JPH0741554A - Production of carboxylated polymer - Google Patents

Abstract

PURPOSE:To effectively produce a carboxylated polymer which has unique functions, such as a high ion-exchange capacity, and is useful as a biodegradable detergent builder from a low-cost material. CONSTITUTION:The carboxylated polymer is produced by subjecting a hydroxyl compd. to catalytic oxidation in the presence of a specific catalyst compsn. to give a carboxyl monomer and polymerizing the monomer. The catalyst compsn. is a mixed supported catalyst and comprises the following: the first component which is at least one element selected from the group consisting of palladium, platinum, rhodium, and ruthenium; the second component which is at least one element selected from the group consisting of bismuth, tellurium, tin. lead, antimony, and selenium; and the third component which is at least one element selected from rare earth elements.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polymer having a carboxyl group. More specifically, it relates to a method for producing a polymer having a carboxyl group, which is useful as a builder for detergents, a neutralizer, a thickener, a raw material for a polymer, a raw material for a water-absorbing polymer, or the like.

[0002]

2. Description of the Related Art Polycarboxylic acids typified by copolymers with polyacrylic acid or maleic acid are used as a polymer having a carboxyl group for water-absorbing polymers and also for detergent builders. Although used, non-biodegradability is becoming a problem.
Monsanto Co., Ltd. of the United States conducts synthetic research on polycarboxylic acid salts (polyglyoxylic acid, Builder U), which is a biodegradable polymer, using expensive glyoxylic acid ester as a raw material, and discloses it in Japanese Examined Patent Publication No. 62-37044 (USP 4144226). There is. The builder U has an extremely high calcium-capturing ability and is excellent as a builder for detergents, but it has a problem in practicality because the raw material is expensive. Therefore, if a biodegradable polymer builder such as Builder U can be manufactured at low cost by using inexpensive raw materials, its ripple effect is immeasurable.

On the other hand, German Laid-Open Publication No. 2347538.
The publication describes a method of using a polyglycerin oxide obtained by oxidizing polyglycerin derived from glycerin which is an inexpensive raw material, as a biodegradable builder. However, since the degree of polymerization of polyglycerin is generally at most 10, the number of carboxyl groups in the polyglycerin oxide obtained by this method is small, and the function as a polycarboxylic acid, for example, the chelating ability is low, so that it is used for detergents. The performance as a builder is not satisfactory.

Further, JP-A-62-212423 and JP-A-62-201926 disclose that in the presence of a transesterification catalyst, high temperature (200 ° C. or lower) and reduced pressure (50 torr).
r or less), a method of dehydrating and condensing tartronic acid or its ester is described. However, under such conditions, decomposition of the produced polymer is likely to occur, so reaction is performed under mild conditions (normal temperature and normal pressure) to produce It is expected to develop a method for expressing a high Ca-capturing ability with almost no polymer decomposition.

[0005]

[Means for Solving the Problems] Considering such a situation,
The inventors of the present invention use glycerin, glyceric acid, ethylene glycol, propylene glycol, hydroxyacetone, lactic acid, a salt of glyceric acid or a salt of lactic acid, which are inexpensive raw materials, or tartronic acid, which is an oxide of glycerin, and tartronic acid. A decarboxylation decomposition product, glycolic acid which is an oxide of ethylene glycol, or a salt thereof is used as a raw material to carry out catalytic oxidation in the presence of a predetermined catalyst composition and an oxidizing agent to produce a monomer having a carboxyl group and a polymerization reaction. As a result of advancing the above, it was found that a polymer having a large amount of carboxyl groups was produced, and the present invention was completed.

That is, the gist of the present invention is to (1) to carry out catalytic oxidation of a hydroxyl group compound in the presence of the following catalyst composition and oxidizing agent to produce a monomer having a carboxyl group and polymerize the monomer. A method for producing a polymer having a carboxyl group having a characteristic, a catalyst composition: one or more elements selected from the group consisting of palladium, platinum, rhodium, and ruthenium as a catalyst first component, bismuth, tellurium, tin, lead, One or more elements selected from the group consisting of antimony and selenium as the catalyst second component, one or more elements selected from rare earth elements as the catalyst third component, (a) catalyst first component and catalyst second component ( (B) catalyst first component and catalyst third component (c) catalyst first component, catalyst second component and catalyst third component,
Or (d) a supported catalyst consisting of only the first component of the catalyst, (2) the hydroxyl compound is glycerin, glyceric acid or a salt of glyceric acid, wherein the production method according to (1), ) The method according to (1) above, wherein the hydroxyl compound is tartronic acid or a salt thereof, (4) The hydroxyl compound is ethylene glycol, glycolic acid or a salt of glycolic acid. 1) The production method described in 1), 5) The hydroxyl compound is propylene glycol, hydroxyacetone, lactic acid or a salt of lactic acid, 6) The production method described in 1), 6) The hydroxyl compound is glycerin and ethylene glycol. (7) The catalyst first component of the catalyst composition of (7) above is a mixture of Arm and platinum catalyst second component is bismuth and / or tellurium,
The production method according to any one of (1) to (6) above, wherein the third component of the catalyst is cerium and / or lanthanum, (8) the reaction is carried out in a fixed bed reactor filled with the catalyst composition. (1) The production method according to any one of (6), (9) The above-mentioned (8), wherein the catalyst composition is diluted with 0.5 to 10 parts by weight of a diluent per 1 part by weight and filled. (10) The weight average molecular weight of the polymer having a carboxyl group is 500 to 1, as determined by gel filtration chromatography.
(1) The production method according to any one of (1) to (9) above, and (11) the polymer having a carboxyl group has a calcium capturing ability of 100 to 600 mg-CaCO ₃ / g. The manufacturing method according to any one of (1) to (10) above.

The reaction scheme of the present invention will be described below with reference to FIG. First, the polymerization in the present invention is mainly oxidative dehydrogenation polymerization. That is, active hydrogen at the polymerization site of a precursor of a monomer (hereinafter sometimes abbreviated as a monomer precursor) which is a reaction raw material catalytically reacts with oxygen supplied from the bulk on the catalyst surface to generate water. That is, a monomer having an aldehyde group or a carbonyl group directly involved in the polymerization (hereinafter sometimes abbreviated as a monomer) is generated on the catalyst surface, and the polymerization reaction of the monomer proceeds.

As the monomer precursor in the present invention,
(1) Glycerin, glyceric acid, or a salt of glyceric acid, (2) tartronic acid or a salt thereof, (3) ethylene glycol, glycolic acid, or a salt of glycolic acid,
(4) Propylene glycol, hydroxyacetone, lactic acid or a salt of lactic acid is used.

Glyceric acid and tartronic acid are oxides of glycerin, and glycolic acid is a decarboxylated decomposition product of tartronic acid or an oxide of ethylene glycol. These are glycerin, as shown in the reaction scheme of FIG.
Glycerin, ethylene glycol, and propylene glycol are the cheapest initial raw materials because they are sequentially produced by catalytic oxidation of ethylene glycol and propylene glycol.

Further, as the monomers directly involved in the polymerization, tartronic aldehyde, ketomalonic acid, glyoxylic acid, pyruvic acid or their obtained by catalytic oxidation of glyceric acid, tartronic acid, glycolic acid, lactic acid or their salts, respectively. Although they are salts, these monomers may be those synthesized by a separate synthesis method.

Although the reaction mechanism of further polymerizing the monomers produced by using these monomer precursors to produce the polymer of the present invention has not been completely elucidated, the conventional knowledge about catalytic oxidation is shown in FIG. Is estimated as. That is, the reaction of the present invention is as follows: (1) an oxidation reaction part for producing a monomer precursor and a monomer;
It is roughly classified into three parts, (2) a polymerized portion into a polymer having a carboxyl group, and (3) a decarboxylation decomposition portion of the polymer.

As an oxidation reaction part for producing a monomer precursor and a monomer, for example, catalytic oxidation of glycerin starts and glyceric acid is produced via glyceraldehyde. Glyceric acid is further oxidized to form tartronic aldehyde, one of the monomers in the present invention. Alternatively, the tartronic aldehyde is further oxidized to form tartronic acid, which in turn forms one of the monomers in the present invention, ketomalonic acid.
In addition, tartronic acid produces glycolic acid by decarboxylation and further produces glyoxylic acid, which is one of the monomers in the present invention.

When ethylene glycol is used as a starting material, it is oxidized to glycolic acid through the corresponding aldehyde, which is the same as that produced by decarboxylation of tartronic acid. Glycolic acid is further oxidized to produce the monomer glyoxylic acid.

When propylene glycol is used as a starting material, the monomer pyruvic acid is produced via hydroxyacetone or lactic acid.

The polymerized portion into the polymer having a carboxyl group is roughly classified into the following five routes ((a) to (e)) corresponding to the above oxidation reaction route.

(A) In the case of using tartronic acid or a salt thereof as a monomer precursor, in this route, a polymerization reaction using ketomalonic acid as a monomer proceeds while the secondary hydroxyl group undergoes oxidative dehydrogenation ( Route 1). As a result, polyketomalonic acid (I) or a salt thereof is produced as a polymer.

(B) when glycerin, glyceric acid, or a salt of glyceric acid is used as a monomer precursor,
In this route, tartronic acid aldehyde or its salt, which is a monomer, is generated by the oxidation of the primary hydroxyl group of glyceric acid or its salt, which is the monomer precursor immediately before it, and the aldehyde group is converted into an ether bond to proceed the polymerization reaction. (Route 2). It is presumed that as a result, polytartronic acid aldehyde (III) or a salt thereof is produced as a polymer, and the secondary hydroxyl group is further oxidized to produce polymesoxalaldehyde acid (IV) or a salt thereof which is a polymer.

(C) Tartronic acid or its salt itself undergoes decarboxylation as described above to become glycolic acid or its salt. In this case, glycolic acid or a salt thereof which is a monomer precursor is further oxidized to proceed a polymerization reaction using glyoxylic acid or a salt thereof as a monomer (route 3). As a result, polyglyoxylic acid (II) or a salt thereof is produced as a polymer. Also, when ethylene glycol is used as a monomer precursor, polyglyoxylic acid (II) is similarly produced via glycolic acid and glyoxylic acid.

(D) A case where a carboxyl group-containing aldolcarboxylic acid (V) is produced via an aldol produced from glyceraldehyde (route 4). In this case, when the pH is 9 or higher and the reaction temperature is 50 ° C. or higher, it is easily generated, but it does not have biodegradability.

(E) In the case of using propylene glycol, hydroxyacetone, lactic acid or a salt of lactic acid as a monomer precursor, both produce polypyruvic acid (VI) via pyruvic acid (route 5).

As the decarboxylative decomposition portion of the polymers ((I) and (IV)), polyketomalonic acid (I), polymesoxalaldehyde acid (IV) or their salts are thermodynamically unstable. Therefore, it is presumed that it is easily decarboxylated at high temperature and decomposed into polyglyoxylic acid (II) or its salt. As is clear from such a reaction scheme, it is effective to suppress the disappearance of the carboxyl group due to the decarboxylation of the polymer as much as possible in order to produce a polymer having a large amount of the carboxyl group.

When a mixture of glycerin and ethylene glycol (for example, an equimolar mixture) is used as a starting material in the present invention, the same polymerization reaction proceeds according to Routes 1-3. In this case, a random copolymer of ketomalonic acid and glyoxylic acid is formed, as compared with the homopolymer of ketomalonic acid of Route 1, so that the copolymerization is good and the copolymer having good thermal stability is formed.

In the present invention, other raw materials such as glycerin, ethylene glycol, glyceric acid, tartronic acid or glycolic acid or salts thereof, for example, 1,
Polyhydric alcohols such as 2-propylene glycol and 1,3-propylene glycol, monohydric alcohols such as methanol, ethanol, propyl alcohol and isopropyl alcohol, or aldehydes such as formaldehyde and acetaldehyde can coexist. Also in this case, the polyhydric alcohol, the corresponding aldehyde or ketone which is an oxide of a monohydric alcohol, or the structural unit of the aldehyde is incorporated in the main chain of the polymer having a carboxyl group of the present invention (random copolymerization. ), Because of the thermodynamic stability of the produced polymer, it may be more effective as a polymer builder for detergent than when glycerin or its oxide is used as a starting material.

A platinum-based noble metal catalyst is effective as the catalyst composition used in the present invention. That is, one or more elements selected from the group consisting of palladium, platinum, rhodium, and ruthenium as the catalyst first component, one or more elements selected from the group consisting of bismuth, tellurium, tin, lead, antimony, and selenium. When the catalyst second component is one or more elements selected from rare earth elements and the catalyst third component is (a) a catalyst composition in which a catalyst first component and a catalyst second component are combined, (b) a catalyst first component And a catalyst composition in which a catalyst third component is combined, (c) a catalyst first component, a catalyst composition in which a catalyst second component and a catalyst third component are combined,
(D) A catalyst composition comprising only the catalyst first component is used.

Since the polymer having a carboxyl group of the present invention is thermally unstable and easily undergoes decarboxylation decomposition, it has a low temperature activity that allows oxidative polymerization to proceed under mild conditions. Noble metal catalysts are particularly effective.
However, other general oxidation catalysts, or oxidation by an inorganic or organic reagent (hydrogen peroxide, peracetic acid, etc.) and oxidative polymerization can also be used together.

The catalyst composition (a) in which the catalyst first component and the catalyst second component are combined is a preferable catalyst composition from the viewpoint of suppressing a decrease in catalyst activity due to oxygen poisoning. As the second component of the catalyst, bismuth, tellurium, tin,
Examples include lead, antimony, and selenium, with no particular limitation, antimony, bismuth, tellurium, and lead being particularly effective. For example, by complexing palladium with bismuth or tellurium, oxygen poisoning can be avoided and the oxidation reaction rate and the raw material conversion rate can be greatly improved. Also known as Lindlar catalyst is Pb / Pd /
CaCO ₃ catalyst can also be used as the catalyst of the present invention. Bismuth, tellurium and antimony are particularly useful.

In the present invention, since the polymerization reaction occurs concurrently with the production of the monomer, the effect of mass transfer is large, and as a result, the poisoning of the product derived from the produced polymer becomes an important problem. In order to promote mass transfer, three methods such as the combined use of a diluent described below, an outer layer supporting method, and control of the oxygen supply amount are proposed, but these are not direct methods. In order to suppress the poisoning of polymer-derived products at the atomic / molecular level, it is necessary to consider the physicochemical interaction between the produced polymer and the catalyst surface on the solid catalyst surface. Taking this into consideration, by eliminating the product poisoning derived from the produced polymer, it is possible to provide an unprecedented new method of applying the fixed bed reactor to the polymerization reaction.

[0028] As a concrete method, the idea of modifying the solid surface based on surface science is required. To achieve this effect, how to add the catalyst second component to the surface of the main catalyst element of the underlying layer. It is determined by whether or not it is possible to carry the highly dispersed particles effectively. This is determined by the physical properties of the base metal and the second component of the catalyst, but depends largely on the catalyst preparation method. The liquid phase equilibrium adsorption step supporting method used in the present invention is an extremely effective method and can be applied to mass production of catalysts.

From these findings, bismuth is particularly effective as the second component of the catalyst in the present invention. That is, bismuth has an ad-atom structure or an ad-layer structure on the surface of the main catalytic element typified by palladium or platinum, especially on the (111) plane, as compared with other catalyst second components.
It is considered that the structure is easy to take, and as a result, the adsorption of the produced polymer is greatly suppressed. This peculiarity of bismuth is that the adsorption amount of palladium or platinum alone is different from that of other catalyst second components such as tellurium and lead in the case of bismuth by measuring the CO adsorption amount of a two-component catalyst with palladium or platinum. It can be understood from the fact that the atomic ratio of Pd / Bi and Pt / Bi on the catalyst surface calculated from the dispersity of palladium or platinum and the surface area becomes 3 compared with the case of 1). .

The catalyst composition (b) in which the catalyst first component and the catalyst third component are combined is a combination of the catalyst third component from the viewpoint of achieving high-speed reactivity. Lanthanum, cerium, praseodymium, neobidium and the like are effective as the rare earth element. This is because the addition of the rare earth element, which is a basic element, causes the catalyst first component, such as palladium, to be in a highly dispersed state and imparts basicity to the catalyst surface, and as a result, high-speed reactivity is achieved. .

The catalyst composition (C) obtained by combining the catalyst first component, the catalyst second component and the catalyst third component is the above-mentioned (A).
It is a composition having both the properties of the catalyst composition of (2) and (2), and it is possible to obtain the effect of suppressing the decrease in catalyst activity due to oxygen poisoning and achieving high-speed reactivity. The catalyst composition is not particularly limited, but may be, for example, Ce.Bi.
・ Pd, Ce ・ Te ・ Pd, Se ・ Bi ・ Pd, Ce ・
Bi / Se / Pd, Ce / Bi / Te / Pd, Bi / P
Examples are t.Pd, Ce.Bi, Pt, Pd, and the like.
Among them, as the catalyst composition of (C), one in which the catalyst first component is palladium and platinum, the catalyst second component is bismuth and / or tellurium, and the catalyst third component is cerium and / or lanthanum is preferably used. . Further, as described above, in the present invention, by using a plurality of catalyst first components, in particular platinum as a co-catalyst, it is possible to reform to a low temperature active catalyst system. In particular, the four-component catalyst of Ce, Bi, Pt, and Pd has remarkable low-temperature activity and polymerization activity, and gives a polycarboxylic acid having a high Ca-capturing ability.

That is, Ce, Bi, P using two kinds of palladium and platinum in combination as the first catalyst component, bismuth as the second catalyst component and cerium as the third catalyst component.
The t-Pd four-component catalyst (catalyst composition (c)) is one of the high-performance low-temperature active catalysts in which the functions of the individual elements are highly complexed, and each element has the following functions. Ce: High dispersant for Pd and Pt, basicity imparting agent Bi: Oxygen poisoning inhibitor, product poisoning inhibitor Pt: Low temperature activator Pd: Primary hydroxyl group oxidizing ability (under basicity), mainly Catalytic element Bi / Pt: Secondary hydroxyl group oxidizing ability (under acidic condition)

This four-component catalyst comprises a composite of a Ce.Bi.Pd catalyst system which exhibits a primary hydroxyl group oxidizing ability and a Bi.Pt catalyst system which exhibits a secondary hydroxyl group oxidizing ability.
Therefore, for example, when glycerin is used as the starting material, the secondary hydroxyl group of tartronic acid produced by oxidation of the primary hydroxyl group of glycerin by the Ce.Bi.Pd catalyst is Bi.Pt.
The catalyst efficiently oxidizes and induces ketomalonic acid. Other components for palladium as the main catalyst element (Pt, B
The catalytic performance and the composition of the product can be largely controlled by the composition of i, Ce).

In the catalyst composition of the present invention, for example, palladium may be used alone as shown in the catalyst composition (d), but it is preferable to use a complex with the catalyst second component (catalyst composition ( A)), by combining with a catalyst third component (catalyst composition (b)), and further by combining with a catalyst second component and a catalyst third component (catalyst composition (c)), each catalyst component By using two or more of them in combination, the catalytic activity and selectivity can be dramatically improved.

The composition of the multi-component catalyst in the present invention is important and has a great influence on the catalytic activity. Therefore, the atomic ratio R1 of the bulk of the catalyst second component to the catalyst first component is
The following range is selected depending on the type of the second catalyst component. When the second catalyst component is selenium, R1 is 0.05 to 0.
3, preferably 0.05-0.10. If the second component of the catalyst is tellurium, bismuth, antimony, tin, R
1 is 0.05 to 1.5, preferably 0.1 to 0.5. When the second component of the catalyst is bismuth or tellurium, the optimum R1 is 0.2 and the surface structure is √3 × √3R.
It is estimated to have a 30 ° structure.

The amount of catalyst supported has an influence on the molecular weight of the polymer to be produced, and the lower the amount of carrier, the larger the molecular weight tends to be. The supported amount of the catalyst first component is usually 0.1 to 10% by weight, preferably 0.1 to 10%, based on the total supported catalyst (including the catalyst carrier).
-5% by weight, particularly preferably 0.1-3% by weight.
Among them, when the catalyst first component is palladium, when it is used alone or when it is used in combination with the catalyst second component and the catalyst third component, 0.5 to 10% by weight is preferable, and 1 to 6% by weight is more preferred. 0.5% by weight
If it is less than 10%, the reaction rate is slow, and if it exceeds 10% by weight, there is a problem in terms of cost. The supported amount of the second component of the catalyst is R1 described above.
From the viewpoint of catalytic activity, it is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight, and particularly preferably 0.5 to 3% by weight.

From the viewpoint of catalytic activity, the atomic ratio R2 of the bulk of the catalyst third component to the catalyst first component is usually 0.01 to.
1.0, preferably 0.05 to 0.5, more preferably 0.1 to 0.3. From the viewpoint of catalytic activity, the supported amount of the third component of the catalyst is usually 0.1 to 5% by weight, preferably 0.3 to 3% by weight, and particularly preferably 0.3 to 1.5% by weight.

In the catalyst composition of the present invention, the catalyst component is supported on the catalyst carrier in water by a conventional impregnation method, co-impregnation method, dipping method or co-precipitation method, and formalin, hydrazine, sodium borohydride, hydrogen, Lower alcohol (methanol, ethanol, glycerin, ethylene glycol, etc.)
It can be easily prepared by an ordinary method such as a reduction treatment by the above. In particular, when a catalyst component is supported on a catalyst carrier in an aqueous solution, a highly active catalyst can be easily obtained by carrying out a reduction treatment in water in a dispersed state without dehydrating and drying the catalyst precursor after the supporting.

In preparing the catalyst, an outer layer supporting (egg shell) in which the catalyst component is mainly supported on the outer layer of the catalyst carrier is used.
The type) is very effective for mass transfer because the reaction of the present invention is a polymerization reaction. As the effect of supporting the outer layer, bismuth, which is the second component of the catalyst used as the oxygen poisoning inhibitor, is particularly effective. This is because the bismuth has an ad-atom structure or an ad-atom structure as compared with other second catalyst components as described above.
It is considered that this is because the layer structure is easily obtained, and as a result, the adsorption of the produced polymer is largely suppressed.
This peculiarity of bismuth is different from that of other second catalyst components, tellurium and lead, in the case of bismuth by measuring the CO adsorption amount of a two-component catalyst with palladium, as compared with the case of palladium alone. It can also be understood from the drastic decrease as described above. The surface structure of the outer layer supported catalyst is
Although it largely depends on the preparation method, it basically depends on the surface properties of the main catalyst element, palladium, and the catalyst second component. When preparing the outer layer supported catalyst, the supporting time is also an important factor. In the liquid phase equilibrium adsorption stage supporting method used in the present invention, the supporting time should be 5 hours or less, preferably 2 hours or less.

Examples of the catalyst carrier include activated carbon, carbon black, calcium carbonate, silica, alumina, molecular sieve, asbestos, oxides of rare earth elements, and the like. Activated carbon having a high surface area, carbon black, alumina and silica are more preferable. preferable. Of these, activated carbon is particularly effective.

The activated carbon as a catalyst carrier used in the present invention may be derived from any raw material such as coconut shell, wood-based, coal-based, beet carbon-based or petroleum pitch-based materials.
In particular, coconut shells, woods and petroleum pitches having a low ignition residue or low ash content are effective. The activated carbon may be activated by either steam activation or chemical activation, but the steam activated product may be more effective as a carrier. The activated carbon as the catalyst carrier used in the present invention may be a commercially available product as it is, but may be used after a suitable pretreatment such as acid treatment to adjust the pore distribution or reduce the ash content. . As the commercially available granular and powdered activated carbon used in the present invention, those for general water treatment and water-soluble food refining are used, for example, granular Shirasagi series (WH, Sx, KL) and carborafine manufactured by Takeda Pharmaceutical Co., Ltd. Powdered activated carbon represented by Norit and granular activated carbon (RO
X, RAX, DARCO, C, ELORIT, etc.) and powder products (AZO
, PN, ZN, etc.), beaded activated carbon (BAC) manufactured by Kureha Chemical Co., Ltd.
Is mentioned.

Commercially available carbon black is also effective as a catalyst carrier when carrying out the reaction of the present invention,
For example, carbon black manufactured by Cavrac Co., Ltd. may be mentioned. However, the activated carbon and carbon black used in the present invention are not particularly limited to these activated carbon and carbon black.

The reaction temperature in the present invention is an extremely important factor and greatly affects the yield of the carboxyl group-containing polymer of the present invention. That is, in order to suppress the decomposition of the carboxyl group in the polymer by decarboxylation as much as possible, it is desirable to carry out the reaction in both the oxidation reaction section and the polymerization section of the reaction scheme as low as possible. The reaction temperature is -30 to
Although it can be carried out at 100 ° C., it is preferably -1 in order to suppress decarboxylation decomposition of the resulting polymer.
It is good to carry out at 0 to 60 ° C, more preferably 0 to 50 ° C, and particularly preferably 20 to 40 ° C.

That is, in the present invention, the lower the reaction temperature, the more easily the polymer is produced, and the by-product of sodium carbonate due to decarboxylation can be kept at several% or less. In addition, the optimum reaction temperatures for the monomer production step and the polymer production step are different, the former being 60 ° C. or lower and the latter being 30 ° C. or lower. . Furthermore, the low temperature is more advantageous in terms of the solubility of oxygen. Therefore, by using the low temperature active catalyst composition of the present invention, oxidative polymerization at room temperature can be efficiently progressed. The reaction time largely depends on the reaction temperature, the type of catalyst and its concentration, etc., but is usually preferably 1 to 30 hours.

In the reaction of the present invention, the step of producing a carboxyl group is carried out in an aqueous solution in a basic atmosphere, so that the produced polymer is generally a carboxylate. Therefore, it is preferable to set the concentration of the starting material in consideration of the solubility of the polymer formed at the applied reaction temperature. That is, the raw material concentration is usually preferably 1 to 80% by weight, and 5 to 50% by weight.
Is more preferable. If the raw material concentration is less than 1% by weight, the concentration of the obtained polymer is too low to be practical, and if it exceeds 80% by weight, the viscosity becomes too high and the mass transfer rate decreases.
As a result, the reaction rate is significantly reduced. Further, it is effective to use water as the reaction solvent from the viewpoint of productivity and efficiency.

In the reaction of the present invention, in order to proceed the synthesis of the monomer precursor and the monomer by the oxidation reaction and the oxidative polymerization reaction in a basic atmosphere, sodium hydroxide, potassium hydroxide and lithium hydroxide are required as the alkaline agents. Alkali metal hydroxides such as, amines such as monoethanolamine and diethanolamine,
Ammonia or the like is used.

In this case, the alkali excess serves as an important reaction factor to control the pH during the reaction and has a great influence on the structure and the degree of polymerization of the polymer of the present invention, and as a result, the Ca trapping ability as a builder for detergents. Have a great influence on.
For example, when the present invention is carried out by the following formula using glycerin as a starting material, sodium hydroxide, for example, as an alkaline agent is used in an amount twice that of glycerin.

[0048]

[Chemical 1]

As a result, sodium hydroxide is consumed up to polyketomalonic acid, but polyketomalonic acid is thermodynamically unstable, so that part of the carboxyl is easily decarboxylated. As a result, the glyoxylic acid skeleton is present in the polymer chain and excess sodium hydroxide is produced. This excess sodium hydroxide usually reacts with carbon dioxide that has been decarboxylated and decomposed to produce sodium hydrogen carbonate and sodium carbonate.

Therefore, when the starting material is glycerin, the equivalence ratio of sodium hydroxide charged to the glycerin is 0.
50 to 0.90 is preferable. Further, when ethylene glycol is used as a raw material, sodium hydroxide may be 0.5 equivalent or less, and when a mixture of glycerin and ethylene glycol is used as a raw material, sodium hydroxide may be used in consideration of the above points. Adjust the excess and adjust the pH of the aqueous reaction mixture.
Is preferably set so as to meet the conditions of the present invention.

The pH during the reaction is 7 to 1 at the time of producing the monomers when the polymers (I) to (IV) and (VI) are produced.
A base of 3 is preferable. On the other hand, the pH is 7 during polymerization.
The following is preferable, 6.0 to 2.5 is preferable, and 4.5 to 3.0 is particularly preferable.

On the other hand, when the polymer (V) is produced, the pH is preferably 9 to 14 during both monomer formation and polymerization. For example, by using a stirred tank reactor, polymerization products (I) to (IV)
In the case of producing (VI) and (VI), the pH is adjusted to 7 to 10 when the monomer production in the early stage of the reaction is main, and the pH is 7 or less when the polymerization reaction from the middle to the end of the reaction is main. It is preferable to control the feed rate of the agent and the oxidant.

Further, when the polymers (I) to (IV) and (VI) are produced using a fixed bed reactor, the monomer production mainly proceeds in the upper stage of the reaction tower and the polymerization occurs in the middle to lower stages of the reaction tower. The reaction mainly proceeds. In this case, the pH in the height direction of the reaction tower tends to greatly drop from the upper stage to the lower stage, and if necessary, the raw materials are supplied (alkaline agent, oxidizing agent) from a plurality of places in the middle stage of the reaction column, The pH of the outlet reaction mixture is preferably maintained at 6.5-2.0. On the other hand, when the polymer (V) is produced in a fixed bed reactor,
The outlet pH should be maintained at 9-14, preferably 10 or higher.

As the oxidant used in the present invention, pure oxygen, a mixed gas of pure oxygen and nitrogen, or air can be used, and air is economical although it is not particularly limited.

In the reaction of the present invention, a monomer which is an oxide of glycerin is mainly produced in the initial stage of the reaction, but a polymerization reaction using these monomers as a raw material proceeds in the middle stage to the final stage of the reaction. Therefore, the influence of mass transfer becomes significant in the process of polymer production, and as a result, the reactivity is greatly reduced due to the poisoning of the product, and therefore the oxygen supply amount may be insufficient. The amount of oxygen supplied should be increased with an increase in the molecular weight of the produced polymer, preferably not more than 3 times the equivalent amount, particularly preferably 0.5 to 2 equivalents.
It is better to set it to double. On the contrary, excessive increase of oxygen supply causes concomitant self-poisoning of the catalyst by oxygen.

The reaction in the present invention may be either a stirred tank reactor or a fixed bed reactor (trickle bed) depending on the form of the catalyst composition. When a fixed bed reactor is used, it is preferable to dilute the catalyst composition of the present invention with a diluent (reactive inert granules) and fill it. At this time, the catalyst composition is preferably diluted with 0.5 to 20 parts by weight of the diluent per 1 part by weight of the catalyst composition, and more preferably 4 to 15 parts by weight. By diluting with a diluent, the product poisoning resulting from the adsorption of the produced polymer is remarkably alleviated, and high productivity can be achieved. If it is not diluted with a diluent, the polymer stays on the surface of the catalyst to a large extent and the mass transfer rate is greatly reduced, which may cause a drastic decrease in the reaction rate.

Further, when the catalyst is packed in the fixed bed reactor as described above, the catalyst effective coefficient is increased by mixing the catalyst with the diluent, and as a result, the catalyst activity is increased by a factor of 2 to 3. Sometimes.

Any material may be used as the diluent as long as it does not adversely affect the reaction of the present invention, and examples thereof include porcelain, ceramics, polymer, glass or metal which is inert to the reaction. The particle size of the diluent is not particularly limited,
A particle size of 1/2 to 5 times that of the catalyst carrier is preferred.

The selection of the reactor is not particularly limited, but when the weight average molecular weight of the obtained polymer is 100,000 or more, and a highly viscous polymer is produced, the stirring tank reactor is preferably applied. . However, the weight average molecular weight is 500
In the case of about 100,000, a fixed bed reactor can be applied, and in this case, there is an advantage that the catalyst separation step can be simplified.

Next, regarding the reaction method in the present invention,
An example of using an aqueous glycerin solution as a starting material will be described. When carrying out the reaction using a stirred tank reactor, a glycerol aqueous solution is added to a stirred tank batch reactor equipped with a stirrer, a thermometer, a pH meter, a raw material gas (oxygen, air, etc.) introduction pipe, and a waste gas line. The catalyst composition is charged and set to a predetermined temperature, oxygen or air as an oxidant is bubbled into the solution, and an aqueous sodium hydroxide solution is continuously added so as to maintain a predetermined pH. By reacting for a predetermined time, the polymerization reaction proceeds along with the formation of the monomer by the oxidation reaction to produce the polymer having a carboxyl group of the present invention.

When a trickle bed type fixed bed reactor is used, for example, a molded catalyst composition is mixed with a diluent and charged into a reaction column, and the packed catalyst is added before carrying out the oxidation reaction of the present invention. It is preferable to carry out the reactivation treatment of. The reason for this is that the surface of the catalyst reduced during the preparation of the catalyst may be oxidized during the storage period and the catalytic activity may be reduced. In carrying out reactivation, 5 to 20% by weight of a hydroxyl compound such as glycerin or ethylene glycol, which is a starting material, is supplied without supplying a basic substance (sodium hydroxide, etc.), which is one of the starting materials for this reaction. It is achieved by supplying the aqueous solution to the reaction tower at a temperature of room temperature to 50 ° C. under air supply overnight. After the catalyst reactivation, the aqueous glycerin solution, the aqueous sodium hydroxide solution, and oxygen or air as an oxidizing agent may be supplied in a downward cocurrent flow from the top of the reaction tower. In this case, the liquid hourly space velocity based on the total of both raw material aqueous solutions is 0.5 to 0.01 h ⁻¹ , preferably 0.1.
Set to 2 to 0.05 h ^-1 .

The composition of the product is 40 to 60% by weight of the monomer and the polymer component is 60 to 40% by weight from 24 to 48 hours after the start of the raw material supply, but the monomer content decreases with the passage of time. In parallel with this, the Ca trapping ability of the polymer obtained in parallel with this greatly increases. The time course of the monomer content in the reaction product can be monitored by HPLC (High Performance Liquid Chromatography) and GPC (Gel Permeation Chromatography), but the baseline of HPLC is usually greatly disturbed by the formation of polymer.

When the pH during the reaction of the present invention exceeds 9, the production of aldolcarboxylic acid (V in the reaction scheme) is promoted, but since this polymer also has a carboxyl group, it is biodegradable. Although not present, it has a Ca capturing ability.

Separation of the resulting polymer from the reaction mixture can be carried out by dehydration by freeze-drying, dialysis using a membrane filter, or solvent reprecipitation using a solvent such as isopropyl alcohol, ethanol or methanol. When the reaction mixture is freeze-dried or reprecipitated by a solvent reprecipitation method, the polymer of the present invention can be obtained as a white powder by drying after solvent separation. However, when the polymer of the present invention is used as a builder for detergent, the aqueous solution of the oxidative polymerization reaction mixture discharged from the reaction tower should be blended into the detergent slurry and spray-dried without separating the polymer. You can

The weight average molecular weight of the thus obtained polymer is 500 to 1, by gel filtration (GPC) analysis.
It reaches up to, 000,000, far exceeding that of conventional polyglycerin (molecular weight of 500 to 1000). However, when used as a builder for detergents, it is preferably from 1000 to 100,000, from the viewpoint of chelating ability, and from 2000 to
20,000 is especially good. In the GPC measurement of the polymer obtained in the present invention, when the terminal stabilization treatment is not particularly performed, the polymer may be easily adsorbed in the column or may be decarboxylated depending on the kind of the packing material. Needs to select the optimal column system.

From the infrared absorption spectrum of the polymer of the present invention, absorption peaks of carboxylate carbonyl vibrational vibration and ether bond vibrational vibration are obtained.
From the proton NMR and C ₁₃ NMR spectra, absorption peaks of the proton bonded to the etheric carbon and the etheric carbon are obtained, respectively. From this, it has been found that the polymer in the present invention is a polymer having a large amount of carboxyl groups.

Its structure is represented by formula (i), formula (ii), formula (ii)
i), a formula (iv), a formula (v), a formula (vi), or a structure containing two or more types of structural units is presumed. This is because the polymerization reaction proceeds under the oxidation reaction, and is one of the features of the production method of the present invention.

[0068]

[Chemical 2]

In the present invention, the polymer obtained by removing the monomer component from the reaction mixture is 100 to 600 mg-C.
Since it has a high ion exchange capacity of aCO ₃ / g, it is useful as a builder for detergents.

[0070]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following examples,% indicated for the amount of supported catalyst means% by weight. Further, the conversion rate of the hydroxyl compound represents the ratio of the number of moles consumed in the oxidation reaction to the charged hydroxyl compound. In addition, all percentages regarding the conversion rate are weight percentages. Further, the polymer yield is
It is a value excluding the molar ratio residual ratio of the hydroxyl compound, the monomer and the monomer precursor remaining in the reaction mixture.

[0071]

[Equation 1]

The analyzes and the like conducted in the examples were carried out by the following methods. (Analysis of Polymer) The reaction mixture was reprecipitated by a solvent reprecipitation method using ethyl alcohol, separated from the solvent, and dried. The hygroscopic white powder thus obtained was analyzed by infrared absorption spectrum, NMR spectrum and gel filtration chromatography (GPC). In addition, GP
The C measurement conditions are shown below. Column: G 2000SW-G 4000SW (Toso-manufactured silica gel packed column) Before the analysis of the polymer, an aqueous solution of the sodium formalin condensate of naphthalene sulfonate is passed through the column, and the condensate is silica gel. It is necessary to be adsorbed on. -Solvent: 0.1 M-NaCl aqueous solution / acetonitrile = 7 / 3-Flow rate: 0.8 ml / min-Temperature: 25 ° C-Detector: UV-8011 (manufactured by Toso), 210 nm
Measured at ・ Sample concentration: 0.1% aqueous solution

(Quantitative analysis by HPLC) The conditions of HPLC are shown below.・ High performance liquid chromatography: D-2500 / L-6
Type 000 manufactured by Hitachi, Ltd.-Detector: L-3300 type (RI monitor) -Column: C-61OS-Eluent: 0.5% phosphoric acid aqueous solution 0.5 ml /
min ・ Pressure: 10 Kg / cm ²・ Temperature: 50 ° C

(Ca-Capturing Ability) The Ca-capturing ability of each of the polymers collected in the following Examples was measured by the following method. That is, the separated aqueous solution of the polymer was freeze-dried to obtain a dried product of the polymer. Weigh precisely 0.1 g of it,
_{0.1M-NH 4 Cl-NH 4} OH buffer (pH 10.
0) to 100 ml to obtain a polymer aqueous solution. After inserting a calcium ion electrode into this solution, it was stirred with a magnetic stirrer and converted into 20,000 in terms of CaCO _3.
A CaCl ₂ aqueous solution (pH 10.0) corresponding to ppm was dropped by a buret and the Ca ion concentration in the solution was measured by an ion analyzer. The Ca trapping ability was obtained from the inflection point by plotting the relationship between titration amount and residual Ca ion concentration.

(Preparation of catalyst composition) Takeda Pharmaceutical Co., Ltd.
Wood-based activated carbon, WH ₂ C (specific surface area: 1200 m ² /
g, bulk density: 500 / liter, pore volume: 0.8 ml
/ G) as a catalyst carrier 0.9% Ce.3.0%
A three-component catalyst composed of Bi · 3.0% Pd / C was prepared by the following method. 93 g of activated carbon dried with hot air at 120 ° C. was dispersed in 1250 ml of ion-exchanged water overnight. Meanwhile, cerium chloride _{(CeCl 3 · 7H 2 O)} 2.
4g, bismuth chloride (BiCl ₃₎ 4.5 g, and palladium chloride (PdCl ₃₎ 5.0g, stirring to aqueous hydrochloric acid solution was added concentrated hydrochloric acid 26ml of ion exchange water 150 ml, and uniformly dissolved therein. The obtained brown homogeneous solution of the catalyst component was added to an aqueous dispersion of activated carbon, and the mixture was stirred for 5 hours.
The catalyst component was loaded at room temperature. The supernatant liquid became colorless and transparent. In order to carry out the reduction treatment of the obtained catalyst precursor, the pH of the aqueous dispersion of the catalyst precursor was maintained at about 12 with 20% sodium hydroxide aqueous solution, and 20 ml of 37% formalin aqueous solution was added. While stirring, raise the temperature to 80 ° C and
The reduction treatment was performed at 30 ° C. for 30 minutes. The resulting catalyst was allowed to cool to room temperature, washed 3 times with 1500 ml of deionized water, and filtered under reduced pressure. By the above operation, the water content of about 50% of 0.
100 g of a 9% Ce / 3.0% Bi / 3.0% Pd / C catalyst was obtained as a dry product. The other catalyst compositions in this example were prepared in the same manner.

Example 1 0.9% Ce.3.0% prepared in the preparation example of the catalyst composition
Inner diameter 2 with jacket of Bi / 3.0% Pd / C catalyst
A 200 ml fixed bed reaction tower made of Pyrex having a height of 0 mm and a height of 700 mm was packed with 100 g as a dry product. The reaction temperature was set to 50 ° C., 100 parts of 50% glycerin aqueous solution and 30% sodium hydroxide aqueous solution were added from the top of the reaction tower.
0 parts of the mixed solution, the liquid hourly space velocity (LHSV) 0.07h
Oxygen gas was supplied at a flow rate of r ⁻¹ and a downward cocurrent flow rate of 5 N liter / hr. After 40 hours, a colorless transparent viscous liquid (pH 10 to 11) was distilled from the outlet of the reaction tower. When this liquid was analyzed by high performance liquid chromatography (HPLC), the conversion of glycerin was 100%, the selectivity of residual tartronic acid was 30%, and the selectivity of glyceric acid was 25%.
Met. On the other hand, GPC (gel permeation chromatograp
This viscous liquid was analyzed by hy) (Fig. 2). As a result, 5.2% by weight of a polymer having a weight average molecular weight of 4.503 × 10 ^{4 based on} sodium polystyrene sulfonate, 7.3
It was confirmed that 6.8% by weight of the polymer (24 × 10 ³ ) was present (12% by weight in total). The viscous liquid was dialyzed to separate the polymer component. The presence of carboxylate and ether bond was confirmed from the infrared absorption spectrum of the obtained polymer, and further proton NMR and C ₁₃ NMR
The existence of carbon and hydrogen of ether bond was confirmed from the spectrum. From these results, it was estimated that the structure of the obtained polymer was composed of the structural units of the above-mentioned formulas (i) to (iv). Moreover, as a result of measuring the Ca ion capturing ability, 440 mg-CaCO ₃ / g was given per unit weight of the preparative polymer.

Example 2 The reaction was carried out under the same conditions as in Example 1 except that a mixed solution of 100 parts of 50% glyceric acid aqueous solution and 130 parts of 26% sodium hydroxide aqueous solution was used. According to GPC measurement of the reaction mixture, 16% of the polymer having a weight average molecular weight of 62,000 based on sodium polystyrene sulfonate was used.
It turned out to exist. It was estimated from the infrared absorption spectrum and the NMR spectrum that the structure of the polymer component obtained by dialysis separation consisted of the structural units of formulas (i) to (iv). Moreover, as a result of measuring the Ca ion capturing ability, it was found that 460 mg-CaCO ₃ / g per unit weight of the preparative polymer.
Was given.

Example 3 The catalyst composition was 0.9% Ce.1.5% Te.3.0% P.
The reaction was carried out in the same manner as in Example 1 except that the ratio was d / C. A colorless transparent viscous liquid (pH
Approximately 10) was analyzed by HPLC. As a result, the conversion rate of glycerin was 100% and the selectivity of residual tartronic acid was 15%.
%, And the glyceric acid selectivity was 22%. On the other hand, GP
It was confirmed by C measurement that 25% of a polymer having a weight average molecular weight of 58,000 based on sodium polystyrene sulfonate was present. The presence of carboxylate and ether bond was confirmed from the infrared absorption spectrum of the polymer after dialysis separation, and the presence of carbon and hydrogen of ether bond was confirmed from proton NMR and C ₁₃ NMR spectra. From these results, it was estimated that the structure of the obtained polymer was composed of the structural units of the above-mentioned formulas (i) to (iv). Moreover, as a result of measuring the Ca ion trapping ability, 450 mg-CaCO ₃ / g was given per unit weight of the preparative polymer.

Example 4 The reaction was carried out under the same conditions as in Example 3 except that a mixed solution of 100 parts of 50% tartronic acid aqueous solution and 130 parts of 23% sodium hydroxide aqueous solution was used. From the GPC measurement of the reaction mixture, it was found that 19% of the polymer having a weight average molecular weight of 47,000 based on sodium polystyrenesulfonate was present. The structure of the polymer component obtained by dialysis separation of the polymer component has an infrared absorption spectrum, N
It was estimated from the MR spectrum that the structural units of formulas (i) to (iv) were used. In addition, as a result of measuring the Ca ion capturing ability, 450 mg-C per unit weight of the preparative polymer.
aCO ₃ / g was given.

Example 5 Various catalyst compositions (1.5% Te.3.0% Pd / C,
1.5% Ce / 3.0% Pd / C, 3.0% Pd / C)
Was reacted in the same manner as in Example 1. For each catalyst composition, the weight average molecular weights of the separated polymers were 58,000, 43,000 and 40,000, respectively. Table 1 summarizes the polymer yield and the Ca ion trapping ability. The structure of the polymer component was estimated from the infrared absorption spectrum and the NMR spectrum to consist of the structural units represented by the formulas (i) to (iv).

Example 6 Using a mixed aqueous solution of 100 parts of 25% glycerin aqueous solution and 145 parts of 15% sodium hydroxide, 0.75% Pt.3.0% Bi.3.0% Pd / C was used as a catalyst composition. Was used in the same manner as in Example 1 except that the reaction temperature was 25 ° C. Table 1 summarizes the polymer yield and Ca ion trapping ability. The pH of the distillate at the outlet of the reaction tower was 5.6. The structure of the polymer component is an infrared absorption spectrum,
It was estimated from the NMR spectrum that it was composed of the structural units of formulas (i) to (iv).

Example 7 The catalyst composition was 0.8% Ce.1.5% Bi.0.75%.
The reaction was performed in the same manner as in Example 6 except that Pt was 3.0% Pd / C. Table 1 summarizes the polymer yield and Ca ion trapping ability. The pH of the distillate at the outlet of the reaction tower was 5.6. The structure of the polymer component was estimated from the infrared absorption spectrum and the NMR spectrum to consist of the structural units represented by the formulas (i) to (iv).

Example 8 The catalyst composition of the first reaction column (reactor similar to that used in Example 1) was 0.8% Ce.1.5% Bi.0.75%.
Pt.3.0% Pd / C, the catalyst composition of the second reaction column (reactor similar to that used in Example 1) was 0.6% Bi.
The reaction was performed in the same manner as in Example 6 except that 3.0% Pt / C was used. The reaction mixture leaving the first reaction column was introduced into the second reaction column at the same flow rate as it was. Reaction tower outlet distillate p
H was 3.5, and white crystals were deposited in the receiver.
This was identified as ketomalonic acid by HPLC.
Table 1 summarizes the polymer yield and Ca ion trapping ability.
The structure of the polymer component is the infrared absorption spectrum, NM
It was estimated from the R spectrum that it was composed of structural units of formulas (i) to (iv).

Example 9 A reaction was carried out in the same manner as in Example 8 except that glycerin and ethylene glycol were mixed at a molar ratio of 1: 1. The pH of the distillate at the outlet of the reaction tower was 3.5. Table 1 summarizes the polymer yield and Ca ion trapping ability. The structure of the polymer component was estimated from the infrared absorption spectrum and the NMR spectrum to consist of the structural units represented by the formulas (i) to (iv).

Example 10 A reaction was carried out in the same manner as in Example 9 except that glycerin and 1,2-propylene glycol were mixed at a molar ratio of 1: 1. The pH of the distillate at the outlet of the reaction tower was 3.5. Table 1
The polymer yield and Ca ion trapping ability are summarized in Table 1. The structure of the polymer component was estimated from the infrared absorption spectrum and the NMR spectrum to consist of the structural units represented by the formulas (i) to (iv).

Example 11 The procedure of Example 11 was repeated, except that the catalyst composition of Example 7 was diluted 4 times by weight with glass beads having a diameter of 0.8 mm as a diluent and the reaction mixture used in Example 1 was charged. The reaction was carried out as in Example 7. The pH of the distillate at the outlet of the reaction tower was 5.4. Table 1 summarizes the polymer yield and Ca ion trapping ability. The structure of the polymer component is an infrared absorption spectrum,
It was estimated from the NMR spectrum that it was composed of the structural units of formulas (i) to (iv).

Example 12 500 g of a 25% glycerol 15% sodium hydroxide mixed solution was used in Example 7 in a 1-liter round bottom flask equipped with a thermometer, a stirrer, a gas inlet, a sampling port and an exhaust gas port. 100 g of the catalyst composition was charged and reacted at a reaction temperature of 25 ° C. and an oxygen supply rate of 1 liter / h for 20 hours. The pH of the reaction mixture was 7.2. The polymer yield and Ca ion trapping ability are summarized in Table 1. The structure of the polymer component was estimated from the infrared absorption spectrum and the NMR spectrum to consist of the structural units represented by the formulas (i) to (iv).

Example 13 The catalyst composition in Example 12 was adjusted to 0.6% Bi, 3.0%.
% Pt / C, exchange with 100g, and air supply rate is 3.0
The reaction was performed in the same manner as in Example 12 except that the reaction product of Example 12 was used as a raw material at a rate of 1 liter / h. The pH of the reaction mixture was 6.2. The polymer yield and Ca ion trapping ability are summarized in Table 1. The structure of the polymer component was estimated from the infrared absorption spectrum and the NMR spectrum to consist of the structural units represented by the formulas (i) to (iv).

Example 14 A reaction was carried out in the same manner as in Example 7 except that the raw material was ethylene glycol. The polymer yield and Ca ion trapping ability are summarized in Table 1. The pH of the distillate at the outlet of the reaction tower was 5.3. The structure of the polymer component was estimated to consist of the structural unit of formula (ii) from the infrared absorption spectrum and the NMR spectrum.

Example 15 A reaction was carried out in the same manner as in Example 7 except that the starting material was glycolic acid. Table 1 shows the polymer yield and Ca ion trapping ability.
Summarized in. The pH of the distillate at the outlet of the reaction tower was 5.3. The structure of the polymer component is an infrared absorption spectrum,
It was estimated from the NMR spectrum that it consisted of the structural unit of formula (ii).

Example 16 Example 7 except that the raw material is propylene glycol.
The reaction was performed in the same manner as in. The polymer yield and Ca ion trapping ability are summarized in Table 1. The pH of the distillate at the outlet of the reaction tower is 5.7.
Met. The structure of the polymer component was estimated to consist of the structural unit of formula (vi) from the infrared absorption spectrum and the NMR spectrum.

Example 17 A reaction was carried out in the same manner as in Example 7 except that the starting material was hydroxyacetone. The polymer yield and Ca ion trapping ability are summarized in Table 1. The pH of the distillate at the outlet of the reaction tower was 6.2. The structure of the polymer component was estimated to consist of the structural unit of formula (vi) from the infrared absorption spectrum and the NMR spectrum.

Example 18 A reaction was carried out in the same manner as in Example 7 except that the raw material was lactic acid. The polymer yield and Ca ion trapping ability are summarized in Table 1. The pH of the distillate at the outlet of the reaction tower was 5.7. The structure of the polymer component was estimated to consist of the structural unit of formula (vi) from the infrared absorption spectrum and the NMR spectrum.

Example 19 The reaction was carried out under the same conditions as in Example 1 except that a 40% aqueous sodium hydroxide solution was used and the reaction temperature was 60 ° C. After 20 hours, a brown reaction solution (pH
13) was distilled. When this liquid was analyzed by HPLC, the glycerin conversion rate was 100%. As a result of GPC analysis, the weight average molecular weight based on polystyrene sulfonic acid was 4
It was confirmed that 500% of the polymer was present at 37% by weight. The structure of the polymer component is infrared spectrum and NM
It was estimated from the R spectrum that it had the structure of formula (v). The reaction mixture has a Ca ion capturing ability of 120 m.
was a g-CaCO ₃ / g.

[0095]

[Table 1]

[0096]

EFFECT OF THE INVENTION According to the production method of the present invention, a polymer having a carboxyl group, which is useful as a biodegradable detergent builder, etc., having a unique function such as a high ion exchange ability using an inexpensive raw material Can be manufactured efficiently.

[Brief description of drawings]

FIG. 1 shows a schematic diagram of a reaction scheme in the present invention.

2 is a GPC of the reaction mixture obtained in Example 1. FIG.
(gel permeation chromatography) chart is shown.
In the figure, peak 1 (area 3.05%) is the polymer of the present invention (weight average molecular weight 4.503 × 10 ⁴ ), peak 2 (area 3.98%) is the polymer of the present invention (weight average). Molecular weight: 7.324 × 10 ³ ), peak 3 (area: 46.06%)
Is a raw material / low molecular weight oxide (weight average molecular weight 3.826 ×
10 ² ), peak 4 (area 46.77%) represents the eluent.

FIG. 3 is a GPC of the reaction mixture obtained in Example 8.
A chart is shown. Peak 1 (area 5.0%) in the figure is
The polymer (weight average molecular weight 6.6 × 10 ⁵ ) and peak 2 (area 17.0%) of the present invention are the polymer (weight average molecular weight 8.2 × 10 ⁴ ) and peak 3 (area 3) of the present invention. 0.0%)
Is the polymer of the present invention (weight average molecular weight 3.7 × 1
0 ⁴ ), peak 4 (area 30%), the polymer of the present invention (weight average molecular weight 2.0 × 10 ⁴ ), peak 5 (area 2
5%) is a polymer of the present invention (weight average molecular weight 600
0) and peaks 6, 7 and 8 have a weight average molecular weight of 200 to 1
000 oligomers and monomers.

Claims (11)

[Claims] 1. A polymer having a carboxyl group, characterized in that a hydroxyl group compound is catalytically oxidized in the presence of the following catalyst composition and an oxidizing agent to produce a monomer having a carboxyl group, and the monomer is polymerized. Manufacturing method. Catalyst composition: One or more elements selected from the group consisting of palladium, platinum, rhodium, and ruthenium as the catalyst first component, and one or more elements selected from the group consisting of bismuth, tellurium, tin, lead, antimony, and selenium. An element is used as a catalyst second component, one or more elements selected from rare earth elements is used as a catalyst third component, and (a) catalyst first component and catalyst second component (b) catalyst first component and catalyst third component (ha) ) A catalyst first component, a catalyst second component and a catalyst third component,
Alternatively, (d) a supported catalyst consisting of only the catalyst first component. 2. The method according to claim 1, wherein the hydroxyl compound is glycerin, glyceric acid or a salt of glyceric acid. 3. The method according to claim 1, wherein the hydroxyl compound is tartronic acid or a salt thereof. 4. The method according to claim 1, wherein the hydroxyl compound is ethylene glycol, glycolic acid or a salt of glycolic acid. 5. The hydroxyl compound is propylene glycol,
The production method according to claim 1, which is hydroxyacetone, lactic acid, or a salt of lactic acid. 6. The method according to claim 1, wherein the hydroxyl compound is a mixture of glycerin and ethylene glycol. 7. The first catalyst component of the catalyst composition of (c) is palladium and platinum, the second catalyst component is bismuth and / or tellurium, and the third catalyst component is cerium and / or lanthanum. Any one of the manufacturing methods. 8. The method according to claim 1, wherein the reaction is carried out in a fixed bed reactor filled with the catalyst composition. 9. 0.5 to 1 with respect to 1 part by weight of the catalyst composition.
The manufacturing method according to claim 8, wherein the filling is performed by diluting with 0 part by weight of a diluent. 10. The polymer having a carboxyl group has a weight average molecular weight of 500 by gel filtration chromatography.
The production method according to any one of claims 1 to 9, wherein the production method is about 1,000,000. 11. The method according to claim 1, wherein the polymer having a carboxyl group has a calcium-capturing ability of 100 to 600 mg-CaCO ₃ / g.