JP2007092051A - Polyalkylene glycol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyalkylene glycol containing less impurities, specifically, a polyalkylene glycol containing a reduced amount of a diol such as polyethylene glycol, a diester, a halogen, a metal, water and a discoloring-causative substance; and to provide a method for producing the polyalkylene glycol. <P>SOLUTION: The polymerizable polyalkylene glycol satisfies the characteristics that: (1) the polymerizable dimer content is 0.001-10% by weight; and/or (2) the metal content is not more than 50 ppm. The polymerizable dimer content is preferably 0.001-3.5% by weight. More preferably, the polymerizable polyalkylene glycol satisfies both the characteristics (1) and (2). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to polyalkylene glycols and a method for producing the same. More specifically, polyalkylenes useful as raw materials for production that can be used in various applications such as various polymeric materials, concrete admixtures, adhesives, adhesives, paints, various additives such as cosmetic additives and inorganic dispersants. The present invention relates to glycols and a method for producing the same.

Polyalkylene glycols are compounds that can be used as various industrial chemical raw materials, and those having an unsaturated bond are particularly useful as monomers or the like that form polymers used in various applications. As a method for producing polyalkylene glycols, for example, a reaction in which a hydroxyalkyl (meth) acrylate is used as an initiator and alkylene oxide (AO) is directly added to synthesize polymerizable polyalkylene glycols is known. In such a reaction, a catalyst for adding an alkylene oxide is used. In the case of an active hydrogen possessed by an initiator, in the case of hydroxyalkyl (meth) acrylate, an alkylene oxide reacts with a terminal hydroxyl group. By addition, a compound having a polyalkylene glycol chain and a terminal unsaturated group derived from hydroxyalkyl (meth) acrylate is produced.

As a conventional method for producing a (meth) acrylate monomer having a polyalkylene glycol chain, oxyalkylation with at least one carbon-carbon unsaturated site and alkylene oxide in the presence of a double metal cyanide complex catalyst. Initiator molecules having at least one possible functional group and no more than one free carboxylic acid group are oxyalkylated with alkylene oxide to produce hydroxyl- and unsaturated-functional polyoxyalkylene polyethers. (For example, refer to Patent Document 1). Moreover, the method of manufacturing polyether from the mixture of an initiator compound, ethylene oxide, and a metal cyanide catalyst complex is disclosed (for example, refer patent document 2).

Moreover, the manufacturing method of the polyethyleneglycol methacrylate which treats a boron trifluoride compound with an adsorbent after carrying out ring-opening polymerization of ethylene oxide to 2-hydroxyethyl methacrylate using a boron trifluoride compound as a catalyst is disclosed ( For example, see Patent Document 3.) However, Lewis acid catalysts such as metal cyano complex compounds such as so-called DMC catalysts, tin chloride, and boron trifluoride compounds are used by being dissolved in the raw material. In order to remove impurities derived from the catalyst, After the reaction, it is necessary to perform extraction with water, an organic solvent, or the like, or to remove using an adsorbent, and it has been difficult to obtain a product of high purity economically.

On the other hand, a production method in which (meth) acrylic acid ester is produced by addition reaction of alkylene oxide in the presence of activated clay is disclosed (for example, see Patent Document 4).
Also disclosed is a method for producing polyalkylene glycol monoacrylate or monomethacrylate by adding alkylene oxide in the presence of a catalytic amount of tin tetrachloride (see, for example, Patent Document 5).

However, activated clay has a problem that the catalytic activity is low and the reaction takes time, while SnCl ₄ has a problem that a large amount of diester, which is a byproduct obtained by esterification of both ends of the product, is generated. . Since the diester contains an unsaturated group in the structure at both ends and acts as a crosslinking agent, there are various (meth) acrylate monomers having a polyalkylene glycol chain containing many diesters as such impurities. In other applications, the effect cannot be exhibited effectively. Therefore, in the production of polyalkylene glycols, it is possible to efficiently add alkylene oxide to the initiator, and to suppress the content of inconvenient components such as diesters in the produced polyalkylene glycols. There is a need for a production method that can be used.
Special table 2001-514280 (page 2-7) Special table 2003-504468 (page 2-3) JP-A-2005-170814 (first page) JP 7-10801 (first page) Shoko 52-30489 (1st page)

The present invention provides polyalkylene glycols with less impurities and a method for producing the same. Specifically, it provides a diol such as polyethylene glycol, a diester, a halogen, a metal, water, a polyalkylene glycol with little coloring-causing substances, and a method for producing the same. In general, polyalkylene glycol mono (meth) acrylates are used as raw materials for (meth) acrylic resins and photocurable resins for the purpose of improving adhesion, imparting lyophilicity, imparting flexibility, and the like. Yes. In particular, polyalkylene glycol mono (meth) acrylates having a small number of moles of alkylene oxide added may be used as reactive diluents. In addition, polyalkylene glycol mono (meth) acrylates having a small number of moles of alkylene oxide added can provide a material having a high storage elastic modulus at room temperature because of low viscosity and the like. However, since it is difficult to remove diols such as polyethylene glycol, diesters, halogens, metals, water, and color-causing substances with conventional techniques, high-quality polyalkylene glycol mono (meth) acrylates can be obtained. I could not. In particular, urethane (meth) acrylates used for electronic materials and the like have been unavoidable problems such as inhibition reaction, high viscosity, gelation, and dynamic viscoelasticity reduction due to these impurities.

The present inventors have studied various methods for producing polyalkylene glycols that can have an unsaturated group in the presence of a catalyst, and in the presence of a catalyst, an alkylene oxide is reacted with an unsaturated initiator to produce a polyalkylene glycol. Focusing on the fact that the method for producing glycols is industrially useful, and conducting catalyst screening with the aim of developing an optimum catalyst for the production method, we found that the solid acid catalyst was effective, I was able to solve this problem. In particular, it is effective to use a solid acid as a catalyst in a reaction in which an alkylene oxide (particularly ethylene oxide) is directly added to an unsaturated initiator such as hydroxyalkyl (meth) acrylate to synthesize polymerizable polyethylene glycol (PEG). In addition, it has been found that a crystalline metal oxide, particularly zeolites, or an aluminum compound having a five-coordinated structure of aluminum can be used as a catalyst, and a more advantageous effect can be obtained.
Moreover, after adding an alkylene oxide using the said solid catalyst, it discovered that a highly purified polyalkylene glycol mono (meth) acrylate was obtained by isolate | separating a catalyst by a well-known method. Further, after addition of alkylene oxide using the above solid catalyst, the catalyst is separated by a known method, and then a high-purity polyalkylene glycol mono (meth) is obtained from a residue obtained by a known method such as distillation. The inventors have found that an acrylate is obtained and have reached the present invention.

That is, the present invention provides the following characteristics (1) and / or (2):
(1) Polymerizable polyalkylene glycols satisfying that the polymerizable dimer content is 0.001 to 10% by weight and (2) the metal content is 50 ppm or less.
The present invention also relates to a method for producing a polyalkylene glycol by reacting an unsaturated initiator with an alkylene oxide, which comprises a crystalline metal oxide and aluminum having a five-coordinate structure of aluminum. It is also a method for producing polyalkylene glycols using at least one solid acid catalyst selected from the group consisting of compounds.
The present invention is described in detail below. In addition, in this specification, the said manufacturing method is demonstrated first, and polymerizable polyalkylene glycol is demonstrated after that.

In the present specification, “above” and “below” include the numerical values. That is, “more than” means less (the value and more than the value).
In the production method of the above polyalkylene glycols, it is preferable to react an alkylene oxide with an unsaturated initiator using a solid acid catalyst as a catalyst. By using a solid acid, an alkylene oxide can be directly added to an unsaturated initiator to obtain a polymerizable polyalkylene glycol.
It is also a preferred embodiment of the present invention that the solid acid catalyst is a crystalline metal oxide that exists as a solid by dispersion or the like in the reaction solution. Examples suitable for the present invention include silica, alumina, silica alumina, various zeolites, activated carbon, diatomaceous earth, zirconium oxide, rutile titanium oxide, tin oxide, lead oxide, and sulfur oxides composed of metals of groups 6-13. , Composite oxides having at least one element selected from the group consisting of 3-6 and 12-15 groups, composite oxides consisting of silicon and at least one metal, crystalline metallosilicates, zirconia, titania, magnesia, etc. Although it is mentioned, it is not restricted to these.

The crystalline metal oxide is not particularly limited as long as it can be suitably used in the production method of the present invention in addition to the above-mentioned examples, and specifically, silica, alumina, crystalline metallosilicate. And zeolite are preferred, and among these, zeolite is preferred. As zeolite, β- and Y-zeolite are preferable, and β-zeolite is more preferable. Zeolites are highly active in alkylene oxide (especially ethylene oxide) addition reactions, and have the advantage of producing less dimers such as diesters as by-products.

As the crystalline metal oxide, it is preferable that the amount of the acid is 0.05mmolNH ₃ / g or more, more preferably 0.1mmolNH ₃ / g or more, more preferably 0.3mmolNH ₃ / g or more, particularly preferably It is 0.5 mmol NH ₃ / g or more. The ammonia TPD method is suitable as a method for measuring these acid amounts.

In the method for producing the polyalkylene glycol, the unsaturated initiator may be reacted with an alkylene oxide using an aluminum compound having an aluminum pentacoordinate structure as the solid acid catalyst. One of the forms. Thereby, an alkylene oxide can be directly added to an unsaturated initiator, and polymerizable polyalkylene glycols can be obtained efficiently.

The aluminum compound preferably has a peak area at 25 to 35 ppm of the 27Al-NMR chart of 40% or more with respect to the sum of peak areas at 0 to 10, 25 to 35, and 45 to 55 ppm. Since such an aluminum compound has a high activity in the method for producing polyalkylene glycol, the polyalkylene glycol can be produced efficiently. This is presumably because the aluminum compound contains a certain amount of aluminum having a pentacoordinate structure. Generally, aluminum (III) is known to have a coordination number of 6 because the electron orbit involved in the coordination bond is d ² sp ³ (octahedral bond). On the other hand, it is known that γ-alumina includes a part of a tetracoordinate structure in addition to a hexacoordinate structure in which all coordinateable electron orbitals are occupied. When such aluminum of γ-alumina is substituted with other elements, a so-called coordinated unsaturated state occurs, and a five-coordinate structure may appear. In addition to oxides (oxo complexes) such as γ-alumina, it is considered that even an amine complex exhibits a coordination unsaturated structure. And whether aluminum has expressed the 5-coordinate structure can be confirmed by measuring 27Al-NMR. The peak at 0-10 ppm appearing in the NMR chart obtained shows a 6-coordinate structure, the peak at 25-35 ppm shows a 5-coordinate structure, and the peak at 25-35 ppm shows a 4-coordinate structure. Therefore, the abundance ratio of aluminum having each coordination structure can be calculated from the ratio of peak areas in the 27Al-NMR chart. Aluminum having a pentacoordinate structure has an appropriate acid-base strength and can activate both oxygen of alcohol (ROH) and oxygen of alkylene oxide. By including, polyalkylene glycol can be manufactured efficiently. On the other hand, when aluminum having a five-coordinate structure is not included, since it is not moderately acidic, ROH and alkylene oxide are not moderately activated, and the effects of the present invention cannot be exhibited. It is considered a thing.
As said aluminum compound, More preferably, the peak area in 25-35 ppm is 50% or more with respect to the sum of the peak area in 0-10, 25-35, and 45-55 ppm. More preferably, it is 54% or more.

The measurement conditions for the 27Al-NMR are preferably as follows. In this specification, the 27Al-NMR measurement conditions are the same as this.
Equipment: ECA600 manufactured by JEOL, Magnet 14.1T
Measurement conditions: 4 mm zirconia rotor tube is filled with sample, MAS (spinning) 18 kHz, room temperature resonance frequency 156.39 MHz, DD / MAS measurement method, pulse width 1.2 microseconds, repetition time 2 seconds, integration number 2000 to 30000 Times (depending on the sample)
Peak separation method: Measurement software (DELTA). Use Gauss-Lorentz function.

The aluminum compound preferably contains aluminum and at least one element of Group 3-15.
Examples of the at least one element of Group 3 to 15 include scandium, titanium, zirconium, hafnium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, boron, gallium, silicon, germanium, and the like. Among these, at least one element selected from titanium, zirconium, hafnium, boron, gallium, silicon, and germanium is particularly preferable. The aluminum compound containing these elements can produce polyalkylene glycol efficiently because the aluminum compound exhibits excellent activity as a catalyst in the production of polyalkylene glycol. Preferably, it is silicon.

The aluminum compound is preferably obtained by supporting aluminum on the silica surface. The amount of aluminum supported after the treatment is preferably 0.5 to 40% based on the total weight of the aluminum compound. More preferably, it is 0.5-10%, More preferably, it is 0.5-5%.
The aluminum compound containing these elements can produce polyalkylene glycol efficiently because the aluminum compound exhibits excellent activity as a catalyst in the production of polyalkylene glycol. In this case, when 27Al-NMR is measured, the peak area having the maximum value at 25 to 35 ppm is 40% or more with respect to the sum of the peak areas at 0 to 10, 25 to 35, and 45 to 55 ppm. preferable.
The above-mentioned support preferably converts a hydroxyl group on the silica surface thermally or chemically and binds to an aluminum atom via an oxygen atom. Thus, it is considered that when aluminum is supported on the silica surface, a five-coordinate structure appears in the aluminum.

The aluminum compound is preferably bonded to at least one element selected from nitrogen, phosphorus, oxygen and sulfur. The aluminum compound bonded to these elements can efficiently produce polyalkylene glycol because the aluminum compound exhibits excellent activity as a catalyst in the production of polyalkylene glycol.

In the method for producing the polyalkylene glycol, the polyalkylene glycol obtained by the production method is characterized by the following characteristics (1) and / or (2):
(1) The polymerizable dimer content is 0.05 to 10% by mass,
(2) One of the preferred embodiments of the present invention is a polymerizable polyalkylene glycol having a metal content of 50 ppm or less.
The physical properties of the polyalkylene glycols obtained by the above production method preferably satisfy the characteristics of the polyalkylene glycols described later.

In the above production method, the reaction format is not particularly defined, and may be a suspended bed or a fixed bed, and may be set as appropriate according to productivity. Although it does not specifically limit regarding the usage-amount of a catalyst, It is preferable that it is 0.1-50 mass% with respect to a raw material unsaturated initiator. More preferably, it is 1-50 mass%. More preferably, it is 3-30 mass%.

The unsaturated initiator in the present invention may be a compound that can undergo an addition reaction with an alkylene oxide, and among them, an active hydrogen compound is preferable. Examples of the active hydrogen compound include a compound having a hydroxyl group.
Moreover, it is preferable that the unsaturated initiator further has an unsaturated group at the terminal, and the method for producing polyalkylene glycols in which the unsaturated initiator is an unsaturated initiator having a terminal unsaturated group is provided. This is one of the preferred embodiments of the present invention. By using an unsaturated initiator having a terminal unsaturated group, the polyalkylene glycol to be produced has an unsaturated group derived from the unsaturated initiator in the terminal structure. Polymerizable polyalkylene glycols having an unsaturated group are useful as polymerizable monomers.

As the unsaturated initiator, the following compounds (I) to (IX) are suitable.
(I) the following general formula (1);
HO-Xm-OCO-CH = CH-COO-Xn-OH (1)
(In the formula, Xm is an alkyl group having a linear or branched chain having 0 to 18 carbon atoms, and Xn is an alkyl group having a linear or branched chain having 1 to 18 carbon atoms). Hydroxyalkyl maleic acid esters or hydroxyalkyl fumarate esters.
In the said General formula (1), carbon number of Xm and Xn is the same or different, More preferably, it is 1-10, More preferably, it is 2-5.

(II) The following general formula (2) or (3);
HO-Xp-CH = CH-Xq-OH (2)

(In the formulas (2) and (3), Xp, Xq, Xr and Xs are the same or different and are alkyl groups having a straight chain or branched chain having 1 to 18 carbon atoms). .
In the general formulas (2) and (3), the carbon number of Xp, Xq, Xr and Xs is the same or different, more preferably 1 to 10, and still more preferably 2 to 5.
(III) The following general formula (4);

(In the formula, Xt and Xu are the same or different and are linear or branched alkyl groups having 0 to 18 carbon atoms, and the carbon number of Xt = the number of carbon atoms of Xu is not 0). Hydroxyalkyl itaconate esters.
In the said General formula (4), carbon number of Xt and Xu is the same or different, More preferably, it is 1-10, More preferably, it is 2-5.
(IV) the following general formula (5);

(Wherein R ¹ represents a hydrogen atom or a methyl group. Xv is a linear or branched alkyl group having 1 to 18 carbon atoms).
In the general formula (5), the carbon number of Xv is more preferably 1 to 10, and further preferably 2 to 5.
(V) the following general formula (6);

(In the formula, R ² represents a hydrogen atom or a methyl group. Xw is an alkyl group having a straight chain or branched chain having 2 to 18 carbon atoms.) Kind.
In the general formula (6), the carbon number of Xw is more preferably 2 to 10, and further preferably 2 to 5.
(VI) the following general formula (7);

(In the formula, R ³ represents a hydrogen atom or an alkyl group having a straight chain or branched chain having 1 to 20 carbon atoms.)

(VII) the following general formula (8);
_{CH 2 = CH-C 6 H} (5-x) - (OH) x (8)
(Wherein x is an integer of 1 to 3).

(VIII) Other general formulas (9) and (10) below;
_{CH 2 = CH-C 6 H} 4 -Xy-OH (9)
_{CH 2 = CH-Xz-C} 6 H 4 -OH (10)
(In the formulas (9) and (10), Xy and Xz are the same or different, and are alkyl groups having a linear or branched chain having 1 to 18 carbon atoms.) Agent.
(IX) An alkylene oxide adduct of the compounds represented by the general formulas (1) to (10).

As described above, the unsaturated initiator used in the present invention is preferably an active hydrogen compound having an unsaturated group, more preferably an active hydrogen compound having a terminal unsaturated group, still more preferably , Hydroxyalkyl compounds having a terminal unsaturated group, particularly preferably (meth) allyl alcohol, hydroxyalkyl esters having a terminal unsaturated group, and most preferably hydroxyalkyl (meth) acrylate. Of these, hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate are most suitable.

The alkylene oxide used in the above reaction is preferably an alkylene oxide having 2 to 18 carbon atoms or styrene oxide, and these may be one kind or a form in which two or more kinds are blended. Moreover, as the carbon number, 2-18 is suitable, However, 2-8 are preferable and 2-4 are more preferable. Specific examples include ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like, and any two or more alkylene oxide adducts are in any form of random addition, block addition, and alternate addition. Also good. In the present specification, “alkylene oxide” means a substance including styrene oxide.
As an average addition mole number of the oxyalkylene group or oxystyrene group in this reaction, a number of 1 to 300 is appropriate, but 1 to 110 is preferable, and 1 to 50 is more preferable. More preferably, it is 1-30. Especially preferably, it is 1-25. Most preferably, it is 1-20. More preferably, it is 1-10. Most preferably, it is 1-5.
As described above, the polymerizable polyalkylene glycols are obtained by reacting an unsaturated initiator with an alkylene oxide, and the average added mole number of the alkylene oxide is 1 to 300. It is one of the preferred embodiments of the invention.

Next, a general embodiment of a method for obtaining a polyalkylene glycol by reacting an unsaturated initiator and an alkylene oxide in the above production method will be described, but the present invention is not limited to this embodiment. .
In the above production method, for example, the reaction is allowed to proceed by appropriately supplying a catalyst, an unsaturated initiator and alkylene oxide to the reactor, and the reaction is performed when the amount of residual alkylene oxide in the reactor becomes a predetermined concentration or less. It is common to end. The above reaction is an exothermic reaction, and the reaction starts when the unsaturated initiator and the alkylene oxide coexist in the presence of the catalyst, and the temperature of the reaction solution is set to a predetermined predetermined value by cooling or the like. The reaction is terminated by lowering the reaction temperature.

The method (order) for charging the unsaturated initiator and the alkylene oxide is not particularly limited. For example, a part or all of the unsaturated initiator is initially charged in the reactor, and then the alkylene oxide or the unsaturated initiator is started. The remaining amount of the agent and the alkylene oxide may be supplied, or a part or all of the alkylene oxide may be initially charged.

The unsaturated initiator and alkylene oxide may be supplied in a batch manner or a sequential manner (continuous introduction and / or intermittent introduction), but the initial charge is preferably introduced all at once. It is preferable to sequentially supply the supply amount. The continuous charging means a mode of continuously charging little by little, and the intermittent supply means a mode of charging in an arbitrary number of times in a pulsed manner or intermittently. In addition, in the case of continuous charging, the charging speed may be made constant while the charging speed is kept constant, or may be advanced while the speed itself is continuously changed arbitrarily. However, when changing the speed in the middle, it is preferable to reduce the speed from before the change to after the change.
When both the unsaturated initiator and the alkylene oxide are charged at the same time, they may be added from separate charging lines, or mixed in advance by piping, a line mixer, a mixing tank, etc. before being charged into the reactor. However, if they are added from separate charging lines, there is a possibility that the molar ratio of alkylene oxide and unsaturated initiator in the system may be biased, so the charging is performed to the reactor. It is preferable to add them after mixing in advance. In addition, when adding from each separate input line, it is not necessary for the raw materials to be the same in terms of the input form (batch input, sequential input), the temperature of the input raw materials, the input speed, and the like.

The temperature at which the unsaturated initiator and alkylene oxide are charged may be charged at room temperature or after preheating to a desired temperature so as not to change the temperature in the system at that time. You may throw it in. In addition, the time required for completing the entire supply of the unsaturated initiator and alkylene oxide is not particularly limited, and may be set as appropriate in consideration of the progress of the reaction, productivity, and the like.

In the reaction between the unsaturated initiator and the alkylene oxide, a polymerization inhibitor may be added to the reaction system as necessary. The polymerization inhibitor is not particularly limited as long as it is generally used industrially. For example, hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 2,4-dimethyl-6-tert-butyl phenol, hydroquinone monomethyl ether, etc. Phenol compounds of N-isopropyl-N′-phenyl-para-phenylenediamine, N- (1,3-dimethylbutyl) -N′-phenyl-para-phenylenediamine, N- (1-methylhebutyl) -N Paraphenylenediamines such as' -phenyl-para-phenylenediamine, N, N'-diphenyl-para-phenylenediamine, N, N'-di-2-naphthyl-para-phenylenediamine; amines such as thiodiphenylamine and phenothiazine Compound: Dibutyl Dialkyldithiocarbamic acid copper salts such as copper thiocarbamate, copper diethyldithiocarbamate, copper dimethyldithiocarbamate; 2,2,4,4-tetramethylazetidine-1-oxyl, 2,2-dimethyl-4,4-di Propylazetidine-1-oxyl, 2,2,5,5-tetramethylpyrrolidine-1-oxyl, 2,2,5,5-tetramethyl-3-oxopyrrolidine-1-oxyl, 2,2,6 6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6, -tetramethylpiperidine-1-oxyl, 6-aza-7,7-dimethyl-spiro (4,5) decane-6 -Oxyl, 2,2,6,6-tetramethyl-4-acetoxypiperidine-1-oxyl, 2,2,6,6-tetramethyl-4 {benzoyloxy One or more of N-oxyl compounds such as piperidine-1-oxyl, 4,4 ′, 4 ″ -tris- (2,2,6,6-tetramethylpiperidine-1-oxyl) phosphite Can be used.

The addition amount of the polymerization inhibitor is preferably 0.0001 to 1% by mass with respect to 100% by mass of the total supply amount of the raw material unsaturated initiator. More preferably, it is 0.001-0.5 mass%. Further, the timing for adding the polymerization inhibitor is not particularly limited, but it is preferable to add it to the reactor first together with the components to be initially charged.
In the above reaction, the reaction may be carried out in the presence of a solvent, if necessary, for the purpose of allowing the reaction to proceed gently. As a solvent, 1 type, or 2 or more types of common solvents, such as toluene, xylene, heptane, and octane, can be used, for example.

The reaction temperature between the unsaturated initiator and the alkylene oxide is usually preferably in the range of 30 to 160 ° C. When the temperature is lower than 30 ° C, the reaction rate is remarkably reduced and the productivity is lowered. When the temperature is higher than 160 ° C, there is a possibility that by-products such as diesters increase and polymerization of the unsaturated initiator occurs. This is because More preferably, it is 30-120 degreeC, More preferably, it is 40-110 degreeC, Most preferably, it is 40-100 degreeC. Moreover, although the pressure in the reactor at the time of the said reaction is based also on the kind of raw material to be used, and its usage ratio, generally it is preferable to carry out under pressure.
The time when the above reaction is completed (in other words, the time when the reaction starts cooling) can be determined from the time when the remaining alkylene oxide has sufficiently disappeared. Moreover, the point at which the alkylene oxide has sufficiently disappeared refers to the point at which the concentration has no problem in terms of safety and productivity.

Since the polyalkylene glycols obtained by the above method have an unsaturated group in the molecule, they are useful as raw materials for polymers used in various applications. For example, it can be used as various dispersants such as various polymer materials, adhesives, adhesives, paints, cosmetic additives, concrete admixtures, cement dispersants, detergents, clay dispersants, metal dispersants for electronic material abrasives, etc. It is.

Next, a method for obtaining a (co) polymer ((co) polymerization product) by polymerizing the monomer component containing the polyalkylene glycol will be described. As such a method, only the above monomer may be polymerized or copolymerized with the above monomer and a polymerizable monomer. The upper limit of the polyalkylene glycols in 100% by mass of all monomer components is preferably 99% by mass, and more preferably 97% by mass. More preferably, it is 95 mass%. Especially preferably, it is 90 mass%. Most preferably, it is 80 mass%.
Moreover, it is preferable that a lower limit is 1 mass%. More preferably, it is 5 mass%. More preferably, it is 10 mass%. Especially preferably, it is 20 mass%. Most preferably, it is 40 mass%.

The monomer polymerizable with the polyalkylene glycol is not particularly limited, and examples thereof include maleic acid and derivatives thereof, and one or more of these can be used. The derivative of maleic acid is not particularly limited. For example, maleic anhydride; half esters of maleic acid and alcohols having 1 to 30 carbon atoms; half amides of maleic acid and amines having 1 to 30 carbon atoms A half amide or half ester of maleic acid and an amino alcohol having 1 to 30 carbon atoms; a compound obtained by adding an average of 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms to an alcohol having 1 to 30 carbon atoms And maleic acid half-esters; a compound obtained by amination of a hydroxyl group at one end of a compound obtained by adding an average of 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to an alcohol having 1 to 30 carbon atoms and maleic acid And half amides; maleic acid and glycols having 2 to 18 carbon atoms or the average of these glycols Half esters of polyalkylene glycols having 2 to 500 moles of addition; other than half amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having an average addition mole number of these glycols of 2 to 500 Monovalent metal salts, divalent metal salts, ammonium salts, and organic ammonium salts. As the monovalent metal, an alkali metal such as sodium or potassium is suitable. As the divalent metal, an alkali metal such as calcium or magnesium is suitable. The organic ammonium is a protonated organic amine. Alkanol ammonium such as ethanolammonium, diethanolammonium and triethanolammonium, and alkylammonium such as triethylammonium are suitable. Among them, it is preferable that at least one monomer selected from the group consisting of maleic acid and salts thereof, maleic anhydride, and maleic acid ester is essential, and maleic anhydride or maleic acid is essential. Particularly preferred.

Further, as monomers other than the maleic acid-based monomer, the following monomers are also exemplified as monomers copolymerized with the polyalkylene glycols of the present invention.
Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic ammonium salts thereof; unsaturated dicarboxylic acids such as fumaric acid, itaconic acid and citraconic acid , And these monovalent metal salts, divalent metal salts, ammonium salts, organic ammonium salts; half esters and diesters of unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, citraconic acid and alcohols having 1 to 30 carbon atoms Half amides and diamides of the above unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; alkyls (poly) obtained by adding 1 to 500 moles of alkylene oxides having 2 to 18 carbon atoms to the above alcohols and amines Half esters and diesters of alkylene glycol and the above unsaturated dicarboxylic acids; Half esters and diesters of saturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 addition moles of these glycols; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth ) Esters of unsaturated monocarboxylic acids such as acrylate, glycidyl (meth) acrylate, methyl crotonate, ethyl crotonate, propyl crotonate and alcohols having 1 to 30 carbon atoms; alcohols having 1 to 30 carbon atoms Esters of alkoxy (poly) alkylene glycols to which 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms have been added and unsaturated monocarboxylic acids such as (meth) acrylic acid; (poly) ethylene glycol monomethacrylate, ( Poly) propire Glycol monomethacrylate, (poly) such as butylene glycol monomethacrylate, (meth) 1 to 500 molar adducts of alkylene oxide having 2 to 18 carbon atoms to unsaturated monocarboxylic acids such as acrylic acid.

(Poly) alkylene glycols such as triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate, etc. Di (meth) acrylates; polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate; triethylene glycol dimaleate, polyethylene glycol (Poly) alkylene glycol dimaleates such as dimaleate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acrylate Xylpropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- ( Unsaturated sulfonic acids such as (meth) acryloxybutyl sulfonate, (meth) acrylamide methyl sulfonic acid, (meth) acrylamide ethyl sulfonic acid, 2-methylpropane sulfonic acid (meth) acrylamide, styrene sulfonic acid, and monovalents thereof Metal salts, divalent metal salts, ammonium salts and organic ammonium salts; amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms such as methyl (meth) acrylamide; styrene, α-methylstyrene, vinyl Vinyl aromatics such as toluene and p-methylstyrene; 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate, etc. Alkanediol mono (meth) acrylates; dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like.
Unsaturated amides such as (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; unsaturated cyanides such as (meth) acrylonitrile and α-chloroacrylonitrile Unsaturated esters such as vinyl acetate and vinyl propionate; aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminobromyl (meth) acrylate , Unsaturated amines such as dibutylaminoethyl (meth) acrylate and vinylpyridine; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; (meth) allyl alcohol, glycidyl (meth) allyl ether, etc. Allyls; polydimethyl Roxanpropylaminomaleamic acid, polydimethylsiloxane aminopropylaminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropyleneaminomaleamic acid), polydimethylsiloxane -(1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1- Siloxane derivatives such as propyl-3-methacrylate).
N-vinylsuccinimide, N-vinylcarbazole, 1-vinylimidazole, N-vinylcaprolactam, N-vinyloxazolidone, N-vinylpyrrolidone, N-vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide, N-vinyl compounds such as N-methyl-N-vinylacetamide.
Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether.

In the polymerization method of the polyalkylene glycols, it is preferable to polymerize the monomer component using a polymerization initiator. The polymerization can be performed by a method such as polymerization in a solvent or bulk polymerization. The solution polymerization can be carried out batchwise or continuously, and the solvent used in that case is not particularly limited. For example, water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol; benzene, toluene, xylene, Aromatic or aliphatic hydrocarbons such as cyclohexane and n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone; cyclic ether compounds such as tetrahydrofuran and dioxane. When maleic anhydride is used as the maleic monomer, aromatic or aliphatic hydrocarbons such as benzene, toluene, xine, cyclohexane, and n-hexane are used to avoid cleavage of the acid anhydride group; acetic acid It is preferable to use an inert solvent such as an ester compound such as ethyl; a ketone compound such as acetone or methyl ethyl ketone. On the other hand, when maleic acid (salt) or the like is used as the maleic monomer, it is preferable to use at least one selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms. It is more preferable to use water as a solvent because the solvent removal step can be omitted.

When the aqueous solution polymerization is performed, a water-soluble polymerization initiator, for example, a persulfate such as ammonium persulfate, sodium persulfate, or potassium persulfate; hydrogen peroxide; 2,2′-azobis is used as the radical polymerization initiator. Azoamidine compounds such as 2-methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, 2-carbamoylazoisobutyronitrile, etc. Water-soluble azo initiators such as azonitrile compounds can be used. In this case, Fe (II) salts such as alkali metal sulfites such as sodium hydrogen sulfite, metabisulfites, sodium hypophosphite and molle salts, hydroxymethanesulfine Acid sodium dihydrate, hydroxylamine hydrochloride, thiourea, L-ascorbic acid (salt), Accelerator such as Rubin acid (salt) (reducing agent) can be used in combination. Among them, a combination of hydrogen peroxide and an organic reducing agent is preferable. As the organic reducing agent, L-ascorbic acid (salt), L-ascorbic acid ester, erythorbic acid (salt), erythorbic acid ester, and the like are preferable. is there. These radical polymerization initiators and accelerators (reducing agents) may be used alone or in combination of two or more.

In addition, when performing solution polymerization using a lower alcohol, aromatic or aliphatic hydrocarbon, ester compound or ketone compound as a solvent, or when performing bulk polymerization, for example, as a radical polymerization initiator, benzoyl peroxide, lauroyl Peroxides such as oxide and sodium peroxide; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azo compounds such as azobisisobutyronitrile can be used. In this case, an accelerator such as an amine compound can be used in combination. Furthermore, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from the above-mentioned radical polymerization initiator or a combination of a radical polymerization initiator and an accelerator. In addition, although superposition | polymerization temperature is suitably determined with the solvent and polymerization initiator to be used, it is normally performed within the range of 0-150 degreeC.

In the above polymerization, the method for charging each monomer into the reaction vessel is not particularly limited, for example, a method in which the entire amount is initially charged into the reaction vessel; a method in which the entire amount is divided or continuously charged into the reaction vessel; Any of a method in which the reaction vessel is initially charged and the remainder is divided or continuously charged into the reaction vessel may be used. The radical polymerization initiator may be charged into the reaction vessel from the beginning, may be dropped into the reaction vessel, or may be combined according to the purpose.

In the above polymerization, a chain transfer agent can be used to adjust the molecular weight of the obtained (co) polymer. The chain transfer agent is not particularly limited. For example, thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, and 2-mercaptoethanesulfonic acid; 2 such as isopropyl alcohol Secondary alcohols: Phosphorous acid, hypophosphorous acid and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, nitrous acid, metabisulfite and salts thereof (sodium sulfite, hydrogen sulfite) Known hydrophilic chain transfer agents such as lower oxides of sodium, sodium nithionite, sodium metabisulfite, and the like and salts thereof can be used. In addition, the use of a hydrophobic chain transfer agent is effective in improving the viscosity of the concrete composition. Hydrophobic chain transfer agents include 3 carbon atoms such as butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 3-mercaptopropionate, etc. It is preferable to use a thiol chain transfer agent having the above hydrocarbon group. Two or more chain transfer agents can be used in combination, and a hydrophilic chain transfer agent and a hydrophobic chain transfer agent may be used in combination. Furthermore, in order to adjust the molecular weight of the (co) polymer, it is also effective to use a monomer having a high chain transfer property such as (meth) allylsulfonic acid (salt) as a monomer component.

In the above polymerization, in order to obtain a copolymer having a predetermined molecular weight with good reproducibility, it is necessary to allow the polymerization reaction to proceed stably. Therefore, in the case of solution polymerization, dissolved oxygen at 25 ° C. in the solvent used. The concentration is preferably in the range of 5 ppm or less. More preferably, it is the range of 0.01-4 ppm, More preferably, it is the range of 0.01-2 ppm, Most preferably, it is the range of 0.01-1 ppm. In addition, when performing nitrogen substitution etc. after adding a monomer to a solvent, it is suitable to make the dissolved oxygen concentration of the system | strain containing a monomer into the said range.

The adjustment of the dissolved oxygen concentration of the solvent may be performed in a polymerization reaction tank, or a solution in which the amount of dissolved oxygen is adjusted in advance may be used. For example, the following (1) ) To (5).
(1) After pressure-filling an inert gas such as nitrogen in a sealed container containing a solvent, the partial pressure of oxygen in the solvent is lowered by lowering the pressure in the sealed container. You may reduce the pressure in an airtight container under nitrogen stream.
(2) The liquid phase portion is vigorously stirred for a long time while the gas phase portion in the container containing the solvent is replaced with an inert gas such as nitrogen.
(3) An inert gas such as nitrogen is bubbled in the solvent in the container for a long time.
(4) The solvent is once boiled and then cooled in an inert gas atmosphere such as nitrogen.
(5) A static mixer (static mixer) is installed in the middle of the pipe, and an inert gas such as nitrogen is mixed in the pipe for transferring the solvent to the polymerization reaction tank.

The (co) polymer obtained by the above polymerization method is used as it is as a main component of a dispersant or the like, but may be used by adjusting the pH range as necessary. It is preferable to adjust to a pH range of weak acid or higher. More preferably, it is pH 4 or more, more preferably pH 5 or more, particularly preferably pH 6 or more. On the other hand, the copolymerization reaction in an aqueous solution may be carried out at a pH of 7 or more. In that case, however, the polymerization rate decreases, and at the same time, the copolymerizability deteriorates and the dispersion performance decreases. It is preferable to carry out a copolymerization reaction in a range. More preferably, it is less than pH 6, more preferably less than pH 5.5, and particularly preferably less than pH 5. Therefore, it is preferable to adjust to a higher pH by adding an alkaline substance after carrying out the copolymerization reaction at a low pH. In a preferred embodiment, for example, after carrying out the copolymerization reaction at a pH of less than 6, the alkaline substance is added. A method of adding and adjusting to pH 6 or higher, a method of adding an alkaline substance after carrying out a copolymerization reaction at a pH of less than 5 and adjusting the pH to 5 or more, a pH of 6 or less after carrying out a copolymerization reaction at a pH of less than 5 The method of adjusting above is mentioned. The pH can be adjusted using, for example, an inorganic salt such as a monovalent metal or divalent metal hydroxide or carbonate; ammonia; an alkaline substance such as an organic amine. When pH needs to be lowered, especially when pH adjustment is required during polymerization, phosphoric acid, sulfuric acid, nitric acid, alkyl phosphoric acid, alkyl sulfuric acid, alkyl sulfonic acid, (alkyl) benzene sulfonic acid The pH can be adjusted using an acidic substance such as phosphoric acid, and among these acidic substances, phosphoric acid is preferred because of its pH buffering action. After the reaction is complete, the concentration can be adjusted if necessary.

The mass average molecular weight of the (co) polymer is not particularly limited. For example, when used as the main component of the dispersant, it is 1000 in terms of polyethylene glycol by gel permeation chromatography (hereinafter also referred to as “GPC”). It is preferably ˜500,000. More preferably, it is 5000-300000, More preferably, it is 10,000-150,000. By selecting such a range of the weight average molecular weight, higher dispersion performance is exhibited.

When the (co) polymer is used for various applications such as a dispersant, an antifoaming agent can also be contained. In this case, the antifoaming agent may be added after the production of the polymer, or may be added before the polymerization starts or during the polymerization. The addition ratio is preferably 0.0001 to 10% by mass with respect to 100% by mass of the total mass of the polymer.
Examples of the antifoaming agent include polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene 2 -Polyoxyalkylene alkyl ethers such as ethyl hexyl ether and oxyethyleneoxypropylene adducts of higher alcohols having 12 to 14 carbon atoms; polyoxyalkylene (alkyl) such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether Aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl-1-butyl Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohol such as n-3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate; polyoxyethylene Polyoxyalkylene sorbitan fatty acid esters such as sorbitan monolaurate and polyoxyethylene sorbitan trioleate; polyoxyalkylene alkyl (aryl) ether sulfate such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenyl ether sulfate Ester salts; polyoxyalkylene alkyl such as polyoxyethylene stearyl phosphate Phosphoric acid esters; polyoxypropylene polyoxyethylene laurylamine (propylene oxide 1-20 mol addition, ethylene oxide 1-20 mol addition product, etc.), cured beef tallow amine added with alkylene oxide (propylene oxide 1-20 mol addition, Polyoxyalkylene alkylamines such as ethylene oxide 1-20 mol adducts, etc .; one or more polyoxyalkylene amides can be used.

When the above (co) polymer is used, it may be used in the form of an aqueous solution, or after neutralization with a divalent metal hydroxide such as calcium or magnesium after polymerization, And then dried or supported on an inorganic powder such as silica-based fine powder, or dried and solidified into a thin film on a support using a drum-type drying device, a disk-type drying device or a belt-type drying device. The powder may be used after being pulverized.

The polyalkylene glycols of the present invention satisfy the above characteristics (1) and / or (2), but preferably satisfy both the above characteristics (1) and (2). Therefore, it is one of the preferred embodiments of the present invention that the polymerizable polyalkylene glycol satisfies the above characteristics (1) and (2).
The polyalkylene glycols of the present invention are characterized in that a high-purity polyalkylene glycol mono (meth) acrylate is obtained by performing a reaction using the solid acid catalyst and performing catalyst separation. Further, it is characterized in that polyalkylene mono (meth) acrylate having higher purity than the residue obtained by distillation is obtained. Since the polyalkylene glycols of the present invention use a solid catalyst, the following effects can be obtained. (1) In general, a catalyst containing a metal can be easily separated from a reaction solution by a simple method such as filtration or centrifugation. (2) For this reason, it is not necessary to add water, an organic solvent, or the like for extraction, and it is not necessary to remove the extraction solvent by a method such as distillation. (3) In general, heating in a state containing a metal may cause modification of the target product. However, since the catalyst can be easily removed from the reaction solution as described above, a high-purity target can be obtained. You can get things. The modification of the target product referred to here means generation of an oxide by oxidation reaction, discoloration and coloring, generation of a polymerizable dimer by disproportionation, generation of a polymer, and the like. The polyalkylene glycols of the present invention preferably have a metal content of 50 ppm or less. More preferably, it is 10 ppm or less, More preferably, it is 100 ppb or less. When the metal content is reduced as described above, the generation of peroxide can be suppressed, so that the polymerizability can be stabilized and the polymer can be polymerized.
In addition to these, it is preferable that the hue (APHA value) Hazen is 40 or less. The hue is preferably Hazen 5 to 35. More preferably, it is 10-20.
As the hue (APHA value) is reduced as described above, the coloring of the resin can be sufficiently reduced. For example, it is suitable as a resin for optical materials described later, and is used for white cement and the like. It will be useful. Thus, it is one of the preferred embodiments of the present invention that the polymerizable polyalkylene glycols have a hue (APHA value) of 1 to 40.
Hue can be measured based on the chemical product color test method of JIS K 0071-1 (1998) -Hazen unit color number (platinum-cobalt scale). The APHA value is a value based on this standard. The metal content can be measured by a commercially available high frequency inductively coupled plasma (ICP) analyzer.

The polymerizable dimer means a crosslinkable compound having two or more double bonds in the molecule. When the polymerizable dimer is contained as an impurity in the polyalkylene glycol, a cross-linked structure is formed when the polyalkylene glycol is polymerized, and the gel is easily gelled, which causes a decrease in dispersion performance.
Therefore, among the crosslinkable compounds having two or more double bonds in the molecule, it is particularly necessary to reduce the crosslinkable compounds having one double bond at each of both ends of the molecule. Examples of the crosslinkable compound having one double bond at each end of the molecule include diesters and di (alkyl) ethers.
Examples of the diesters include crosslinkable diester compounds produced as a by-product by reaction of the unsaturated initiator with the polyalkylene glycols that are the object of the present invention. Examples of the di (alkyl) ethers include di (meth) allyl ether and vinyl ether-containing compounds. An ether compound in which two molecules of the polyalkylene glycol are combined to form a dimer, an ether compound in which two molecules of the active hydrogen compound are combined to form a by-product, and the polyalkylene glycols and the active hydrogen compound It is also necessary to reduce the ether compound and the like produced by the reaction.
The content of the polymerizable dimer is preferably measured by a high performance liquid chromatography method. For example, it is preferable to measure in accordance with the following measuring device and conditions.
Equipment: CCP & 8020 series manufactured by TOSOH, Capsclpak C18 manufactured by Shiseido
UG120 column (φ4.6mm × 150mm)
Condition: Column temperature 40 ° C
Eluent: H ₂ O / CH 3 CN = 65/35 (volume ratio)
Flow rate: 1 ml / min The polyalkylene glycols of the present invention preferably have a polymerizable dimer content of 0.001 to 10% by weight. More preferably, it is 0.001 to 3.5 weight%. More preferably, it is 0.01 to 1.0% by weight. Particularly preferred is 0.01 to 0.7% by weight.
By reducing the content of the polymerizable dimer as described above, the molecular weight distribution can be narrowed and the gelation of the polymer can be prevented, so that the performance of the cement dispersant is improved. Is possible. The polyalkylene glycols of the present invention are those in which the above polymerizable dimer is sufficiently reduced, and have high transparency and sufficient dispersibility. The above polyalkylene glycols can be produced by the production method of the present invention.
Therefore, it is one of the preferred embodiments of the present invention that the polyalkylene glycols of the present invention are polyalkylene glycols produced by the production method of the present invention.

The polymerizable polyalkylene glycols are obtained by reacting an unsaturated initiator with an alkylene oxide, and the number of moles of alkylene oxide added to 1 mol of the unsaturated initiator in 100% by mass of the polymerizable polyalkylene glycols. It is also one of the preferred embodiments of the present invention to contain 2% by mass or more of the compound having a mol of 15 mol or more and 20 mol or less.
Thus, it is possible to obtain a dispersant exhibiting higher dispersion performance by including 2% by mass or more of the alkylene oxide added in an amount of 15 mol to 20 mol with respect to 1 mol of the unsaturated initiator. Become. The polymerizable polyalkylene glycols of the present invention are not merely those having a large molecular weight, and the content of the polymerizable dimer is sufficiently reduced as described above, and relative to 1 mol of the unsaturated initiator. By containing 2% by mass or more of alkylene oxide having an addition mole number of 15 mol or more and 20 mol or less, gelation does not easily occur even when polymerized, and high dispersion performance is exhibited. This is because the function as a dispersant is considered to be effective when the added mole number is in the range of 15 to 20.
It is preferable to contain 2% by mass or more of a polymerizable polyalkylene glycol having 15 to 20 mol of alkylene oxide added to 1 mol of the unsaturated initiator. More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more, Most preferably, it is 25 mass% or more, Most preferably, it is 50 mass% or more.

In addition, the polyalkylene glycol of this invention may add another additive in the range which does not prevent the effect of invention. For example, as a polymerization inhibitor, methoquinone (hydroquinone monomethyl ether), BHT (2,6-di-tert-butylhydroxytoluene), BHA (di-tert-butylhydroxyanisole), α-tocopherol, β-tocopherol, γ-tocopherol Hydroquinone and the like are preferable. Moreover, you may use combining these. Metoquinone (hydroquinone monomethyl ether) and BHT (2,6-di-tert-butylhydroxytoluene) are preferred.

Since the polyalkylene glycols of the present invention have a low content of diols such as polyethylene glycol, polymerizable dimers such as diesters, metal content, water, and color-causing substances, the polyalkylene glycols of the present invention A good quality resin can be obtained as a raw material. More specifically, the polyalkylene glycols of the present invention include a transparent resin, a plastic optical material, a urethane resin, a UV curable resin, a resist material, an electrochemical device material (secondary battery, a capacitor, etc.), a wood material primer, It can be used as a raw material for a curable resin composition raw material (paint, etc.), an adhesive for dental technology, and the like. As described above, the polyalkylene glycols of the present invention are used as raw materials for resins that can be used in various applications by polymerization.
That is, a polyalkylene glycol polymer obtained by polymerizing a monomer component essentially containing the polymerizable polyalkylene glycol of the present invention is also one aspect of the present invention.
In addition, a method of using the polyalkylene glycol polymer in which the polyalkylene glycol polymer is used for a dispersant, a cement admixture, a urethane resin, or an optical material is also one aspect of the present invention.
That is, a dispersant, a cement admixture, a urethane resin, or a resin for optical materials comprising the polyalkylene glycol polymer is also a preferred embodiment of the present invention.

The method for producing polyalkylene glycols of the present invention has the above-described structure and can be used as various industrial chemical raw materials. Particularly, those having an unsaturated bond are those that form polymers used in various applications. It is a production method capable of obtaining polyalkylene glycols useful as a monomer, etc., and the addition of alkylene oxide to an unsaturated initiator is efficiently performed, and the content of by-products is suppressed, This is a method by which polyalkylene glycols can be produced.
Further, the polyalkylene glycols of the present invention have the above-described configuration, have a low impurity content, and have a good hue, so various polymer materials, concrete admixtures, adhesives, adhesives, paints, cosmetic additives are added. It is suitable as a production raw material that can be used for various uses such as various dispersants such as a dispersant and an inorganic dispersant.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Note that “%” means “mass%” unless otherwise specified.

[Conversion rate calculation method]
After the production of polyalkylene glycols (after the reaction), hydroxyethyl methacrylate was quantified by gas chromatography, and the conversion rate was calculated based on the weight ratio charged.
Apparatus: GC-15A manufactured by Simadzu, Capital column DB-1 manufactured by J & W (0.53 mmφ × 30 m)
Conditions: Hold at 40 ° C. for 5 min, 10 ° C./min temperature rise, hold at 300 ° C. for 5 min [moisture content measurement]
Measurement was carried out using the following apparatus.
Apparatus: MK-510, manufactured by Kyoto Electronics Industry Co., Ltd. (KEM)
Standard sample: Karl Fischer SS manufactured by Mitsubishi Chemical Corporation
(Hue measurement)
About 30 cc of a sample was collected and measured based on the color test method of chemical products of JIS K0071-1 (1998) -Hazen unit color number (platinum-cobalt scale).
(Measurement of content of polymerizable dimer)
Measurement was performed using the following measuring apparatus and measurement conditions.
Equipment: CCP & 8020 series manufactured by TOSOH, Capsclpak C18 manufactured by Shiseido
UG120 column (φ4.6mm × 150mm)
Conditions: The column temperature was 40 ° C., and the eluent was H ₂ O / CH ₃ CN = 65/35 (volume ratio) and analyzed at a flow rate of 1 ml / min.
[Metal content measurement]
The metal content was measured by the ICP method.
Device: Rigaku CIROS-120

Example 1 (HEMA-3EO addition reaction)
In a SUS autoclave (1,000 cc), 329.7 g (2.53 mol) of hydroxyethyl methacrylate (HEMA), 0.1648 g of methoquinone, and silica alumina (N633HN manufactured by JGC Chemical Co., Ltd., calcined at 350 ° C. for 4 hours) 33 .2 g was charged at room temperature, and the container was sealed and then replaced with nitrogen. After raising the temperature inside the reaction vessel to 70 ° C., a total of 449.1 g (10.2 mol) of ethylene oxide was added over 4.7 hours. After further aging for 1.3 hours, the mixture was cooled and the remaining ethylene oxide was purged. The reaction solution obtained after opening the pressure was filtered under reduced pressure using 4 μ filter paper, and as a result, a colorless and transparent liquid was obtained.
(Light boiling cut)
This liquid was transferred to a 1 L glass container, and vacuum distillation was performed at a bath temperature of 80 ° C. and 20 mmHg to obtain 570.7 g of liquid at the bottom. This obtained polyalkylene glycol (1).
(result of analysis)
The obtained polyalkylene glycol (1) was analyzed. The water content was measured by Karl Fischer method, the hue was Hazen method, the polymerizable dimer content and the polyethylene glycol content were measured by high performance liquid chromatography. The measurement apparatus etc. used what was shown above.
The water content was 0.07% by mass, and the hue APHA was less than 10, although Hazen was not less than 10. Moreover, 0.14 mass% of polymerizable dimers and metal were not detected. Moreover, it was 88.0 mass% of active ingredients. The active ingredient mentioned here refers to a polyethylene glycol compound having a methacrylic ester structure at the terminal.
Moreover, it was 6.6 when pH of the aqueous solution (5 wt%) of obtained polyalkylene glycol (1) was measured at 25 degreeC.

Example 2
(Preparation of silica-supported Al catalyst for HEMA-9EO synthesis)
After 37.1 g of aluminum nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 1 L of water, 200.0 g of silica (CAriACT • Q-6 manufactured by Fuji Silysia) was charged at room temperature and stirred. Thereafter, water was distilled off under reduced pressure at 70 ° C. with stirring, and the obtained white powder was dried at 120 ° C. for 8 hours under a flow of dry air, and then calcined at 550 ° C. for 4 hours to obtain a silica-supported Al catalyst. .
(HEMA-9EO addition reaction)
In a 10 mL autoclave, hydroxyethyl methacrylate (HEMA, 1494.7 g, 11.48 mol), p-methoxyphenol (1.50 g, 121 mmol) and the above catalyst (silica-supported Al catalyst, 150.65 g) were charged in a greenhouse. After adjusting the phase partial oxygen concentration to 2%, the gauge pressure was set to 1.0 kg · cm ⁻² . While stirring, ethylene oxide (EO, 4572.2 g, 103.79 mol) was injected at a temperature of 70 ° C. and reacted for 19.2 hours. After the reaction, 5963.8 g of the reaction solution was recovered. When this liquid was analyzed by gas chromatography, the conversion rate of the raw material HEMA was 95.9%. As a result of analysis by liquid chromatography, the content of the polymerizable dimer was 0.29 wt%, and as a result of the Karl Fischer (KF) method analysis, the water content was 0.20 wt%.
(Light boiling cut)
Into a 1 L flask, 709.1 g of the reaction solution and 35.5 g of water were charged, and simple distillation was performed at a pressure of 20 mmHg and a bottom temperature of 25 to 80 ° C. As a result, polyethylene glycols (2) were obtained.
(result of analysis)
The polyalkylene glycols (2) obtained by removing light boiling components were analyzed. As a result of the analysis, 596.6 g of a purified solution having an active ingredient of 85.3 wt%, a polymerizable dimer content of 0.66 wt%, and a water content of 0.16 wt% was recovered. The component mentioned here refers to a polyethylene glycol compound having a methacrylic ester structure at the terminal. The hue (APHA) was not less than 10, but less than 20. No metal was detected.

Reference example 1
An autoclave was charged with 20.0 g of hydroxyethyl methacrylate, 0.026 g of hydroquinone and 0.20 g of tin chloride (SnCl4, manufactured by Wako Pure Chemical Industries, Ltd.) at room temperature, and then the gas phase portion was replaced with nitrogen gas, and the gauge pressure was changed. The pressure was 0.15 MPa. While stirring, 20.4 g of ethylene oxide (EO) was injected over 2 hours at a temperature of 50 ° C., and then aging was performed for 1.5 hours. As a result, polyethylene glycols (3) were obtained.
As a result of analyzing the obtained polyalkylene glycols (3), the polymerizable dimer content was 3.6% by mass. The amount of metal was 2243 ppm, Sn could be calculated from the charged amount. The hue (APHA) was 50.
Comparative Example 1
An autoclave was charged with 95.4 g of hydroxyethyl methacrylate, 0.42 g of benzoquinone, and 0.15 g of a double metal cyanide (DMC) catalyst at room temperature, the gas phase portion was replaced with nitrogen gas, and the system was depressurized. . While stirring, 49.1 g of ethylene oxide (EO) was added over 6.2 hours while maintaining the internal pressure at 0.1 MPa or less at a temperature of 100 ° C., but the reaction did not proceed and the feed of EO was interrupted. . The DMC catalyst was prepared on the basis of the examples of the open patent, Japanese Patent Laid-Open No. 8-104741.

Example 3 (HEMA-9EO)
As a monomer solution, 3.48 g of methacrylic acid (MAA), polyalkylene glycols (2) obtained in Example 2 (HEMA-9EO: ethylene oxide adduct of hydroxyethyl methacrylate, average ethylene oxide (EO) addition mole number 9) Was added to water to adjust the total amount to 64 g.
As an initiator solution, water was added to 0.1551 g of ammonium persulfate (APS) to adjust the total to 8 g. As a chain transfer agent solution, water was added to 0.3607 g of 3-mercaptophenylpropionic acid (MPA) to adjust the total to 8 g.
The monomer solution was charged into a 100 mL glass reaction vessel having a diameter of 35 mm and heated to 70 ° C. while stirring with a magnetic stirrer. Subsequently, an initiator solution and a chain transfer agent solution were simultaneously added to the reaction vessel to start the polymerization reaction, and the polymerization reaction was completed by maintaining at 70 ° C. for 2 hours.
Example 4 (HEMA-9EO)
Polymerization was conducted in the same manner as in Example 3 except that the amount of chain transfer agent (MPA) was changed to 0.1202 g.

Comparative Example 2
Polymerization was carried out in the same manner as in Example 3, except that the polyalkylene glycol (3) obtained in Reference Example 1 was used instead of the polyalkylene glycol (2). Since the content of the polymerizable dimer was large, Mw was extremely increased as shown in Table 1.
Comparative Example 3
Polymerization was carried out in the same manner as in Comparative Example 2 except that the polymerization was carried out by increasing the amount of chain transfer agent. As a result, the copolymer Mw was almost the same as in Example 3.
Comparative Example 4
Polymerization was carried out in the same manner as in Comparative Example 2 except that the polymerization was carried out with a reduced amount of chain transfer agent. As a result, gelation occurred during the polymerization. These results are shown in Table 1.

Table 1 will be described below. In Table 1, MPA is the said chain transfer agent, and the numerical value described in Table 1 is the quantity (g) used at the time of superposition | polymerization. Mw is a weight average molecular weight, and Mn is a number average molecular weight.

Example 5 Mortar Test Results <Mortar Formulation>
The mortar formulation was C / S / W = 550/1350/220 (g).
However, C, S, and W in the above formula mean the following.
C: Ordinary Portland cement (manufactured by Taiheiyo Cement)
S: ISO standard sand W: polymer, defoaming ion exchange aqueous solution <mortar experimental environment>
The experimental environment was 20 ° C. plus / minus 1 ° C., humidity 60% plus / minus 10%.
<Mortar kneading procedure>
Take 10.18 g of the 10% aqueous solution of the polymer obtained in Example 3, add 10 wt% of the antifoaming agent MA-404 (Pozoris product) to the polymer, and add 220 g of ion-exchanged water. And sufficiently homogeneously dissolved.
The mortar kneading procedure and flow value measurement procedure were based on JIS R5201 (1997). The mixer used was an N-50 mixer manufactured by HOBART equipped with a stainless steel heater (stirring blade).
<Mortar air volume measurement procedure>
About 200 mL of mortar was packed in a 500 mL Pyrex (registered trademark) measuring cylinder and pierced with a round bar having a diameter of 8 mm, and the container was vibrated to remove coarse bubbles. Further, about 200 mL of mortar was added to remove bubbles in the same manner, the weight was measured, and the amount of air was calculated from the weight and the density of each material.
<Molecular weight and molecular weight measurement conditions of copolymer>
Device: Waters Alliance (2605)
Analysis software: Waters Empower Professional + GPC option column: TSKgel guard column (inner diameter 6.0 × 40 mm) + G4000SWXL + G3000SWXL + G2000SWXL (each inner diameter 7.8 × 300 mm)
Detector: differential refractometer (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996)
Eluent: A mixture of acetonitrile / 50 mM sodium acetate ion exchange aqueous solution = 40/60 (vol%) adjusted to pH 6.0 by adding acetic acid Flow rate: 1.0 ml / min Column / Measurement temperature: 40 ° C.
Measurement time: 45 minutes Sample solution injection amount: 100 μl (eluent solution with sample concentration of 0.5 wt%)
GPC standard sample: Polyethylene glycol manufactured by Tosoh Corporation Mp = 272500, 219300, 107000, 50000, 24000, 11840, 6450, 4250, 1470 Calibration curve: cubic equation using Mp value of polyethylene glycol Analysis method: In the obtained RI chromatogram, the polymer was detected / analyzed by connecting the portions where the polymer was flat and stable in the baseline immediately before and after elution, with a straight line. However, when the monomer peak was measured to overlap the polymer peak, the polymer part and the monomer part were separated by vertical division at the most concave part of the overlapping part of the monomer and the polymer, and the molecular / molecular weight distribution of only the polymer part was measured. In addition, when a plurality of types of monomer peaks were detected, the monomer and polymer peaks were divided so that the monomer peak having the largest molecular weight was excluded. When oligomers higher than dimer were detected, they were included in the polymer part.

Comparative Example 5 Mortar Test Using the comparative copolymer of Comparative Example 2, a mortar test was conducted.
Comparative Example 6
A mortar test was conducted using the comparative copolymer of Comparative Example 3. These results are shown in Table 2.

Table 2 will be described below. In Table 2, “added amount / wt% vs. C” is the mass ratio (%) of the polymer to the normal Portland cement. The zero stroke flow value is an average value of the major axis of the mortar that spreads on the flow table when the flow cone is raised vertically and the diameter relative to 90 ° C., and the 15 stroke flow value is obtained after measuring the zero stroke flow value The average value of the diameter of the mortar that spreads after the flow table was vibrated up and down 15 times and the diameter relative to 90 ° C.

Example 6
Polyalkylene glycols (4) were prepared by adding methoquinone so as to contain 750 ppm of methoquinone as a polymerization inhibitor to the polyalkylene glycols obtained in Example 1. Water containing 1.5% by mass of V-50 (manufactured by Wako Co., Ltd., granule) as a polymerization initiator was charged with 5.0 g of the obtained polyalkylene glycol (4) in a glass test tube provided with a thermometer. 1.0 g was added and nitrogen bubbling was performed, followed by polymerization in an oil bath at 55 ° C. In 13 minutes, the temperature showed a maximum value of 82.3 ° C., indicating that the polymerization had proceeded. The obtained polymer was a colorless and transparent solid.

The flow value of the copolymer of the present invention of Example 5 is larger than that of the comparative copolymers of Comparative Examples 5 and 6, and the copolymer of the present invention has a dispersion performance as a cement dispersant. It turns out that it is excellent.

FIG. 4 is a diagram showing the molecular weight distribution of the polymer obtained in Example 3.

Claims (8)

The following characteristics (1) and / or (2);
(1) Polymerizable polyalkylene glycols satisfying that the polymerizable dimer content is 0.001 to 10% by weight and (2) the metal content is 50 ppm or less. The polymerizable polyalkylene glycol according to claim 1, wherein the content of the polymerizable dimer is 0.001 to 3.5% by weight. The polymerizable polyalkylene glycols satisfy the characteristics (1) and (2),
The polymerizable polyalkylene glycol according to claim 1 or 2, wherein the polymerizable dimer content is 0.001 to 3.5 wt%. The polymerizable polyalkylene glycols are
The polymerizable polyalkylene glycol according to any one of claims 1 to 3, wherein the hue (APHA value) is 1 to 40. The polymerizable polyalkylene glycols are obtained by reacting an alkylene oxide with an unsaturated initiator,
The polymer polyalkylene glycols contain 100% by mass of 2% by mass or more of an alkylene oxide added in an amount of 15 to 20 mol per mol of the unsaturated initiator. The polymerizable polyalkylene glycol according to any one of the above. A process for producing polyalkylene glycols by reacting an unsaturated initiator with an alkylene oxide,
The production method uses at least one solid acid catalyst selected from the group consisting of a crystalline metal oxide and an aluminum compound having a five-coordinate structure of aluminum. . A polyalkylene glycol polymer obtained by polymerizing a monomer component essentially comprising the polymerizable polyalkylene glycol according to any one of claims 1 to 5. A method for using a polyalkylene glycol polymer, wherein the polyalkylene glycol polymer according to claim 7 is used for a dispersant, a cement admixture, a urethane resin, or an optical material.

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