WO1995032233A1

WO1995032233A1 - Process for producing carboxylated polymer

Info

Publication number: WO1995032233A1
Application number: PCT/JP1994/001995
Authority: WO
Inventors: Hiroshi Kimura; Yasuhisa Fukumoto; Yukinaga Yokota; Shoichi Jho
Original assignee: Kao Corporation
Priority date: 1994-05-24
Filing date: 1994-11-28
Publication date: 1995-11-30

Abstract

A process for producing a carboxylated polymer which comprises catalytically oxidizing a hydroxy compound in the presence of a specified catalyst composition and an oxidizing agent to yield a carboxylated monomer and polymerizing the monomer. The catalyst composition used comprises a supported catalyst mixture suitably selected from those composed of at least one element selected from the group consisting of palladium, platinum, rhodium and ruthenium as the first catalyst component, at least one element selected from the group consisting of bismuth, tellurium, tin, lead, antimony and selenium as the second catalyst component, and at least one element selected from rare earth elements as the third catalyst component.

Description

TECHNICAL FIELD The present invention relates to a method for producing a polymer having a lipoxyl group.

The present invention relates to a method for producing a polymer having a carbonyl group. More specifically, the present invention relates to a method for producing a carboxyl-containing polymer useful as a detergent builder, a neutralizer, a thickener, a polymer material, or a water-absorbing polymer material. Background art

Polyboronic acid, typified by a copolymer with polyacrylic acid or maleic acid, is used as a carboxyl-containing polymer in water-absorbing polymers and other detergent builders, but is non-biodegradable. Is becoming a problem. Monsanto of the United States has been conducting research on the synthesis of a biodegradable polymer, polycarboxylate (polyglyoxylic acid, builder U), using expensive glyoxylate as a raw material, and has disclosed Japanese Patent Publication No. 62-37044. USP 4 1 4 4 2 2 6). Although builder U has an extremely high calcium-capturing ability and is an excellent detergent builder, the high price of the raw materials still poses a problem in terms of practicality. Therefore, if a biodegradable polymer builder such as builder U can be produced at low cost using inexpensive raw materials, the ripple effect is incalculable.

On the other hand, German Offenlegungsschrift No. 2 347 738 discloses that polyglycerin oxide obtained by oxidizing polyglycerol derived from glycerin, which is a cheap material, is used as a biodegradable builder. The method is described ing. However, since the polymerization degree of polyglycerin is generally at most 10 at most, the number of carboxy groups in the polyglycerin oxide obtained by the method is small, and the function as a polycarboxylic acid, for example, the chelating function, is low. It is of low quality and its performance as a detergent builder is not satisfactory.

In addition, JP-A-62-211243 and JP-A-62-192026 disclose that, in the presence of a transesterification catalyst, a high temperature (200 or less), A method of dehydrating and condensing tartronic acid or its ester under reduced pressure (50 torr or less) is described. However, under such conditions, the formed polymer is likely to decompose. It is expected to develop a method for expressing the high Ca capture ability with little degradation of the generated polymer by reacting in step (1). Disclosure of the invention

In view of such a situation, the present inventors have made inexpensive raw materials glycerin, glyceric acid, ethylen glycol, propylene glycol, hydroxyacetone, lactic acid, a salt of glyceric acid or a salt of lactic acid, or Presence of the specified catalyst composition and oxidizing agent, starting from tartronic acid, which is an oxide of glycerin, decarboxylated decomposition product of tartronic acid, or glycolic acid, which is an oxide of ethylene glycol, or a salt thereof As a result of producing a monomer having a carboxyl group by catalytic oxidation below and proceeding the polymerization reaction, it was found that a polymer having a large amount of a carboxyl group was formed, and the present invention was completed.

That is, the gist of the present invention is:

(1) A hydroxyl group compound is prepared in the presence of the following catalyst composition and oxidizing agent. A method for producing a carboxyl-containing polymer, which comprises producing a monomer having a carboxyl group by catalytic oxidation and polymerizing the monomer.

Catalyst composition:

One or more elements selected from the group consisting of palladium, platinum, rhodium, and ruthenium are used as the catalyst first component, and one or more elements selected from the group consisting of bismuth, tellurium, tin, lead, antimony, and selenium are used as the catalyst first component. Two or more components, one or more elements selected from rare earth elements as the third component of the catalyst,

(B) Catalyst first component and catalyst second component

(Mouth) Catalyst first component and catalyst third component

(C) Catalyst first component, catalyst second component and catalyst third component, or (2) Catalyst first component only

A supported catalyst consisting of any of

(2) The method according to (1), wherein the hydroxyl group compound is glycerin, glyceric acid or a salt of glyceric acid.

(3) The production method according to the above (1), wherein the hydroxyl compound is tart baltic acid or a salt thereof.

(4) The method according to (1), wherein the hydroxyl compound is a salt of ethylene glycol, glycolic acid or glycolic acid.

Droxacet (1)

Cole mixture

The production method according to the above (1), wherein (7) The catalyst composition of (c), wherein the first catalyst component is palladium and platinum, the second catalyst component is bismuth and / or tellurium, and the third catalyst component is cerium and Z or lanthanum. 6) Any of the manufacturing methods described,

(8) The method according to any one of the above (1) to (6), wherein the reaction is carried out in a fixed bed reactor filled with the catalyst composition.

(9) The method according to (8), wherein the catalyst composition is diluted with 0.5 to 10 parts by weight of diluent per 1 part by weight of the catalyst composition and filled.

(10) The weight average molecular weight of the polymer having a carboxyl group is from 500 to 1,000, 000 by gel filtration chromatography, according to any one of the above (1) to (9). A method of manufacturing, and

(1 1) calcium trapping ability of the polymer having a carboxyl group is 1 0 0~6 0 O mg - C a C 0 8 above, wherein the a Zg (1) ~ (1 0) according to any one Manufacturing method. BRIEF DESCRIPTION OF THE FIGURES

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

₀ Figure 2 is showing a Chiya one Bok of GPC of the reaction mixture obtained in Example 1 (gel permeatio n chromatography)

Peak 1 (area 3.05%) in the figure is the polymer of the present invention (weight average molecular weight 4.503 X 10 *), and beak 2 (area 3.98%) is the present invention. Polymer (weight average molecular weight 7.32 4 10 ³ ), beak 3 (area 46.06%) is a raw material low molecular oxide (weight average molecular weight 3

826 × 10 ² ) and peak 4 (area 46.777) indicate the eluent.

FIG. 3 shows a GPC chart of the reaction mixture obtained in Example 8. . Peaks in FIG. 1 (area 5.0%), the polymer of the present invention (weight average molecular weight 6. 6 X 1 0 ^6), peak 2 (area 1 7.0%), the present onset Ming polymerization Product (weight average molecular weight 8.2 × 10 ⁴ ), peak 3 (area 3.0) is the polymer of the present invention (weight average molecular weight 3.7 × 10 ⁴ ), peak 4 (area 30%) The polymer of the present invention (weight average molecular weight 2.

0 X 10 ⁴ ), peak 5 (area 25%) is the polymer of the present invention (weight average molecular weight 600,000), and peaks 6, 7, 8 have a weight average molecular weight of 20

0 to 1000 oligomers and monomers. BEST MODE FOR CARRYING OUT THE INVENTION

The reaction scheme in the present invention is described below with reference to FIG.

First, the polymerization in the present invention is mainly oxidative dehydrogenation polymerization. In other words, active hydrogen at the polymerization site of the monomer precursor (hereinafter sometimes abbreviated as monomer precursor), which is a reaction raw material, reacts with oxygen supplied from the bulk on the catalyst surface to form water. A monomer having an aldehyde group or a carbonyl group (hereinafter, sometimes abbreviated as a monomer) which is directly involved in polymerization is formed on the catalyst surface, and the polymerization reaction of the monomer proceeds. It is.

Examples of the monomer precursor in the present invention include (1) glycerin, glycerin, or a salt of glyceric acid, (2) tartronic acid or a salt thereof, (3) ethylene glycol, glycolic acid, or glycol. Salts of phosphoric acid, (4) provylene glycol, hydroxyacetone, lactate and phosphoric acid salts can be used. ^:::

Glyceric acid and tanothrenic acid are oxides of glycerin, and glycolic acid is a decarboxylated product of tartronic acid or ethylene glycol. Is an oxide of As shown in the reaction scheme in Fig. 1, these are formed sequentially by the catalytic oxidation of glycerin, ethylene glycol, and propylene glycol, so that glycerin, ethylene glycol, and propylene glycol are It is the cheapest starting material. In addition, monomers involved in direct polymerization include glyceric acid, tartronic acid, glycolic acid, lactic acid or their salts, which are obtained by catalytic oxidation of their salts, ketomalonic acid, glyoxylic acid, pyruvine, respectively. An acid or a salt thereof is used, and these monomers may be those synthesized separately by a synthesis method.

The reaction mechanism for producing the polymer of the present invention by further polymerizing the monomer produced using these monomer precursors has not been completely elucidated. It is estimated as follows.

That is, the reaction of the present invention is carried out as follows: (1) an oxidation reaction part for producing a monomer precursor and a monomer; (2) a polymerization part to a polymer having a carboxyl group; and (3) It is roughly divided into three parts: decarboxylation of polymer.

In the oxidation reaction section for producing the monomer precursor and the monomer, for example, catalytic oxidation of glycerin starts, and glyceric acid is produced via glyceraldehyde. Glyceric acid is further oxidized to produce tartronic aldehyde, one of the monomers in the present invention. Alternatively, the tartronic acid aldehyde is further oxidized to produce tartronic acid, which in turn produces ketomalonic acid, one of the monomers in the present invention. 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 via the corresponding aldehyde, which is the same as that produced by decarboxylation of tartronic acid. Glycolic acid is further oxidized to produce monomeric glyoxylic acid.

In addition, when propylene glycol is used as a starting material, pyruvate, which is a monomer, is produced via hydroquinacetone or lactic acid.o

The polymerized portion to 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 where tartronic acid or a salt thereof is used as a monomer precursor, in this route, the polymerization reaction using apparently ketosulfonic acid as a monomer proceeds while its 2-hydroxyl group undergoes oxidative dehydrogenation. (Root 1). This produces boriketomalonic acid (I) or a salt thereof as a polymer.

(b) When glycerin, glyceric acid, or a salt of glyceric acid is used as the monomer precursor, in this route, the tartaronic acid aldehyde or its salt, which is a monomer, is the monomer precursor immediately before it. The polymerization reaction proceeds by oxidation of the primary hydroxyl group of a certain glyceric acid or a salt thereof, and the aldehyde group is converted into an ether bond (route 2). As a result, boritaltronic acid aldehyde (III) or a salt thereof is formed as a polymer, and its secondary hydroxyl group is oxidized to form polymerized polymesoxal aldehyde (IV) or a salt thereof. Presumed.

(c) Tartronic acid or a salt thereof also undergoes decarboxylation as described above to become glycolic acid or a salt thereof. In this case, the monomer precursor The glycolic acid or a salt thereof is further oxidized, and a polymerization reaction using glyoxylic acid or a salt thereof as a monomer proceeds (route 3). As a result, polyglyoxylic acid (II) or a salt thereof is produced as a polymer. When ethylene glycol is used as a monomer precursor, polyglyoxylic acid (II) is similarly produced via glycolic acid and glyoxylic acid.

(d) In this case, aldolcarboxylic acid (V) containing a hydroxyl group is generated via aldol generated from glyceraldehyde (route 4). In this case, the pH is 9 or more and the reaction temperature is 50 ° C or more.

(e) Propylene glycol, hydroquinone acetone, lactic acid or a salt of lactic acid as a monomer precursor, all of which produce polyvirbic acid (VI) via pyruvic acid (route 5).

As the decarboxylation part of the polymer ((I) and (IV)), borike tomalonic acid (I), polymesoxal aldehyde (IV) or salts thereof are thermodynamically unstable. Therefore, it is presumed that under high temperature, it easily decarboxylates and decomposes to boroglioxylic 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 decarboxylation of the polymer as much as possible in producing a polymer having a large amount of hydroxyl group.

Further, 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 to 3. In this case, a random copolymer of ketomalonic acid and glyoxylic acid is generated, so that the polymer has better polymerizability and higher thermal stability than the ketomalonic acid homopolymer of root 1. A copolymer is formed.

In the present invention, in addition to raw materials such as glycerin, ethylene glycol, glyceric acid, tartronic acid or glycolic acid or a salt thereof, for example, 1,2-propylene glycol, 1,3-propylene glycol And monohydric alcohols such as methanol, ethanol, propyl alcohol, and isopropyl alcohol, or aldehydes such as formaldehyde and acetate aldehyde. Also in this case, the corresponding aldehyde or ketone, which is an oxide of the polyhydric alcohol or monohydric alcohol, or the structural unit of the aldehyde is incorporated into the main chain of the polymer having a carboxyl group of the present invention. However, due to the thermodynamic stability of the resulting polymer, it may be more effective as a polymer builder for detergents than when glycerin or its oxide is used as a starting material. As the catalyst composition used in the present invention, a platinum-based noble metal catalyst is effective. That is, at least one element selected from the group consisting of palladium, platinum, rhodium, and ruthenium is used as the catalyst first component, and at least one element selected from the group consisting of bismuth, tellurium, tin, lead, antimony, and selenium. When the element is the catalyst second component and one or more elements selected from rare earth elements are the catalyst third component, (a) a catalyst composition combining the first catalyst component and the second catalyst component; A catalyst composition combining the first component and the third catalyst component, (c) a catalyst composition combining the first catalyst component, the second catalyst component and the third catalyst component, and (ii) a catalyst composition comprising only the first catalyst component. Catalyst compositions are used.

Since the polymer having a carboxyl group of the present invention is thermally unstable and easily undergoes decarboxylation, the above-mentioned noble metal catalyst having a low-temperature activity capable of promoting oxidative polymerization under mild conditions. Is particularly effective It is. However, oxidation and oxidative polymerization using other general oxidation catalysts or inorganic or organic reagents (hydrogen peroxide, peracetic acid, etc.) can also be used in combination.

The catalyst composition (a) in which the catalyst first component and the catalyst second component are combined is a preferable catalyst composition in terms of suppressing a decrease in catalyst activity due to oxygen poisoning. Examples of the second component of the catalyst include bismuth, tellurium, tin, lead, antimony, and selenium, and although not particularly limited, antimony, bismuth, tellurium, and lead are particularly effective. For example, by combining palladium with bismuth or tellurium, oxygen poisoning can be avoided, and the oxidation reaction rate and the conversion of raw materials can be greatly improved. Also, P b · P d / C a C 0 8 catalyst, known as re-emission Dollar catalysts can also be used as catalysts of the present invention. Bismuth, tellurium and antimony are particularly useful.

In the present invention, since the polymerization reaction occurs simultaneously with the production of the monomer, the influence of the 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 are proposed, such as the use of a diluent described later, the outer layer supporting method, and the control of the amount of oxygen supply, but these methods are not direct methods. In order to suppress the poisoning of polymer-derived products at the atomic and molecular levels, it is necessary to consider the physicochemical interaction between the formed polymer and the catalyst surface on the solid catalyst surface. In consideration of this, by eliminating the poisoning of the product derived from the formed polymer, it is possible to provide an unprecedented new method of applying a fixed bed reactor to a polymerization reaction.

As a concrete method, if the solid surface is modified based on the surface science, an idea is needed. To achieve this effect, how the catalyst second component is applied to the surface of the underlying main catalyst element Can high dispersion be supported effectively? Is determined by This is determined by the physical properties of the base metal and the second component of the catalyst, but largely depends on the catalyst preparation method. The liquid phase equilibrium adsorption stage loading method employed in the present invention is a very effective method and can be applied to mass production of catalysts.

From these findings, bismuth is particularly effective as the second catalyst component in the present invention. In other words, bismuth has a surface of the main catalyst element represented by palladium or platinum, particularly

It is likely that the ad-atom structure or ad-layerr structure is easily formed in the 1 1 1) plane, and as a result, adsorption of the produced polymer is greatly suppressed. This specificity of bismuth is measured by measuring the amount of adsorption of C0 of a two-component catalyst with palladium or platinum.In the case of bismuth, the adsorption amount of palladium is different from that of other catalysts such as tellurium and lead. Alternatively, the atomic ratio of PdZBi and Pt / Bi on the catalyst surface calculated from the dispersity and surface area of palladium or platinum is 3 It can be understood from becoming. The catalyst composition (mouth) combining the first catalyst component and the third catalyst component is a combination of the third catalyst component from the viewpoint of achieving high-speed reactivity. As rare earth elements, lanthanum, cerium, brassium, neovisium, etc. are effective. This is because the addition of the rare earth element, which is a basic element, makes the first component of the catalyst, such as palladium, into a highly dispersed state and imparts basicity to the catalyst surface, thereby achieving high-speed reactivity. .

The catalyst composition (C) in which the first catalyst component, the second catalyst component, and the third catalyst component are combined is a composition having both the properties of the catalyst compositions (a) and (mouth) described above. However, it is possible to obtain an effect of suppressing a decrease in catalytic activity due to oxygen poisoning and achieving high-speed reactivity. As such a catalyst composition, Although not particularly limited, for example, CeBiPd, CeBe * Pd, SeBi * Pd, CeBiSePd, C e-Bi-Te-Pd, Bi-Pt-Pd, Ce-Bi-Pt-Pd.

Above all, as the catalyst composition (c), those in which the first component of the catalyst is palladium and platinum, the second component of the catalyst is bismuth and / or tellurium, and the third component of the catalyst is cellium and / or lanthanum are preferably used. . As described above, in the present invention, a catalyst system having a low-temperature activity can be reformed by using a plurality of catalyst first components, in particular, platinum as a co-catalyst.

Particularly, the four-component catalyst of Ce'Bi'Pt'Pd has remarkable low-temperature activity and polymerization activity, and gives a polycarboxylic acid having high Ca-capturing ability. That is, a four-component catalyst of Ce'Bi'Pt'Pd that uses two kinds of catalysts, palladium and platinum, as the first component of the catalyst, uses bismuth as the second component of the catalyst, and cerium as the third component of the catalyst. (Catalyst composition (c)) is one of the high-performance low-temperature active catalysts in which the functions of individual elements are highly complexed. Each element has the following functions.

C e: Pd and Pt high dispersing agent, basicity imparting agent

B i: oxygen poisoning inhibitor, product poisoning inhibitor

P t: Low temperature activator

P d: 1 极 hydroxyl oxidizing ability (under basic conditions), main catalytic element B i · P t: Secondary hydroxyl oxidizing ability (under acidic conditions)

This four-component catalyst is composed of a composite of a Ce · Bi-Pd catalyst system that exhibits primary hydroxyl oxidizing ability and a Bi · Pt catalyst system that exhibits secondary hydroxyl oxidizing ability. Therefore, for example, when glycerin is used as a starting material, the primary hydroxyl groups of glycerin are oxidized by the Ce, Bi, and Pd catalysts. The secondary hydroxyl group of the resulting tartaric acid is efficiently oxidized by the Bi-Pt catalyst to induce keto-σ-acid. The composition of the other components (Pt, Bi, Ce) with respect to palladium as the main catalytic element can greatly control the catalytic performance and product composition.

As shown in the catalyst composition (2), for example, palladium alone may be used as the catalyst composition in the present invention, but preferably, the catalyst composition is combined with the second component of the catalyst (catalyst composition (a)) By combining with the third catalyst component (catalyst composition (mouth)) and further combining with the second catalyst component and third catalyst component (catalyst composition (c)), two more catalyst components can be used. By using them together, 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 significant effect on catalytic activity. Accordingly, the following range of the atomic ratio R 1 of the bulk of the second catalyst component to the first catalyst component is selected depending on the type of the second catalyst component. When the second component of the catalyst is selenium, R 1 is 0.05 to 0.3, preferably 0.05 to 0.10. When the second component of the catalyst is tellurium, bismuth, antimony, or 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 R 1 is 0.2. At this time, it is estimated that the surface structure has a ^ 3X ^ 3R30 ° structure.

The amount of catalyst supported affects the molecular weight of the polymer produced, and the lower the supported amount, the higher the molecular weight. The supported amount of the first component of the catalyst is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight, particularly preferably 0.1 to 3% by weight of the total supported catalyst (including the catalyst support). % By weight. In particular, when the first component of the catalyst is palladium, when used alone, or when combined with the second and third components of the catalyst to form a composite Is preferably 0.5 to 10% by weight, more preferably 1 to 6% by weight. If the amount is less than 0.5% by weight, the reaction rate is low. If the amount exceeds 10% by weight, there is a problem in cost.

The loading amount of the second component of the catalyst depends on R 1 described above, but is usually 0.1 to 10% by weight, preferably 0.1 to 5% by weight, particularly preferably 0.1 to 5% by weight from the viewpoint of catalytic activity. 5 to 3% by weight.

The atomic ratio R2 of the bulk of the third catalyst component to the first catalyst component is usually 0.01 to 1.0, preferably 0.05 to 0.5, and more preferably 0.1, from the viewpoint of catalytic activity. ~ 0.3.

The loading amount of the third component of the catalyst is usually 0.1 to 5% by weight, preferably 0.3 to 3% by weight, particularly preferably 0.3 to 5% by weight from the viewpoint of catalytic activity.

The catalyst composition according to the present invention comprises a catalyst component supported on a catalyst carrier in water by a usual impregnation method, co-impregnation method, immersion method, or co-precipitation method, formalin, hydrazine, sodium borohydride, hydrogen, It can be easily prepared by a usual method such as reduction treatment with low alcohol (methanol, ethanol, glycerin, ethylene glycol, etc.). In particular, when the catalyst component is supported on the catalyst carrier in an aqueous solution, a highly active catalyst can be easily obtained by carrying out the reduction treatment in the water in a dispersed state without dehydrating and drying the catalyst precursor after the support. In preparing the catalyst, the outer layer (eg, eggshe 11 type) in which the catalyst component is mainly supported on the outer layer of the catalyst carrier is very effective for mass transfer since the reaction of the present invention is a polymerization reaction. Bismuth, which is the second component of the catalyst used as an oxygen poisoning inhibitor, is particularly effective for the effect of supporting the outer layer. This is because, as described above, bismuth has an ad-atom structure or ad-1 ayer structure in comparison with the other catalyst second component. This is likely to be due to the large suppression of the adsorption of the formed polymer. This specificity of bismuth was measured by measuring the amount of C0 adsorbed on the two-component catalyst with palladium.In the case of bismuth, unlike the other second component of the catalyst, tellurium and lead, the amount of adsorbed palladium alone was It can be understood from the sharp decrease as mentioned above. The surface structure of the outer layer-supported catalyst largely depends on the preparation method, but basically depends on the surface properties of the main catalyst element palladium and the second catalyst component. In preparing the outer-layer supported catalyst, the supporting time is also an important factor. In the liquid phase equilibrium adsorption stage loading method performed in the present invention, the loading time is 5 hours or less, preferably 2 hours or less.

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

Activated carbon as a catalyst carrier used in the present invention may be derived from any of coconut shell, woody, coal-based, beet coal-based or petroleum pitch-based raw materials, but in particular, ignition residue or ash content It is effective to use coconut shell, woody or petroleum pitch based on low oil content. The activated carbon may be activated by either steam activation or chemical activation, but a water vapor activated product may be more effective as a carrier. Commercially available activated carbon as the catalyst carrier used in the present invention may be used as it is, but it may be used after adjusting the pore distribution or reducing ash content by appropriate pretreatment, for example, acid treatment. Good. As the commercially available granular and powdered activated carbon used in the present invention, those for general water treatment and for water-soluble food purification are used. For example, granular white purple series (WH, Sx, KL) and powdered activated carbon represented by carboraffin, granular activated carbon manufactured by Norit (R0X, RAX, DARCO, C, ELORIT, etc.) and powdered products (AZ0, PN, ZN, etc.), Kureha Chemical bead-shaped activated carbon (BAC) is an example.

Commercially available carbon black is also effective as a catalyst carrier for carrying out the reaction in the present invention, and includes, for example, carbon black manufactured by Cablack Corporation. 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 a very important factor, and greatly affects the yield of the polymer having a carbonyl group 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 at the lowest possible temperature in both the oxidation reaction section and the polymerization section of the reaction scheme. The reaction can be carried out at a temperature of from 130 to 100, but preferably from 110 to 60, more preferably from 0 to 60, in order to suppress decarboxylation of the produced polymer as much as possible. It is preferably carried out at 50, particularly preferably at 20 to 40.

That is, in the present invention, the lower the reaction temperature, the more easily a polymer is formed, and the by-product of sodium carbonate due to decarboxylation can be kept at several percent or less. In addition, the optimal reaction temperature in the monomer formation stage and the polymer formation stage is different.The former is less than 60 and the latter is less than 30.However, in order to give priority to polymer production, the reaction should be performed at as low a temperature as possible. Is good. Furthermore, lower temperatures are more advantageous in terms of oxygen solubility. Therefore, the use of the catalyst composition having a low temperature activity in the present invention allows the oxidation polymerization at room temperature to proceed efficiently. The reaction time largely depends on the reaction temperature, the type of catalyst and its concentration, etc., but usually 1 to 30 hours Is preferred.

In the present invention, since the carboxyl group generation step is carried out in an aqueous solution in a basic atmosphere, the resulting 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 produced at the applied reaction temperature. That is, the raw material concentration is usually preferably from 1 to 80% by weight, more preferably from 5 to 50% by weight. If the raw material concentration is less than 1%, 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 is reduced, resulting in a large reaction rate. descend.

It is effective to use water as the reaction solvent from the viewpoint of productivity and efficiency.

In the reaction of the present invention, the synthesis of a monomer precursor and a monomer by an oxidation reaction in a basic atmosphere and the progress of the oxidative polymerization reaction require sodium hydroxide, potassium hydroxide, and hydroxide as alkaline agents required for the synthesis. Hydroxides of alkali metals such as lithium, amines such as monoethanolamine and diethanolamine, and ammonia are used.

In this case, the excess amount of alcohol becomes an important reaction factor and controls pH during the reaction, and has a great influence on the structure and degree of polymerization of the polymer of the present invention. As a result, C a as a builder for detergents is obtained. It has a significant effect on capture performance. For example, when the present invention is carried out using glycerin as a starting material as in the following formula, sodium hydroxide, for example, is used as an alcohol agent in a molar amount twice that of glycerin. CH ₂ OH C 0 ON a C 0 ON a

I

CHOH CHOH C = 0

I

CH ₂ OH C 0 ON a C 0 ON a

C 0 ON a C 0 ON a

I I

(C-1 0) — (C-1 0) —

I I

C 0 ON a H

As a result, sodium hydroxide is consumed in the same amount up to polyketomalonic acid, but boriketomalonic acid is thermodynamically unstable, so that part of carboxyl is easily decarboxylated. As a result, glyoxylic acid skeleton is present in the polymer chain and excess sodium hydroxide is generated. This excess sodium hydroxide usually reacts with decarbonated carbon dioxide to produce sodium bicarbonate-sodium carbonate.

Therefore, when the raw material is glycerin, the equivalent ratio of charged sodium hydroxide is preferably 0.50 to 0.90 with respect to glycerin. Also, 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, water based on the above points is taken into consideration. It is preferable to adjust the excess of sodium oxide and to set the pH of the aqueous solution of the reaction mixture so as to meet the conditions of the present invention.

In the case of producing the polymers () to (IV) and (VI), the pH at the time of the reaction is preferably 7 to 13 when producing the monomer. On the other hand, during polymerization, the pH is preferably 7 or less, preferably 6.0 to 2.5, and particularly preferably 4.5 to 3.0.

On the other hand, when producing the polymer (V), the pH is preferably from 9 to 14 for both the production of the monomer and the polymerization. For example, using a stirred tank reactor When producing the polymers (I) to (IV) and (VI), the PH is set to 7 to 10 when the production of the monomer is mainly at the beginning of the reaction, and the polymerization reaction during the middle to the end of the reaction is mainly performed. At this point, it is advisable to control the feed rate of the raw materials (alkaline and oxidizing agents) so that the pH is 7 or less.

In addition, when the polymers (I) to (IV) and (VI) are produced using a fixed bed reactor, the production of mozomers mainly proceeds in the upper stage of the reaction tower, and the polymerization reaction proceeds in the middle to lower stages of the reaction tower. Mainly progress. In this case, the PH in the height direction of the reaction tower tends to drop greatly from the upper stage to the lower stage, and the raw materials (alkaline agent, oxidizing agent) are supplied from a plurality of locations in the middle stage of the reaction tower as needed. It is preferable to maintain the pH of the reaction mixture at the outlet of the reaction column at 6.5 to 2.0. On the other hand, when the polymer (V) is produced in a fixed-bed reactor, the outlet pH is preferably maintained at 9 to 14, preferably at least 10.

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

In the reaction of the present invention, monomers which are oxides of glycerin are mainly formed in the initial stage of the reaction, but in the middle to late stages of the reaction, the polymerization reaction using these monomers as a raw material proceeds. Therefore, the effect of mass transfer becomes significant in the polymer production process, and as a result, the reactivity is greatly reduced due to the poisoning of the product. is there. The amount of oxygen supplied is preferably increased with the increase in the molecular weight of the produced polymer, preferably 3 times or less of the equivalent, particularly preferably 0.5 to 2 times the equivalent. Is good. Excessive increases in oxygen supply, on the other hand, also result in self-poisoning of the catalyst by oxygen.

The reaction in the present invention is a stirred tank type reaction depending on the form of the catalyst composition Vessel or fixed bed reactor (tricklebed). When a fixed bed reactor is used, it is preferable to dilute and fill the catalyst composition of the present invention with a diluent (reactive inert particulate matter). At this time, the catalyst composition is preferably diluted with 0.5 to 20 parts by weight of a diluent with respect to 1 part by weight of the catalyst composition, and more preferably 4 to 15 parts by weight. By diluting with a diluent, product poisoning due to adsorption of the produced polymer is remarkably mitigated, and high productivity can be achieved. If not diluted with a diluent, the retention of the polymer on the catalyst surface will be large, and the reaction rate may decrease drastically due to a large decrease in mass transfer rate.

In addition, when the fixed bed reactor is filled with the catalyst as described above, the catalyst is mixed with a diluent and charged, thereby increasing the catalyst effectiveness coefficient, and as a result, the catalyst activity is increased by two to three times. There is.

The material of the diluent may be any material that does not adversely affect the reaction of the present invention, and examples thereof include reaction-inactive particulates such as porcelain, ceramics, polymers, glass and metals. The particle size of the diluent is not particularly limited, but is preferably 1/2 to 5 times the size of the catalyst carrier.

The choice of the reactor is not particularly limited, but if the obtained polymer has a weight-average molecular weight of 100,000 or more and a high-viscosity polymer is produced, use a stirred tank reactor. Is preferred. However, when the weight average molecular weight is about 500 to 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. You.

Next, the reaction method of the present invention will be described with reference to an example in which an aqueous glycerin solution is used as a starting material. When the reaction is carried out using a stirred tank reactor, a stirrer, thermometer, pH meter, Feed gas (oxygen, air, etc.) An aqueous glycerin solution and a catalyst composition are charged into a stirred tank batch reactor equipped with an inlet pipe and waste gas line, set to a predetermined temperature, and oxygen or air as an oxidizing agent. Is introduced, and an aqueous solution of sodium hydroxide is added continuously so as to maintain a predetermined pH. By reacting for a predetermined time, the polymerization reaction proceeds together with the production of the monomer by the oxidation reaction, and the polymer having a carboxyl group of the present invention is produced.

When a trickle bed fixed bed reactor is used, for example, the molded catalyst composition is mixed with a diluent and charged into a reaction tower, and the mixture is placed in a reaction tower before the oxidation reaction of the present invention is carried out. It is preferable to perform a reactivation treatment of the charged catalyst. 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 decrease. In carrying out the reactivation, without supplying a basic substance (such as sodium hydroxide), which is one of the starting materials for this reaction, for example, it is possible to use a starting material such as glycerin, ethylene glycol, etc. This is achieved by feeding a 20% by weight aqueous solution to the reaction tower all day and night at a temperature between room temperature and 50 under an air supply. After the reactivation of the catalyst, an aqueous glycerin solution, an aqueous sodium hydroxide solution, and oxygen or air as an oxidizing agent may be supplied from the top of the reaction tower in a downward cocurrent flow. In this case, the liquid hourly space velocity of the total standard of Ryohara charge aqueous solution is 0 5-0 0 1 -.. ^1, the preferred properly set to 0. 2 to 0 0 5 h- ^1...

The composition of the product up to 24 to 48 hours after the start of the raw material supply is 40 to 60% by weight of the monomer, and the polymer component is 60 to 40% by weight. The amount decreases, and at the same time, the ability of the polymer obtained to capture Ca greatly increases. Changes in the monomer content of the reaction product over time were measured by HPLC (high-performance liquid chromatography). E) and GPC (Gel Vermillion Chromatography), but the HPLC baseline is usually significantly disrupted by polymer formation.

If the pH of the reaction at the time of carrying out the reaction of the present invention exceeds 9, the production of aldehyde carboxylic acid (V in the reaction scheme) is promoted. However, since this polymer also has a carboxyl group, the biodegradability is low. No, but has C a capture ability.

Separation of the resulting polymer from the reaction mixture should be carried out by lyophilization by dehydration 透析 Dialysis using a membrane filter 溶剤 Solvent reprecipitation using a solvent such as isopropyl alcohol, ethanol or methanol Can be done. When the reaction mixture is subjected to freeze-drying or reprecipitation by a solvent reprecipitation method, the polymer according to the present invention can be obtained as a white powder by drying after the solvent is separated.

However, when the polymer according to the present invention is used as a builder for a detergent, the aqueous solution of the oxidative polymerization reaction mixture discharged from the reaction tower is mixed with a detergent slurry and spray-dried without separating the polymer. Can be.

The weight average molecular weight of the polymer obtained in this way reaches 500 to 1,000,000 by gel filtration (GPC) analysis, and that of the conventional polyglycerin (molecular weight 500,000). 1 100 000). However, when it is used as a detergent builder, it is preferably from 100,000 to 100,000, particularly preferably from 200,000 to 20,000 in terms of chelating ability.

In the GPC measurement of the polymer obtained in the present invention, particularly when the terminal stabilization treatment is not performed, the polymer may be easily adsorbed on the column り or may be decarboxylated depending on the type of the packing material. Hit the measurement It is necessary to select the optimal column system.

In the polymer of the present invention, absorption peaks of carboxylate vibrational vibration and ether bond vibrational vibration of the carboxylate are obtained from the infrared absorption spectrum, and proton NMR and C ₁₃ NMR spectra are obtained. From the vector, the absorption peaks of the proton and the etheric carbon bonded to the etheric carbon are obtained. This proves that the polymer in the present invention is a polymer having a large amount of carboxyl groups.

1 •

The structure includes any one of the formulas (i), (ii), (iii), (iv), (V), and (vi), or includes two or more structural units. It is presumed to consist of a structure. This is derived from the fact that the polymerization reaction proceeds during the oxidation reaction, and is a characteristic of the production method of the present invention.

C 0 OM C 0 OM

(C-0) (C-1 0) (ii) C 00M H

C 0 OM COO

C HOH C = 0

(C-0) (iii) (C-0) (iv) H H

COOM

(C = C) (v) — (C-1 0) — (vi) MO-0 ■ C OH ...... '' ^ CH ₈ ;

(Where M is a hydrogen atom, an alkali metal, an ammonium group,

Represents monoethanolamine, diethanolamine, etc. ) Further, the polymer was removed monomer components from the reaction mixture in the present invention, 1 0 0~6 0 0 mg - from having a C a CO ₃ as high as Zg ion exchange換能useful as detergent builders.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

In the following examples, the percentages indicated with respect to the amount of catalyst carried indicate weight%. The conversion rate of the hydroxyl compound indicates the ratio of the number of moles consumed in the oxidation reaction to the charged hydroxyl compound. All conversion percentages are by weight. Further, the polymer yield is a value excluding the molar residual ratio of the hydroxyl compound, the monomer and the monomer precursor remaining in the reaction mixture. Polymer yield (mol = hydroxyl compound in reaction product + monomer 10 monomer precursor (mol)

Hydroxyl compound charged (mol)

X 100 Each analysis performed in Examples was performed by the following method.o

(Analysis of polymer)

The reaction mixture was reprecipitated by a solvent reprecipitation method using ethyl alcohol, and the solvent was separated, followed by drying. The obtained hygroscopic white powder was analyzed by infrared absorption spectrum, NMR spectrum and gel filtration chromatography (GPC).

The GPC measurement conditions are shown below.

'Column: G 2 0 0 S-G 4 0 0 SW (Tosoichi Before conducting the analysis of the polymer, it is necessary to pass an aqueous solution of a formalin condensate of sodium naphthalene sulfonate through the column and adsorb this condensate to silica gel. It is.

Solvent 0.1 M-N aC 1 aqueous solution acetonitrile = 7/3 Flow rate 0.8 ml / min

Temperature 25 ^e C

Detector U V-8 0 1 1 (manufactured by Tosoichi), measured at 210 nm Sample concentration 0.1% aqueous solution

(Quantitative analysis by HP LC)

The conditions of HPLC are shown below.

'' High-speed liquid chromatography: D-250 / L-600, manufactured by Hitachi, Ltd.

Detector L-330 type (RI monitor)

Column C-6 1 0 S

Eluent 0.5%-phosphate aqueous 0. 5 m 1 / min Pressure 1 0 K g / cm ²

Temperature 50 ^e C

(Ca capture ability)

Using the polymer fractionated in the following examples, its ability to capture Ca 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. The 0.1 g was precisely weighed and adjusted to 100 ml with 0.1 により -ΝΗ4 C 1 -NH * OH buffer solution (pH 10.0) to obtain an aqueous polymer solution. After inserting a calcium ion electrodes in the solution, under stirring at Maguneti Kkusutara, C a C 1 ₂ aqueous solution (pH 1 0 corresponding to 2 0, 0 0 0 p pm at C a C 0 ₃ conversion calculated. 0) was dropped by a burette, and the Ca ion concentration in the liquid was measured by an ion analyzer. The Ca capture ability was determined from the inflection point by plotting the relationship between the titer and the residual Ca ion concentration.

(Preparation of catalyst composition)

Wood-based activated carbon from Takeda Pharmaceutical Co., Ltd., catalyzes WH ₂ C (specific surface area: 1200 m ² / g, bulk density: 500 / liter, pore volume: 0.8 ml Zg) A three-component catalyst consisting of 0.9% Ce '3. Q% i-3.0%? DZC as a carrier was prepared by the following method. 93 g of activated carbon dried with hot air at 120 ° C for 24 hours was dispersed in 125 ml of ion-exchanged water. Meanwhile, cerium chloride _{(C e C l 3 · 7} Η 2 0) 2. 4 g, bismuth chloride (B i C 13) 4. 5 g and chloride palladium (P d C l ₃₎ of 5. 0 g, The mixture was uniformly dissolved in 150 ml of ion-exchanged water with stirring in an aqueous hydrochloric acid solution in which 26 ml of concentrated hydrochloric acid was added. The resulting homogeneous brown solution of the catalyst component was added to an aqueous dispersion of activated carbon, and the catalyst component was loaded at room temperature for 5 hours with stirring. The supernatant 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 a 20% aqueous sodium hydroxide solution, and a 37% aqueous solution of formalin 20 m 1 Was added. Under stirring, the temperature was raised to 80, and a reduction treatment was performed at 80 at 30 minutes. The resulting catalyst was allowed to cool to room temperature, washed three times with 1500 ml of ion-exchanged water, and filtered under reduced pressure. By the above operation, 0.9 g of 0.9% Ce · 3.0% Bi · 3.0% PdZC catalyst having a water content of about 50% was obtained in terms of a dry product. one

The other catalyst compositions in this example were prepared in the same manner.

Example 1 0.9% Ce'3.0% Bi3.0% PdZC catalyst prepared in the preparation example of the catalyst composition was prepared with a jacketed inner diameter of 2 Omm and a height of 700 mm. A fixed-bed reactor made of Pyrex having an m of 1 was charged with 100 g in terms of a dried product. The reaction temperature was set at 50, and a mixed solution of 100 parts of a 50% aqueous glycerin solution and 130 parts of a 30% aqueous sodium hydroxide solution was poured from the top of the reaction tower with a liquid hourly space velocity (LHSV ) At a flow rate of 0.07 hr- ¹ , oxygen gas was supplied in a downward cocurrent flow at a flow rate of 5 N liter r. After 40 hours, a colorless and transparent viscous liquid (pH 10 to 11) was distilled off from the reaction tower outlet. When this liquid was analyzed by high performance liquid chromatography (HP LC), the conversion of glycerin was 100%, the selectivity of residual tartaric acid was 30%, and the selectivity of glyceric acid was 25%. 0 which was at - how, GPC (gel permeation Chromatography) analysis of this viscous liquid (FIG. 2) the place, the weight average molecular weight of Helsingborg styrenesulfonic acid sodium criteria ^{4. 5 0 3 X 1 0 4} . It was confirmed that a polymer of 5.2 was 96 in weight, and a polymer of 7.23 × 10 ³ in weight was 6.8% by weight (total 12 weight). This viscous liquid was dialyzed to separate one component of Bolima. From the obtained infrared absorption scan Bae-vector of Borima, confirmed the presence of Karubokishire bets and ether bond, and further confirmed the presence of carbon and hydrogen ether linkages than pro tons NMR and C ₁₃ NMR spectrum . From these results, it was estimated that the structure of the obtained polymer was composed of the structural units of the above-described formulas (i) to (iv). In addition, as a result of measuring the Ca ion trapping ability, it was found to be 440.0 mg—C a C 03 / g per unit weight of the preparative polymer.

Example 2

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% aqueous sodium hydroxide solution was used. Reaction. GPC measurement of the reaction mixture revealed that 16% of a polymer having a weight average molecular weight of 62,000 based on sodium borostyrene sulfonate was present. From the infrared absorption spectrum and the NMR spectrum, it was estimated that the structure of one component of the polymer obtained by dialysis separation was composed of the structural units of the formulas (i) to (iv). In addition, as a result of measuring the C a ion trapping ability, it was found to be 450 mg-C a C 03 / g per unit weight of the preparative polymer.

Example 3

The reaction was carried out in the same manner as in Example 1 except that the catalyst composition was 0.9% Ce and 5% Te · 3.0% Pd / C. When a colorless and transparent viscous liquid (pH approx. 10) distilled out from the outlet of the reaction tower was analyzed by HP LC, the conversion of glycerin was 100% and the selectivity of residual taltronic acid was 15%. Glyceric acid selectivity was 22%. On the other hand, GPC measurement confirmed that 25% of a polymer having a weight average molecular weight of 58,000 based on sodium polystyrenesulfonate was present. The presence of carboxylate and ether bonds was confirmed from the infrared absorption spectrum of the polymer after dialysis separation, and the presence of carbon and hydrogen at the ether bond was confirmed by proton NMR and C ₁₃ NMR spectra. confirmed. From these results, it was estimated that the structure of the obtained polymer was composed of the structural units of the above-described formulas (i) to (iv). In addition, as a result of measuring Ca ion trapping, 45 Omg-Ca CO 3 / g was obtained 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 an aqueous solution of 50 tartronic acid and 130 parts of an aqueous solution of 23¾ sodium hydroxide was used. From the GPC measurement of the reaction mixture, It was found that 19% of a polymer having a weight average molecular weight of 47,000 based on sodium phosphate was present. From the infrared absorption spectrum and the NMR spectrum, the structure of the polymer component obtained by dialysis-separating the polymer component was estimated to be composed of the structural units of formulas (i) to (iv). Also, as a result of measuring the Ca ion trapping ability, 45 O mg-Ca C Os was given per unit weight of the preparative polymer.

Example 5

Examples for various catalyst compositions (1.5% T e '3.0%? D / C, 1.5% Ce · 3.0% P d / C, 3.0% P d / C) The reaction was carried out as in 1. For each catalyst composition, the weight average molecular weight of the fractionated polymer was 58,000, 43,000, 40,000, respectively. Table 1 summarizes the yield of bolimer and the ability to capture C ion. The structure of the polymer component was estimated from the infrared absorption spectrum and the NMR spectrum to be composed of the structural units of formulas (i) to (iv).

Example 6

Using a mixed solution of 100 parts of a 25% glycerin aqueous solution and 150 parts of a 15% sodium hydroxide solution, 0.75% Pt.3.0% Bi-3 as a catalyst composition The reaction was carried out in the same manner as in Example 1 except that 0.0% PdZC was used and the reaction temperature was 25. Table 1 summarizes the polymer yield and C a 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 estimated to be composed of the structural units of formulas (i) to (iv) from the infrared absorption spectrum and the NMR spectrum.

~ O

Example 7

When the catalyst composition is 0.8% C e 'l. 5 ¾B i · 0.75 ¾P t-3 The reaction was carried out in the same manner as in Example 6, except that 0.0% PdZC was used. 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 presumed to be composed of the structural units of the formulas (i) to (iv) from the infrared absorption spectrum and the NMR spectrum.

Example 8

The catalyst composition of the first reaction tower (same reactor as used in Example 1) was 0.8% Ce'l. 5% Bi-0.75% Pt-3.0% Ρ CNO C, Example 6 except that the catalyst composition of the second reaction tower (same reactor as used in Example 1) was 0.6% Bi '3.0% Pt ZC. The reaction was performed similarly. The reaction mixture leaving the first reaction tower was directly introduced into the second reaction tower at the same flow rate. The pH of the distillate at the outlet of the reaction tower was 3.5, and white crystals were precipitated in the receiver. It was identified as ketomalonic acid by HPLC. Table 1 summarizes the polymer yield and Ca ion capture capacity. The structure of the polymer component was estimated to be composed of the structural units of formulas (i) to (iv) from the infrared absorption spectrum and the NMR spectrum.

Example 9

The 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 to be composed of the structural units of formulas (i) to (iv) from the infrared absorption spectrum and the NMR spectrum.

Example 10

Glycerin and 1,2-propylene glycol in a molar ratio of 1: 1 The reaction was carried out in the same manner as in Example 9 except for mixing. The pH of the distillate at the outlet of the reaction tower was 3.5. Table 1 summarizes the polymer yield and the ability to capture Ca ions. The structure of the polymer component was estimated to be composed of the structural units of the formulas (i) to (iv) from the infrared absorption spectrum and the NMR spectrum.

Example 1 1

Same as Example 7 except that the catalyst composition of Example 7 was diluted 4 times in terms of weight using glass beads with a diameter of 0.8 mm as a diluent and then charged into the reaction tower used in Example 1. The reaction was performed. 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 was estimated to be composed of the structural units of formulas (i) to (iv) from the infrared absorption spectrum and the NMR spectrum.

Example 1 2

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

Example 1 3

In Example 12, the catalyst composition was replaced with 0.6% Bi, 3.0% Pt / C, 100 g, and the air supply rate was changed to 3.0 liter Zh. Example 12 except that the reactant of 12 was used as a raw material. Reacted similarly. The pH of the reaction mixture was 6.2. Table 1 summarizes the volima yield and Ca ion trapping ability. The structure of the polymer component was estimated from the infrared absorption spectrum and the NMR spectrum to be composed of the structural units of the formulas (i) to (iv).

Example 14

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

Example 15

The reaction was carried out in the same manner as in Example 7, except that the starting material was glycolic acid. Table 1 summarizes the polymer yield and Ca ion trapping ability. The pH of the distillate at the outlet of the reaction tower was 5.3. The structure of the polymer component was estimated from the infrared absorption spectrum and the NMR spectrum to be composed of the structural unit of the formula (ii).

Example 16

The reaction was carried out in the same manner as in Example 7, except that the raw material was propylene glycol. Table 1 summarizes the polymer yield and the ability to capture C ion. The pH of the distillate at the outlet of the reaction tower was 5.7. The structure of the polymer component was presumed to be composed of the structural unit of the formula (vi) from the infrared absorption spectrum and the NMR spectrum.

Example 17

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

Example 18

The reaction was carried out in the same manner as in Example 7, except that the raw material was lactic acid. Table 1 summarizes the polymer yield and Ca ion capture ability. The pH of the distillate at the outlet of the reaction tower was 5.7. The structure of the polymer component was estimated to be composed of the structural unit of the 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.

After 20 hours, a brown reaction solution (pH 13) was distilled from the outlet of the reaction tower. Analysis of this solution by HPLC showed a glycerin conversion of 100%. As a result of GPC analysis, it was confirmed that 37 weight of a polymer having a molecular weight average molecular weight of 450,000 based on polystyrenesulfonic acid was present.

The structure of the polymer component was estimated from the infrared spectrum and the NMR spectrum to be composed of the structure of the formula (V). Further, C a ion trapping ability of the reaction mixture was _{1 2 Omg- C a C0 3 Zg} .

table 1

Industrial applicability

According to the production method of the present invention, a polymer having a carboxyl group, which is useful as a biodegradable detergent builder or the like, having a unique function such as high ion exchange ability, can be efficiently produced using inexpensive raw materials. Can be manufactured 0

Claims

The scope of the claims

1. A hydroxyl compound is contact-oxidized in the presence of the following catalyst composition and oxidizing agent to produce a monomer having a carboxyl group, and has a carboxyl group characterized by polymerizing the monomer. A method for producing a polymer.

Catalyst composition:

One or more elements selected from the group consisting of palladium, platinum, rhodium, and ruthenium are used as the first catalyst component, and one or more elements selected from the group consisting of bismuth, tellurium, tin, lead, antimony, and selenium are included. The second component of the catalyst, at least one element selected from rare earth elements is the third component of the catalyst,

(B) Catalyst first component and catalyst second component

(Mouth) Catalyst first component and catalyst third component

(C) catalyst first component, catalyst second component and catalyst third component, or

(2) Catalyst first component only

A supported catalyst comprising:

2. The method according to claim 1, wherein the hydroxyl compound is glycerin, glyceric acid or a salt of glyceric acid.

3. The production method according to claim 1, wherein the hydroxyl group compound is tart baltic acid or a salt thereof.

4. The production method according to claim 1, wherein the hydroxyl compound is a salt of ethylene glycol, glycolic acid or glycolic acid.

5. The method according to claim 1, wherein the hydroxyl group compound is propylene glycol, hydroxyaceton, 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 catalyst composition according to any one of claims 1 to 6, wherein the first catalyst component of the catalyst composition (c) is palladium and platinum, the second catalyst component is bismuth and / or tellurium, and the third catalyst component is cerium and / or lanthanum. Production method.

8. The process according to any one of claims 1 to 6, wherein the reaction is carried out in a fixed bed reactor filled with the catalyst composition.

9. The production method according to claim 8, wherein the mixture is diluted with 0.5 to 10 parts by weight of a diluent per 1 part by weight of the catalyst composition and filled.

10. The production method according to any one of claims 1 to 9, wherein the polymer having a carboxyl group has a weight average molecular weight of 500 to 1, 000, 0000 by gel filtration chromatography.

11. The production method according to any one of claims 1 to 10, wherein the calcium capturing ability of the polymer having a carboxyl group is from 100 to 600 mg-CaC08.