015-08-26 2016-08-10 Procédé de production de polymère à base de polyisobutylène à terminaison (méth)acryloyle WO2017033749A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018155401A1 (fr) * 2017-02-22 2018-08-30 株式会社カネカ Composition durcissable

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5322583A (en) * 1976-08-12 1978-03-02 Nippon Petrochemicals Co Ltd Purification of buten polymer
JP2004203922A (ja) * 2002-12-24 2004-07-22 Kanegafuchi Chem Ind Co Ltd イソブチレン系重合体及びその製造方法
JP2009007386A (ja) * 2006-02-17 2009-01-15 Kaneka Corp イソブチレン系重合体の製造方法
WO2013047314A1 (fr) * 2011-09-27 2013-04-04 株式会社カネカ Polymère de polyisobutylène terminé par (méth)acryloyle, son procédé de fabrication et composition durcissable sous l'action d'un rayonnement d'énergie active
JP2013216782A (ja) * 2012-04-09 2013-10-24 Kaneka Corp 硬化性組成物およびその用途
JP2016145268A (ja) * 2015-02-06 2016-08-12 株式会社カネカ 重合体の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5322583A (en) * 1976-08-12 1978-03-02 Nippon Petrochemicals Co Ltd Purification of buten polymer
JP2004203922A (ja) * 2002-12-24 2004-07-22 Kanegafuchi Chem Ind Co Ltd イソブチレン系重合体及びその製造方法
JP2009007386A (ja) * 2006-02-17 2009-01-15 Kaneka Corp イソブチレン系重合体の製造方法
WO2013047314A1 (fr) * 2011-09-27 2013-04-04 株式会社カネカ Polymère de polyisobutylène terminé par (méth)acryloyle, son procédé de fabrication et composition durcissable sous l'action d'un rayonnement d'énergie active
JP2013216782A (ja) * 2012-04-09 2013-10-24 Kaneka Corp 硬化性組成物およびその用途
JP2016145268A (ja) * 2015-02-06 2016-08-12 株式会社カネカ 重合体の製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018155401A1 (fr) * 2017-02-22 2018-08-30 株式会社カネカ Composition durcissable
JPWO2018155401A1 (ja) * 2017-02-22 2019-12-12 株式会社カネカ 硬化性組成物

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