JP4996342B2 - Method for producing graft polymer - Google Patents

Description

  The present invention relates to a method for producing a graft polymer. In detail, it is related with the manufacturing method of the graft polymer which can prevent adhesion of the gel-like substance in a reactor.

  Various graft polymers obtained by reacting a polyalkylene glycol compound and an unsaturated compound have been proposed so far (Patent Documents 1 to 10). These are used, for example, in detergent builders, scale inhibitors, fiber treatment agents, dispersants, and water treatment agents.

  However, it has been found that the above-described methods for producing a graft polymer have a problem in that a gel-like substance adheres to the wall surface and upper part in the reactor. It has been found that this problem occurs even when the reaction is performed in an inert gas atmosphere. Since the gel-like substance as described above is hardly soluble in water and various solvents, it becomes insoluble when mixed into the reaction system. As a result, the performance of the obtained graft polymer is lowered, and the productivity is lowered.

As a method for preventing the adhesion of the gel substance as described above, the monomer in the gas phase is condensed, polymerized, and gelated on the wall surface in the reactor by performing polymerization in the presence of an organic solvent having a specific boiling range. A method for suppressing this has been proposed (Patent Document 11). However, in this method, a considerable amount of organic solvent is required, and a process to be removed later is required, so that the operation is complicated.
Japanese Patent Publication No. 47-47999 Japanese Patent Publication No.48-32191 Japanese Patent Publication No. 64-10540 JP-A-3-177406 Japanese Patent Publication No. 50-15894 Japanese Examined Patent Publication No. 6-86503 Japanese Patent No. 2945822 Japanese Patent No. 2918798 Japanese Patent No. 2918799 Japanese Patent Laid-Open No. 11-60652 JP 2002-327029 A

  An object of the present invention is a method for producing a graft polymer by reacting a polyalkylene glycol compound and an unsaturated compound in a reactor, and effectively preventing adhesion of a gel-like substance into the reactor. Another object of the present invention is to provide a method for producing a graft polymer, which can avoid a decrease in performance and productivity of the obtained graft polymer.

  The method for producing a graft polymer of the present invention is a method for producing a graft polymer by reacting a polyalkylene glycol compound and an unsaturated compound in a reactor, the reactor comprising a gas inlet and a gas exhaust. The gas inlet and the gas outlet do not have protrusions on the inner surface of the reactor, and the reaction is carried out while introducing an inert gas from the gas inlet.

  In a preferred embodiment, the unsaturated compound comprises an unsaturated monocarboxylic acid and / or an unsaturated dicarboxylic acid.

  In a preferred embodiment, the unsaturated compound includes (meth) acrylic acid.

  In preferable embodiment, the (meth) acrylic acid density | concentration in the gaseous-phase part in the said reactor is 2.0 volume% or less.

  In a preferred embodiment, the polyalkylene glycol compound has a hydrophobic group. More preferably, the hydrophobic group is a long chain alkyl group and / or an aromatic group.

  In a preferred embodiment, the inert gas is at least one selected from nitrogen, carbon dioxide, helium, and argon.

  According to the present invention, a method for producing a graft polymer by reacting a polyalkylene glycol compound and an unsaturated compound in a reactor, and effectively preventing the adhesion of a gel substance into the reactor. In addition, it is possible to provide a method for producing a graft polymer, which can avoid performance degradation and productivity degradation of the obtained graft polymer.

  Such an effect is achieved by using a reactor having a gas inlet and a gas outlet of a specific shape when the polyalkylene glycol compound and the unsaturated compound are reacted in the reactor. This can be achieved by carrying out the reaction while introducing the active gas.

  The method for producing a graft polymer of the present invention is a method for producing a graft polymer by reacting a polyalkylene glycol compound and an unsaturated compound in a reactor, the reactor comprising a gas inlet and a gas exhaust. The gas inlet and the gas outlet do not have protrusions on the inner surface of the reactor, and the reaction is carried out while introducing an inert gas from the gas inlet.

  The reactor includes a gas inlet and a gas outlet, and any appropriate reactor is adopted as long as each of the gas inlet and the gas outlet does not have a protruding portion on the inner surface side of the reactor. obtain. Any appropriate size can be adopted as the size of the reactor. The size at which the effect of the present invention is further exhibited is preferably 1 L or more, more preferably 50 L or more, and even more preferably 100 L or more.

  The gas inlet and the gas outlet may be provided at any appropriate position of the reactor as long as the object of the present invention can be achieved. Preferably, it is an arbitrary appropriate position in a portion that becomes a gas phase portion during the reaction.

  As the shapes of the gas inlet and the gas outlet, any appropriate shape can be adopted as long as the object of the present invention can be achieved. For example, a substantially circular shape, an elliptical shape, a rectangular shape, and the like can be given. From the viewpoint that the effects of the present invention can be further exhibited, a substantially circular shape and an elliptical shape are preferable, and a substantially circular shape is more preferable.

  Each of the gas inlet and the gas outlet does not have a protruding portion toward the inner surface of the reactor. That is, each of the gas inlet and the gas outlet does not have a portion protruding from the inner wall surface of the reactor toward the inside of the reactor. For example, a reactor 100 as shown in FIG. 1 is a reactor in which “the gas inlet 10 and the gas outlet 11 do not have protrusions to the inner surface of the reactor”, and a reactor as shown in FIG. Reference numeral 200 denotes a reactor in which the gas inlet 20 and the gas outlet 21 have protrusions 22 and 23 on the inner surface side of the reactor, respectively. As shown in FIG. 2, when each of the gas inlet and the gas outlet has a protruding portion toward the inner surface of the reactor, the gel substance may easily adhere to the vicinity of the protruding portion.

  In the present invention, the gas inlet and the gas outlet may each have a protruding portion on the outer surface side of the reactor, as shown in FIGS.

  Any appropriate inert gas can be adopted as the inert gas introduced from the gas inlet. Preferably, it is at least one selected from nitrogen, carbon dioxide, helium, and argon. Nitrogen is more preferred from the viewpoint of economy.

  In the present invention, the amount of the inert gas introduced per minute is preferably equal to or more than the amount of the gas generated by the reaction per minute. More preferably, it is 2 times or more, more preferably 5 times or more, and further preferably 10 times or more. When the amount of the inert gas introduced per minute is equal to or greater than the amount of the gas generated by the reaction per minute, the effect of the present invention can be further exhibited.

  In the present invention, when the unsaturated compound contains (meth) acrylic acid, the (meth) acrylic acid concentration in the gas phase portion in the reactor is preferably 2.0% by volume or less. It is more preferably no greater than volume%, even more preferably no greater than 1.5 volume%, and particularly preferably no greater than 1.0 volume%. The (meth) acrylic acid concentration in the gas phase portion in the reactor is 2.0 vol% or less, thereby effectively preventing the (meth) acrylic acid-derived gel substance from adhering to the reactor. Can do. In particular, since the gel-like substance derived from (meth) acrylic acid easily adheres to the vicinity of the gas inlet and the gas outlet, the concentration of (meth) acrylic acid in the gas phase portion in the reactor is 2.0 vol. % Or less is a preferable form for further exhibiting the effects of the present invention. In the present invention, the (meth) acrylic acid concentration in the gas phase part is preferably 2.0% by volume or less, preferably 2.0% by volume or less throughout the reaction time. It is not limited. Substantially 2.0% by volume or less is preferable throughout. When (meth) acrylic acid is continuously added, it is preferable that 80% or more of the addition time be the above-mentioned (meth) acrylic acid concentration in the gas phase part when adding acrylic acid. In the case where the polymerization initiator is continuously added without continuously adding the acid, at the time of addition of the polymerization initiator, 80% or more of the addition time is determined so that the gas phase portion is the above (meth) acrylic acid concentration. It is preferable to do. When the reaction is carried out by heating, it is preferable that 80% or more of the heating time is set to the above (meth) acrylic acid concentration in the gas phase during heating. Further, from the viewpoint of suppressing adhesion of the gel substance, the (meth) acrylic acid concentration in the gas phase is most preferably 0% by volume. Considering ease of control, the (meth) acrylic acid concentration in the gas phase during the reaction is preferably 0.0001 to 2.0% by volume.

  Any appropriate polyalkylene glycol compound can be adopted as the polyalkylene glycol compound. For example, it can be obtained by adding a cyclic ether using an alkali compound in the presence of a compound to be reacted that is a starting point of polymerization. Only one cyclic ether may be used, or two or more cyclic ethers may be used in combination.

  Any appropriate compound can be adopted as the compound to be reacted as long as it is a compound serving as a starting point of addition of a cyclic ether. Preferably, it has active hydrogen. The said to-be-reacted compound may use only 1 type, and may use 2 or more types together.

  Examples of the compound to be reacted include water; alcohols such as aliphatic alcohols and aromatic alcohols; hydrogen halides; ammonia; amines; hydroxylamines; carboxylic acids; and other acid halides; lactones; aldehydes; Is mentioned. Preferred are water, alcohol and amine, and more preferred is alcohol.

  Examples of the alcohol as an example of the reaction compound include methanol, ethanol, n-propanol, and n-butanol primary aliphatic alcohol having 1 to 22 carbon atoms; phenol, cresol, ethylphenol, cumylphenol, Aromatic alcohols such as xylenol, octylphenol, tert-butylphenol, nonylphenol and naphthol; secondary alcohols having 3 to 18 carbon atoms such as alcohol obtained by oxidizing iso-propyl alcohol and n-paraffin; 3 such as tert-butanol Diols such as ethylene glycol, diethylene glycol, propanediol, butanediol and propylene glycol; triols such as glycerin and trimethylolpropane; polyols such as sorbitol; And the like. Among these, aromatic alcohol is preferable and phenol is more preferable. This is because the performance when the finally obtained graft polymer is used for a detergent builder, a scale inhibitor, a fiber treatment agent, a dispersant and the like is easily improved.

  Examples of the cyclic ether include ethylene oxide, propylene oxide, 1-butene oxide, styrene oxide, epichlorohydrin, glycidol, allyl glycidyl ether, phenyl glycidyl ether, α-olefin oxide, and other alkylene copolymerizable therewith. An oxide (for example, tetrahydrofuran) can be mentioned.

  As the cyclic ether, ethylene oxide and propylene oxide are preferable and ethylene oxide is more preferable from the viewpoint of easy availability and practical use. Moreover, it is preferable that the total amount of ethylene oxide and propylene oxide is 50 mol% or more in the total cyclic ether to be used.

  A commercial item may be used for the said polyalkylene glycol type compound, and what was prepared may be used for it. Any appropriate method can be adopted as a preparation method. For example, 1) anionic polymerization using alkali metal hydroxide, alcoholate or other strong alkali, or alkylamine as a base catalyst, 2) cationic polymerization using metal or metalloid halide, mineral acid, acetic acid or the like as a catalyst. 3) Coordination polymerization using a combination of alkoxides of metals such as aluminum, iron and zinc, alkaline earth compounds, Lewis acids, and the like.

  The polyalkylene glycol compound may be a derivative derived from polyalkylene glycol. Examples of such a derivative include a terminal group-converted product obtained by converting a terminal functional group of polyalkylene glycol, a polyalkylene glycol, and a crosslinking agent having a plurality of groups such as a carboxyl group, an isocyanate group, an amino group, and a halogen group. And a cross-linked product obtained by reacting. As the terminal group converter, at least one terminal hydroxyl group of the above polyalkylene glycol is selected from fatty acids having 2 to 22 carbon atoms such as acetic acid and acetic anhydride and acid anhydrides thereof, succinic acid, succinic anhydride, adipic acid, and the like. Those esterified with a dicarboxylic acid are preferred.

  The polyalkylene glycol compound preferably has a hydrophobic group. Any appropriate hydrophobic group can be adopted as the hydrophobic group. For example, a linear or branched long chain alkyl group or an aromatic group can be mentioned. Preferably, it is a C1-C30 linear or branched long chain alkyl group or a phenyl group. This is because the performance when the finally obtained graft polymer is used for a detergent builder, a scale inhibitor, a fiber treatment agent, a dispersant, a water treatment agent and the like is easily improved.

  The number average molecular weight of the polyalkylene glycol compound is preferably 100 to 100,000, more preferably 150 to 50,000, still more preferably 150 to 20,000, and particularly preferably 150 to 10,000. When the number average molecular weight is less than 100, the graft ratio may be decreased, and unreacted alkylene oxide may be increased. When the number average molecular weight exceeds 100,000, the viscosity becomes high and it may be difficult to handle during polymerization.

  Any appropriate unsaturated compound can be adopted as the unsaturated compound as long as it is a compound having an unsaturated double bond. In the present invention, the unsaturated compound may be used alone or in combination of two or more.

  The unsaturated compound preferably includes an unsaturated monocarboxylic acid and / or an unsaturated dicarboxylic acid. Furthermore, it may contain other unsaturated compounds copolymerizable with unsaturated monocarboxylic acids and / or unsaturated dicarboxylic acids, if necessary.

  Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid, and the like. (Meth) acrylic acid is preferable, and acrylic acid is more preferable. This is because the performance when the finally obtained graft polymer is used for a detergent builder, a scale inhibitor, a fiber treatment agent, a dispersant and the like is easily improved.

  Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, maleic anhydride, itaconic acid, and the like.

  Examples of the other unsaturated compound include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, and 1 to 1 carbon atoms. Alkyl (meth) acrylate obtained by esterification with 18 alcohols; Amide group-containing monomers such as (meth) acrylamide, dimethylacrylamide and isopropylacrylamide; Vinyl esters such as vinyl acetate; Alkenes such as ethylene and propylene; Styrene , Aromatic vinyl monomers such as styrenesulfonic acid; maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; aldehyde groups such as (meth) acrolein Vinyl monomer; 2 A sulfonic acid group-containing monomer such as acrylamido-2-methylpropanesulfonic acid, (meth) allylsulfonic acid, vinylsulfonic acid, 2-hydroxy-3-allyloxy-1-propanesulfonic acid, 2-hydroxy-3-butenesulfonic acid, etc. 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α- Hydroxyl-containing monomers such as hydroxymethylethyl (meth) acrylate; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; other functional groups such as vinyl chloride, vinylidene chloride, allyl alcohol and vinyl pyrrolidone Containing monomer; and the like.

  The content ratio of the total amount of unsaturated monocarboxylic acid and unsaturated dicarboxylic acid in the unsaturated compound is preferably 50 to 100 mol%, more preferably 70 to 100, in order to further exert the effects of the present invention. It is mol%, More preferably, it is 90-100 mol%, More preferably, it is 95-100 mol%, Most preferably, it is 100 mol%.

  The graft polymer obtained by the production method of the present invention has a structure in which a polyalkylene glycol compound is a main chain, and an unsaturated compound is graft polymerized to the main chain.

  The graft ratio of the unsaturated compound is such that the weight ratio of the part derived from the polyalkylene glycol compound and the part derived from the unsaturated compound is preferably 50:50 to 90:10, more preferably 55:45. It is -85: 15, More preferably, it is 60: 40-80: 20. If the amount of the portion derived from the unsaturated compound (graph portion) is too small, the performance as a graft polymer may not be sufficiently exhibited. If the amount of the portion derived from the unsaturated compound (graft portion) is too large, the reaction system may be thickened and cannot be stirred, or a large amount of unreacted unsaturated compound may remain.

  In the graft polymer obtained by the production method of the present invention, the molar ratio of the portion derived from the unsaturated compound (graph portion) in the graft polymer is preferably 90 mol% or more with respect to the total graft chain, More preferably, it is 95 mol% or more, More preferably, it is 100 mol%. When the molar ratio of the portion derived from the unsaturated compound (graph portion) is 90 mol% or more, the stability of the resulting graft polymer is improved.

  The number average molecular weight of the graft polymer obtained by the production method of the present invention is preferably 1000 to 500,000, more preferably 1500 to 100,000, and still more preferably 2000 to 50,000. If the value of the number average molecular weight is within the above range, the handleability and performance of the obtained graft polymer can be improved.

  In the method for producing a graft polymer by reacting the polyalkylene glycol compound and the unsaturated compound in a reactor, as described above, the reactor includes a gas inlet and a gas outlet, Any appropriate method can be adopted as long as the gas introduction port and the gas discharge port do not have protrusions on the inner surface of the reactor and the reaction is performed while introducing an inert gas from the gas introduction port. Can do.

  In producing the graft polymer in the present invention, first, the polyalkylene glycol compound serving as the main chain of the graft polymer and the unsaturated compound serving as the side chain of the graft polymer are respectively prepared in desired amounts. Then, graft polymerization is performed.

  In carrying out the graft polymerization, any appropriate radical polymerization initiator can be used as the polymerization initiator. The radical polymerization initiator is preferably an organic peroxide. Specifically, for example, ketone peroxides such as cyclohexanone peroxide, methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, 3,3,5-trimethylcyclohexanone peroxide; 1,1-bis (tert -Hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) cyclohexane, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane 1,1-bis (tert-butylperoxy) -2-methylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, n-butyl -4,4 Peroxyketals such as bis (tert-butylperoxy) valerate and 2,2-bis (tert-butylperoxy) octane; p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, cumene hydroperoxide, tert-hexyl hydroperoxide, tert-butyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2- (4-methylcyclohexyl) ) -Hydroperoxides such as propane hydroperoxide; α, α′-bis (tert-butylperoxy) p-diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (tert- The Tilperoxy) hexane, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexyne-3, α, α′-bis (tert- Dibutyl peroxides such as butylperoxy) p-isopropylhexyne; isobutyryl peroxide, 3,3,5-trimethylcyclohexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide Diacyl peroxides such as oxide, m-toluyl peroxide, benzoyl peroxide, acetyl peroxide, decanoyl peroxide, 2,4-dichlorobenzoyl peroxide; di-n-propyl peroxydica Bonate, di-isopropyl peroxydicarbonate, bis- (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-3- Methoxybutyl peroxydicarbonate, di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, dimyristyl peroxydicarbonate, di-methoxyisopropyl peroxydicarbonate, diallyl Peroxydicarbonates such as peroxydicarbonate; α, α′-bis (neodecanoperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyne Decanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, tert-hexylperoxyneodecanoate, tert-butylperoxyneodecanoate, tert-hexylperoxybivalate, tert-butylperoxy Vivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dibutyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl- 1-methylethylperoxy-2-ethylhexanoate, tert-hexylperoxy-2-ethylhexanoate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, tert -Hexylperoxyisopropyl mono -Bonate, tert-butylperoxymaleic acid, tert-butylperoxy-3,5,5-trimethylcyclohexanoate, tert-butylperoxylaurate, 2,5-dibutyl-2,5-bis (m-toluyl) Peroxy) hexane, tert-butylperoxyisopropyl monocarbonate, tert-butylperoxy-2-ethylhexyl monocarbonate, tert-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane Tert-butylperoxyacetate, tert-butylperoxy-m-toluylbenzoate, tert-butylperoxybenzoate, bis (tert-butylperoxy) isobutarate, cumylperoxyoctoate, Peroxyesters such as tert-hexylperoxyneohexanoate and cumylperoxyneohexanoate; other organic peroxides such as tert-butylperoxyallyl carbonate, tert-butyltrimethylsilyl peroxide, acetylcyclohexylsulfonyl peroxide And the like. Of these organic peroxides, di-tert-butyl peroxide, tert-butyl hydroperoxide, octanoyl peroxide, lauroyl peroxide, benzoyl peroxide, and cumene hydroperoxide can be suitably used. These organic peroxides may be used alone or in combination of two or more.

  As a usage-amount of the radical polymerization initiator used for the said graft polymerization, arbitrary appropriate amounts can be employ | adopted within the range which can achieve the objective of this invention. For example, it is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, and still more preferably 1 to 8% by weight, based on the total amount of monomer components used for graft polymerization. If the amount of the radical polymerization initiator used is too small, the graft ratio may decrease. If the amount of the radical polymerization initiator used is too large, there is a risk that it may be disadvantageous in terms of cost, or the initiator fragment may affect the physical properties of the graft polymer.

  As the addition form of the radical polymerization initiator, any appropriate form can be adopted as long as the object of the present invention can be achieved.

  In the graft polymerization, in addition to the radical polymerization initiator, a decomposition catalyst for the radical polymerization initiator or a reducing compound may be added to the reaction system.

  Examples of the decomposition catalyst for the radical polymerization initiator include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid and nitric acid. Metal salts of inorganic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, benzoic acid and the like; esters thereof and metal salts thereof; heterocyclic amines such as pyridine, indole, imidazole and carbazole; Etc. As for these decomposition catalysts, only 1 type may be used independently and 2 or more types may be used together.

  Examples of the reducing compound include organic metal compounds such as ferrocene; metals such as iron, copper, nickel, cobalt, and manganese, such as iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, and manganese naphthenate. Inorganic compounds capable of generating ions; inorganic compounds such as boron trifluoride ether adduct, potassium permanganate, perchloric acid; sulfur dioxide, sulfite, sulfate, bisulfite, thiosulfate, sulfoxide, benzene Sulfuric acid and its substitution products, sulfur-containing compounds such as homologues of cyclic sulfinic acid such as para-toluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid, thiopropionic acid, α- Sodium thiopropionate sulfopropyl ester , Mercapto compounds such as α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethyl hydrazine, hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde Aldehydes; ascorbic acid; and the like. These reducing compounds may be used alone or in combination of two or more.

  Any appropriate solvent can be used in the graft polymerization. With respect to the amount of the solvent used, for example, the solvent content is preferably 50% by weight or less, more preferably 10% by weight or less, and still more preferably substantially 0 with respect to the total amount of the reaction system. “Substantially 0” means a form in which no solvent is positively added at the time of graft polymerization, and it means that mixing of a solvent to the extent of impurities is acceptable. By making the usage-amount of a solvent into the said range, it becomes possible to graft efficiently.

  Any appropriate temperature can be adopted as the temperature during the graft polymerization within a range in which the object of the present invention can be achieved. For example, it is preferably 50 ° C. or higher, more preferably 70 ° C. or higher, and further preferably 100 to 150 ° C. If the temperature at the time of graft polymerization is too low, the viscosity of the reaction solution becomes too high, the graft polymerization is difficult to proceed, and the graft rate may be reduced. If the temperature during the graft polymerization is too high, the polyalkylene glycol compound and the resulting graft polymer may be thermally decomposed.

  The temperature at the time of the graft polymerization need not always be kept constant during the progress of the polymerization reaction. For example, the polymerization is started from room temperature, and the temperature is increased to a set temperature at an appropriate temperature increase time or temperature increase rate. Thereafter, the set temperature may be maintained, or the polymerization temperature may be varied (increased or decreased) over time during the course of the polymerization reaction, depending on the dropping method of the monomer component, initiator, and the like. Also good.

  As the polymerization time at the time of the graft polymerization, any appropriate time can be adopted as long as the object of the present invention can be achieved. Preferably it is 60-420 minutes, More preferably, it is 90-390 minutes, More preferably, it is 120-360 minutes. In the present invention, the time when the initiator is charged is 0 minute (polymerization start time).

  As the reaction pressure at the time of the graft polymerization, any appropriate pressure can be adopted as long as the object of the present invention can be achieved. For example, it may be under normal pressure (atmospheric pressure), reduced pressure, or increased pressure.

  Any appropriate form can be adopted as the form of the graft polymerization within a range in which the object of the present invention can be achieved. For example, a batch system, a semi-batch system, a continuous system, etc. are mentioned.

  In the above graft polymerization, after adding a polyalkylene glycol compound or an unsaturated compound as a raw material into the reactor, stirring may be continued while maintaining the polymerization temperature for the purpose of reducing residual monomers. Good. As stirring time in this case, Preferably it is 30 to 360 minutes, More preferably, it is 60 to 180 minutes, More preferably, it is 60 to 120 minutes.

  For the purpose of further reducing the residual monomer, a post-treatment of adding a peroxide and / or an azo compound may be performed on the reaction product obtained by the graft polymerization.

  In the post-treatment, considering the actual use, the graft polymer is preferably an aqueous solution. The concentration of the aqueous solution of the graft polymer is preferably higher from the viewpoint of economics (transportation cost) of the product form, preferably 40% by weight or more, more preferably 50% by weight or more, and still more preferably 60% by weight. % Or more.

  Any appropriate peroxide can be adopted as the peroxide within the range in which the object of the present invention can be achieved. For example, inorganic peroxides (hydrogen peroxide, persulfates (sodium persulfate, potassium persulfate, ammonium persulfate, etc.), belloxoborate, dithionite, bisulfite, disulfite, etc.); organic peroxides (Such as those exemplified as the polymerization initiator, peracetic acid, peracetic acid salts (such as sodium peracetate), percarbonates (such as sodium percarbonate)). These peroxides may be used alone or in combination of two or more. Among these, water-soluble ones are preferable, inorganic peroxides are more preferable, and hydrogen peroxide is most preferable. In addition, when using a peroxide as an additive in post-processing, it is preferable that the peroxide differs from the polymerization initiator used at the time of superposition | polymerization. Moreover, when using a peroxide in post-processing, it is preferable to use together with the peroxide the decomposition accelerator which can accelerate | stimulate decomposition | disassembly of a peroxide. Examples of the decomposition accelerator include reducing agents such as amines, ascorbic acid and iron, and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. These decomposition accelerators may be used alone or in combination of two or more. As the decomposition accelerator, a reducing agent is preferable, and ascorbic acid is most preferable.

  Any appropriate azo compound may be employed as the azo compound within a range in which the object of the present invention can be achieved. For example, 1,1′-azobis (cyclohexane-1-force rubonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis Azonitrile compounds such as (2,4-dimethylvaleronitrile) and 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile); 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, Azoamidine compounds such as 2,2′-azobis [2- (2-imidazolin-2-yl) propane]; 2,2′-azobis {2-methyl-N- [1, 1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2-methyl) -Azoamide compounds such as propionamide) dihydrate; azoalkyl compounds such as 2,2'-azobis (2,4,4-trimethylpentane) and 2,2'-azobis (2-methylpentane); 2-cyano- 2-propylazoformamide; 4,4'-azobis (4-cyanovaleric acid); dimethyl 2,2'-azobis (2-methylpropionate); 2,2'-azobis (2-hydroxymethylpropio) Nitrile); and the like. These azo compounds may be used alone or in combination of two or more. Of these, water-soluble ones are preferred, such as (2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane]. Dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2-cyano-2-propylazoformamide) are more preferable.

  Any appropriate temperature can be adopted as the temperature during the post-treatment within a range in which the object of the present invention can be achieved. For example, it is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and further preferably 70 ° C. or lower. Moreover, room temperature or more is preferable. You may carry out under recirculation | reflux.

  Arbitrary appropriate time can be employ | adopted for the time of the said post-process within the range which can achieve the objective of this invention. For example, 10 minutes or more is preferable, 30 minutes or more is more preferable, and 60 minutes or more is more preferable.

  As a use amount of the peroxide and / or the azo compound in the post-treatment, any appropriate amount can be adopted as long as the object of the present invention can be achieved. For example, it is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight, and still more preferably 0.06 to 2% by weight based on the graft polymer.

  When a reducing agent is used in combination with the peroxide in the post-treatment, any appropriate amount can be adopted as the amount used within the range in which the object of the present invention can be achieved. For example, it is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight, and still more preferably 0.06 to 2% by weight based on the graft polymer.

  As a method for adding the peroxide or azo compound in the post-treatment, any appropriate method can be adopted within a range in which the object of the present invention can be achieved.

  Each of the peroxide and the azo compound in the post-treatment may be in the form of powder or liquid. A liquid is preferred for ease of production. When used as a liquid, it is most preferably used as an aqueous solution.

  The graft polymer obtained in the present invention has good compatibility with a surfactant. For this reason, it is possible to improve cleaning performance by adding to a cleaning agent, more preferably a liquid cleaning agent, and even more preferably a body liquid cleaning agent.

  Since the graft polymer obtained by the present invention is very excellent in the dispersion action of solid particles, it is useful as a detergent builder, water treatment agent, fiber treatment agent, dispersant, cement dispersant and the like. The graft polymer obtained by the present invention can be used as it is by dissolving it in a solvent such as water or alcohol, or by adding a base. Examples of the base include monovalent metal salts such as sodium salts and potassium salts; divalent metal salts such as calcium salts; trivalent metal salts such as aluminum salts; ammonium salts; organic amine salts such as monoethanolamine and triethanolamine. And the like.

  When using the graft polymer obtained by this invention as a water treatment agent, it can also be set as the composition which mix | blended the polymerization phosphate, the phosphonate, the anticorrosive, the slime control agent, and the chelating agent. In any case, it is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a valve digester, a black liquor concentration tank, and the like. Further, any appropriate water-soluble polymer may be included as long as it does not affect performance and effects.

  When using the graft polymer obtained by this invention as a fiber processing agent, you may contain the other additive as needed. Examples of the other additive include at least one component selected from the group consisting of a dye, a peroxide, and a surfactant. Any appropriate additive can be adopted as the staining agent, peroxide, and surfactant.

  When using the graft polymer obtained by this invention as a dispersing agent, another component can also be included as needed. Examples of the other components include at least one compound selected from the group consisting of polymerized phosphoric acid, polymerized phosphate, phosphonic acid, phosphonate, polyvinyl alcohol, and anionized modified polyvinyl alcohol.

  When using the graft polymer obtained by this invention as a cement dispersing agent, another component can also be included as needed. When the cement dispersant containing the graft polymer obtained in the present invention is used for a cement composition such as cement mortar or concrete, the graft polymer obtained in the present invention improves the dispersibility, and a large cure retardance by addition. In this case, high fluidity can be exhibited and the stool time can be extended. For this reason, workability of mortar construction and concrete construction is remarkably improved.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, parts and% in the examples are based on weight.

[Example 1]
Phenoxypolyethylene glycol melted at 60 ° C. or higher in a SUS reactor equipped with a thermometer, a stirrer, a gas inlet and a gas outlet that do not have protrusions on the inner surface of the reactor, and a reflux condenser Average molecular weight: 974, ethylene oxide unit average added mole number: 20) 510 parts by weight, 37 parts by weight of maleic anhydride, and 1.4 parts by weight of water were charged, and nitrogen was added at 5.0 L / min as an inert gas. While flowing, the mixture was stirred at 60 ° C. for 1 hour. Subsequently, the temperature was raised to 128 ° C., 8 parts by weight of di-tert-butyl peroxide was continuously added dropwise over 195 minutes as an initiator while maintaining the temperature at 125 to 133 ° C., and 124 parts by weight of acrylic acid. Was continuously added dropwise over 245 minutes from 20 minutes after the start of the initiator addition. Thereafter, stirring was continued for about 1 hour to obtain a graft polymer (1). The (meth) acrylic acid concentration in the gas phase part of the reactor during the polymerization was 1.0% by volume or less.
When the inner surface of the reactor was observed after polymerization, no gel-like substance was observed on the inner surface of the reactor.

[Comparative Example 1]
As a SUS reactor, a SUS reactor equipped with a thermometer, a stirrer, a gas inlet and a gas outlet having protrusions on the inner surface side of the reactor, and a reflux condenser was used. Under a nitrogen atmosphere (nitrogen flow rate = 0.0 L / min: nitrogen was not circulated), and the same procedure as in Example 1 was performed to obtain a graft polymer (C1). The (meth) acrylic acid concentration in the gas phase part of the reactor during the polymerization was 3.2% by volume or less.
When the inner surface of the reactor was observed after polymerization, adhesion of a gel substance was observed on the inner surface side of the reactor. In particular, a lot of gel-like substance was observed in the vicinity of the gas inlet.

[Comparative Example 2]
As a SUS reactor, a SUS reactor equipped with a thermometer, a stirrer, a gas inlet and a gas outlet having protrusions toward the inner surface of the reactor, and a reflux condenser was used. A graft polymer (C2) was obtained in the same manner as in Example 1 except that the flow rate was 1 L / min. The (meth) acrylic acid concentration in the gas phase part of the reactor during the polymerization was 2.9% by volume or less.
When the inner surface of the reactor was observed after polymerization, adhesion of a gel substance was observed on the inner surface side of the reactor. In particular, a lot of gel-like substance was observed in the vicinity of the gas inlet and the gas outlet.

[Example 2]
Phenoxypolyethylene glycol melted at 60 ° C. or higher in a SUS reactor equipped with a thermometer, a stirrer, a gas inlet and a gas outlet that do not have protrusions on the inner surface of the reactor, and a reflux condenser Average molecular weight: 974, ethylene oxide unit average added mole number: 20) 465 parts by weight were charged, and the temperature was raised to 128 ° C. with stirring while flowing nitrogen at 3.0 L / min as an inert gas. Next, while maintaining the temperature at 125 to 133 ° C., 7.8 parts by weight of di-tert-butyl peroxide was continuously dropped over 195 minutes as an initiator, and 181 parts by weight of acrylic acid was started to be dropped. After 20 minutes, it was continuously added dropwise over 245 minutes. Thereafter, stirring was continued for about 1 hour to obtain a graft polymer (2). The (meth) acrylic acid concentration in the gas phase part of the reactor during the polymerization was 1.2% by volume or less.
When the inner surface of the reactor was observed after polymerization, no gel-like substance was observed on the inner surface of the reactor.

[Comparative Example 3]
As a SUS reactor, a SUS reactor equipped with a thermometer, a stirrer, a gas inlet and a gas outlet having protrusions on the inner surface side of the reactor, and a reflux condenser was used. Under a nitrogen atmosphere (nitrogen flow rate = 0.0 L / min: a graft polymer (C3) was obtained in the same manner as in Example 2 except that nitrogen was not passed. The (meth) acrylic acid concentration in the gas phase portion of the reactor during the polymerization was 3.0% by volume or less.
When the inner surface of the reactor was observed after polymerization, adhesion of a gel substance was observed on the inner surface side of the reactor. In particular, a lot of gel-like substance was observed in the vicinity of the gas inlet.

[Comparative Example 4]
As a SUS reactor, a SUS reactor equipped with a thermometer, a stirrer, a gas inlet and a gas outlet having protrusions toward the inner surface of the reactor, and a reflux condenser was used. A graft polymer (C4) was obtained in the same manner as in Example 2 except that the flow rate was 1 L / min. The (meth) acrylic acid concentration in the gas phase part of the reactor during the polymerization was 2.8% by volume or less.
When the inner surface of the reactor was observed after polymerization, adhesion of a gel substance was observed on the inner surface side of the reactor. In particular, a lot of gel-like substance was observed in the vicinity of the gas inlet and the gas outlet.

Example 3
Phenoxy melted at 60 ° C. or higher in a SUS reactor having an internal volume of 140 L equipped with a thermometer, a stirrer, a gas inlet and a gas outlet that do not have protrusions on the inner surface of the reactor, and a reflux condenser 4780 parts by weight of polyethylene glycol (number average molecular weight: 974, average number of added moles of ethylene oxide unit: 20) was charged, and the temperature was raised to 128 ° C. with stirring while flowing nitrogen at 210.0 L / min as an inert gas. Next, while maintaining the temperature at 125 to 133 ° C., 80 parts by weight of di-tert-butyl peroxide as an initiator is continuously dropped over 195 minutes, and 1860 parts by weight of acrylic acid is added for 20 minutes from the start of initiator dropping. After that, it was continuously dropped over 245 minutes. Thereafter, stirring was continued for about 1 hour to obtain a graft polymer (3). The (meth) acrylic acid concentration in the gas phase part of the reactor during the polymerization was 1.5% by volume or less.
When the inner surface of the reactor was observed after polymerization, no gel-like substance was observed on the inner surface of the reactor.

[Comparative Example 5]
As a SUS reactor, a SUS reactor equipped with a thermometer, a stirrer, a gas inlet and a gas outlet having protrusions on the inner surface side of the reactor, and a reflux condenser was used. 0.0 L / min: nitrogen was not circulated), and the same procedure as in Example 3 was performed to obtain a graft polymer (C5). The (meth) acrylic acid concentration in the gas phase part of the reactor during the polymerization was 3.3% by volume or less.
When the inner surface of the reactor was observed after polymerization, adhesion of a gel substance was observed on the inner surface side of the reactor. In particular, a lot of gel-like substance was observed in the vicinity of the gas inlet.

[Comparative Example 6]
As a SUS reactor, a SUS reactor equipped with a thermometer, a stirrer, a gas inlet and a gas outlet having protrusions on the inner surface of the reactor, and a reflux condenser, and 10 L of nitrogen as an inert gas A graft polymer (C6) was obtained in the same manner as in Example 3 except that the flow rate was 1 minute. The (meth) acrylic acid concentration in the gas phase portion of the reactor during the polymerization was 3.0% by volume or less.
When the inner surface of the reactor was observed after polymerization, adhesion of a gel substance was observed on the inner surface side of the reactor. In particular, a lot of gel-like substance was observed in the vicinity of the gas inlet and the gas outlet.

  The graft polymer obtained by the production method of the present invention can be used for, for example, a detergent builder, a scale inhibitor, a fiber treatment agent, a dispersant and the like.

It is a schematic sectional drawing of the reactor which can be used by preferable embodiment of this invention. It is a schematic sectional drawing of the reactor which cannot be used by embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Gas inlet 11 Gas outlet 20 Gas inlet 21 Gas outlet 22 Protrusion part 23 Protrusion part 100 Reactor 200 Reactor

Claims (7)

  A method for producing a graft polymer by reacting a polyalkylene glycol compound and an unsaturated compound in a reactor, the reactor comprising a gas inlet and a gas outlet, the gas inlet and the gas A method for producing a graft polymer, wherein each of the discharge ports does not have a protruding portion toward the inner surface of the reactor, and the reaction is carried out while introducing an inert gas from the gas inlet.   The manufacturing method of Claim 1 in which the said unsaturated compound contains unsaturated monocarboxylic acid and / or unsaturated dicarboxylic acid.   The manufacturing method of Claim 2 with which the said unsaturated compound contains (meth) acrylic acid.   The manufacturing method of Claim 3 whose (meth) acrylic acid density | concentration in the gaseous-phase part in the said reactor is 2.0 volume% or less.   The production method according to any one of claims 1 to 4, wherein the polyalkylene glycol compound has a hydrophobic group.   The production method according to claim 5, wherein the hydrophobic group is a long-chain alkyl group and / or an aromatic group.   The production method according to any one of claims 1 to 6, wherein the inert gas is at least one selected from nitrogen, carbon dioxide, helium, and argon.

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