KR820001098B1 - Improved ion exchange resin - Google Patents

Abstract

Peroxyester (I; R1 = branched C3-12 alkyl; X = 1-2) and peroxydicarbonates (II; Y, Z = lower alkyl, cycloalkyl, alkyl-substituted cycloalkyl, aralkyl) are used as catalyst in the manuf. of thermosetting ion exchange particle. Thus, a mixt. contg. styrene 500.4, divinylbenzene 85.6, and t-Bu peroctoate 1.9 g was mixed with water 510, poly (diallyldimethylammonium chloride) 20.1, gelatin 1.6, and boric acid 0.88g and a 50% NaOH soln. was added to adjust the pH to 10.0-10.5. The mixt. was heated to 75≰C in 45 min and kept at this temp for 4 hr to give copolymer particles which were treated with H2SO4.

Description

Process for preparing hard and segmented crosslinked copolymer beads

The present invention relates to a process for the preparation of hard, segmented crosslinked copolymer beads for making ion exchange resins.

More specifically, the present invention relates to an improved process for using special groups of peroxy esters and peroxydicarbonate catalysts as polymerization catalysts for the polymerization of monomers to make ion exchange beads. Techniques for preparing bead-shaped crosslinked vinyl copolymers (preparatives for conversion to ion exchange resins) by free catalyst polymerization of monomer mixtures in aqueous solutions are well known.

"Cross-linked vinyl copolymer" and similar terms are used to succinctly represent the main elements. That is to say it contains 50-99.5 mole percent, preferably 80-99% of monovinyl monomers.

Examples of the main component are monovinyl aromatic monomers such as styrene, vinyltoluene, vinylnaphthalene, ethylvinylbenzene, vinylchlorobenzene, chloromethylstyrene and the like and esters of acrylic acid and methacrylic acid, namely methyl acrylate and ethyl acrylate. , Propyl acrylate, isopropyl acrylate, butyl acrylate, t-butyl acrylate, ethylhexyl acrylate, cyclohexyl acrylate, isobronyl acrylate, benzyl acrylate, phenyl acrylate, alkylphenyl acrylate, epoxy Methyl acrylate, epoxypropyl acrylate, propoxypropyl acrylate, ethoxyphenyl acrylate, ethoxybenzyl acrylate, ethoxycyclohexyl acrylate and its corresponding esters of methacrylic acid.

The minor component is polyvinyl compounds having about 0.5-50 mole percent, preferably 1-20%, which is polymerizable with the aforementioned monovinyl monomers to form crosslinked insoluble, incompatible copolymers. Have at least two active vinyl groups, and known polyvinyl compounds are, for example, divinylbenzene, trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, divinyltoluene, trivinylbenzene, divinylchlorobenzene, Diallyl phthalate, divinylpyridine, divinyl naphthalene, ethylene glycol diacrylate, neopentyl glycol dimethacrylate, diethylene glycol divinyl ether, bisphenol A-dimethacrylate, pentaerythritol tetra- & trimethacrylate , Divinyl styrene, divinyl ethyl benzene, divinyl sulfone, divinyl ketone, divinyl sulfide, allyl acrylate, Allyl maleate, diallyl humarate, diallyl succinate, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, diallyl silicate, diallyl sebacate, divinyl sebacate, diallylate Rate, triallyl tricarbarate, triallyl aconitate, triallyl citrate, triallyl sulfate, N, N'-methylenediazorylamide, N, N'-methylenediacrylamide, N, N'- Ethylene-diacrylamidetrivinylnaphthalene, polyvinylanthracene and glycol, glycerol, penterythritol, polyallyl and polyvinylethers of resorcinol and monoti and dithio derivatives of glycols.

The copolymer may also have other vinyl monomers therein that do not affect the basic properties of the resin material, exceeding about 5% by polymer, polymerized units therein. Examples include methyl acrylate, acrylonitrile, butadiene and other known ones.

Conventional polymerization conditions used so far lead to cross-linked vinyl copolymers, which have some functional drawbacks that result from physical weakness when introducing functional groups into the ion exchange resin.

The use of the present invention results in an ion exchange resin in which polymer beads have greater mechanical strength, a complete complete bead count, and increased resistance to expansion pressures generated in the beads during acid / base circulation.

The greater mechanical strength of the beads by themselves clarifies the increased resistance to physical breakdown by external forces such as the weight of the resin column bed or high flow rates.

Therefore, the physically stronger ion exchange resins expressed here are particularly suited for the treatment of high flow rate fluid streams, eg for wiping down concentrated concentrates of lower quality resins that are prone to mechanical breakdown or short life. useful.

In pending US patent applications, Ser. No. 766,120 (filed Feb. 7, 1977) and 797,716 (May 17, 1977), each of the "reaction modifiers" was added to the oxygen content of the monomer mixture and / or to the monomer mixture during the polymerization reaction. "I suggest improving the properties of the ion exchange resin as a way to control the addition."

The teachings of these pending applications may be used in conjunction with the present invention and therefore they should be regarded as linked herein by reference.

The present invention resides in the discovery that a special group of peroxide catalysts which have not been known to have an advantage in the production of ion exchange polymers, when functionalized, actually produce polymers which are actually and surprisingly better than the equivalent materials ever available.

Catalysts that yield this advantage can generally be characterized as peroxyesters and peroxycarbonates.

Peroxyesters generally include alkylesters and alkenylenebis (esters) of peroxycarboxylic acids having the general formula:

Wherein R ₁ is a branched alkyl group having 3-12 carbon atoms, having secondary or tertiary carbon linked to a carbonyl group.

X is 1 or 2.

When X is 1, R ₂ is a branched alkyl group containing a tertiary carbon attached to oxygen.

In other words,

Wherein R ', R ", R"' are independently selected from straight or branched lower alkyl groups.

When X is 2, R ₂ is an alkylene or aralkylene group.

In each case however, all terminate as tertiary carbons attached to oxygen.

In other words,

Wherein R ', R "are as above and R"' is phenylene or lower alkylene.

Peroxyester catalysts are currently commercially available under the Rushidmark (Rushdolvision, Penwalt Corporation) and are also required for vinyl polymerization.

Peroxydicarbonate catalysts have the following general formula and are useful by the present invention.

Wherein Y and Z are independently selected from lower alkyl, cycloalkyl, alkyl substituted cycloalkyl and alalkyl.

These materials were made commercially available under the name Lucifer Division, "Lupezol" at the Penwalt Company, and "Percadox" at Woori Chemical.

Preferred groups of peroxyester catalysts are t-butyloctoate, t-butylperoxy-2-ethyl-hexanoate, t-butyl peroxyisobutyrate, t-butylperoxy neodecanoate, t-amylpere Octoate, and 2,5-dimethyl-2,5-bis (2-ethyl-hexanoylperoxy) -hexane.

In accordance with the present invention, vinyl monomers, cross-linking monomers and any other monomers are peroxide catalysts (ie "free radical initiators") and, if desired, additionally oxygen and / or as defined in the aforementioned pending US application. It is polymerized in the dispersion solution containing "reaction regulator". In general, about 0.1-2.0%, more preferably 0.3-1.0% of the weight of the monomer mixture, catalyst is required to obtain the advantages of the present invention.

The method of polymerization employed by the present invention is generally no different from the well known methods used so far to prepare ion exchange polymers and resins.

The polymerization is carried out in the usual temperature range of 30-90 ° C., preferably 45 ° -80 ° C., even more preferably 50 ° -75 ° C.

More specifically, it is preferable to use a lower reaction temperature until the initial stage of the polymerization reaction, ie at least 50%, preferably 75% or more of the monomers in the dispersion have reacted.

The above-mentioned temperature is for the initial stage of the polymerization reaction, and it is preferable to raise the temperature by 20 ° -30 ° C. above the initial stage temperature in the final stage of the polymerization reaction. As noted in the pending US application already mentioned, it is possible to operate at temperatures 15 ° -35 ° C. below the temperatures normally used in existing technical methods.

Benzoyl peroxide, t-butylperoctoate, t-butylper about 0.05-0.1% of the monomer weight when reacting at low temperatures, i.e., 30 ° -60 ° C, using the catalysts of the invention (percadox type) In order to obtain a high yield of crosslinked vinyl polymer from initiators such as oxyisobutyrate and the like, a so-called secondary "chase catalyst" active at higher temperatures, i. It may be desirable to use.

Aqueous media in which the polymerization is carried out in dispersed form include small amounts of conventional suspension additives, such as xanthene gum (biosynthetic polysaccharides), poly- (dialkyldiethyl ammonium chloride), polyacrylic acids (and salts), polya Dispersants such as cruamide, magnesium silicate and hydrolyzed poly (styrene-maleic anhydride): protection such as carboxymethyl cellulose, hydroxyalkyl cellulose, methylcellulose polyvinyl alcohol, gelatin and alginate Buffers such as colloids, phosphates, borate salts, and pH adjusting chemicals such as caustic soda, sodium carbonate and the like.

The crosslinked high molecular weight copolymer is regenerated from the reaction vessel as hard, separated beads having particle sizes in the range of 0.02-0.2 mm and average particle sizes of about 0.2-1 mm.

These copolymers are converted to ion exchange resins by attaching functional groups to them in a conventional manner, such functional groups being sulfonamides, trialkyls, amino groups, tetraalkylammoniums, carboxyl groups, carboxylates, amine oxides, phosphates and their techniques. Includes others known from.

Functionalizing reactions that can be performed on vinylaromatic copolymers that yield ion exchange resins can be illustrated as follows.

Sulfonation with concentrated sulfuric acid, chlorosulfonation with chlorosulphonic acid followed by amination, reaction with sulfuryl chloride or thionyl chloride followed by amination, chloromethylation followed by amination. Typical functionalizing reactions for (vinyl) acrylic copolymers include hydrolysis, amidolisis, transesterification of acrylic resins and the like.

Ion exchange resins can be further described by the following forms. Ie a weak acid cation containing a sulfonic (-SO ₃ H) or sulfonate (-SO ₃ M, where M is usually an alkali metal ion) group: carboxy (CO ₂ H) or carboxylate (-CO ₂ M, Where M is usually a weak acid cation comprising an alkali metal ion) group: a strong base anion comprising a tetraalkyl ammonium group, —NR ₃ X, where R is an alkyl or hydroxy alkyl group and X is usually a chlorine or hydroxyl group. And a trialkylamino group, -NR ₂ (R is a weak base anion comprising an alkyl or hydroxyalkyl group.

The improvement in the properties of the resin produced according to the present invention is not apparent until the crosslinked copolymer is converted into an ion exchange resin by the attachment of the aforementioned functional groups.

However, the improved physical strength of these converted resins is evident not only by visual inspection before and after use in ion exchange, but also by the resistance to grinding, which is conveniently measured by the capillary instrument.

For example, strong acid, styrene-type resins produced by the preferred methods of the present invention often exhibit a Catillon value of about 1,000-5,000 gm / bead, while from copolymers prepared by conventional polymerization techniques. Derived resins have a captylon value of about 50-500 gm / bead. Likewise, the strong base styrene-type resins of the present invention often exhibit a capillary value of 500-1500, while the resins derived from copolymers prepared by the prior art have a capillary value of 25-400.

The method of the present invention is made clear by the following examples which are not to be construed as limiting thereto.

[Example 1]

The polymerization vessel is a two-necked three-liter round bottom flask equipped with a two blade wide stirrer, a thermometer, a cooler, a heating lid with a thermostat and an inert gas.

The vessel is filled with a monomer mixture consisting of 500.4 g of styrene, 85.6 g of divinylbenzene and 1.9 g of t-butylperoctoate. The upper space is swept away with nitrogen and the following liquid phase is added. : 510 g water, 20.1 g poly (diallyldimethyl ammonium chloride) dispersant 1.6 g geloprotective colloid, 0.88 g boric acid, and 50% caustic soda solution sufficient to maintain pH between 10.0-10.5, stirrer The reaction mixture is heated from room temperature to 75 ° C. for 45 minutes and held at this temperature for 4 hours.

The polymerization reaction is then completed by maintaining the reaction mixture at 95 ° C. for 1 hour, and the copolymer is separated, washed and prepared for functionalization.

The strong acid resin can be prepared from the copolymer of Example 1 by one of the following two methods.

Sulfonated A

The copolymer beads (110 g) prepared above were added to 600 g of 95% sulfuric acid and placed in a 1 L flask equipped with a stirrer, a cooler, a drop funnel, a thermometer, a cleaning brush, and a heating device. 39 g of ethylenedichloride (bead swelling agent is added and the suspension is heated for 3 h intervals from 30 ° C. to 130 ° C. The next product is hydrated with water to cool the product. The sulfonated product is then wiped off and the residue acid is removed.

The physical properties of strong acid resin products are described in Table 1 below.

Sulfonated B

50 g of the copolymer beads prepared in Example 1 was added to 315 g of 94% sulfuric acid, and put into a 1 L flask equipped with a stirrer, a cooler, a dropping funnel, a thermometer, a cleaning brush, and a heating device. After adding 30 g of ethylene dichloride (bead expanding agent) the suspension is heated to 60-65 ° C. and held for 1 hour. The mixture is then heated to 115 ° C. and held at that temperature for 4 hours.

Hydrate by adding water to cool the product, then wash the sulfonated product and remove the residue acid.

Examples 1, 2, 4-7, and 11-18 of the specific examples 1-18 shown here were functionalized by the sulfonation method "A" and the other examples used the sulfonation method "B".

[Example 2]

Using the same method as described in Example 1, a copolymer ion exchange resin preliminary material was prepared from the same amount of the same starting material.

The properties of this product after sulfonation are given in Table 1.

Example 3

According to the process of Example 1, 254.5 g of styrene, 42.4 g of divinylbenzene, 3.0 g of methyl acrylate and 1.5 g of t-butylperoctoate are charged to the reactor.

The liquid phase is 270 g H ₂ O, 10.0 g poly (diallyldimethylammonium chloride), 0.8 g gelatin protective colloid, 0.45 g boric acid and 50% caustic soda solution sufficient to maintain a pH between 10.0-10.5. It is composed.

The reaction mixture is heated to 75 ° C. for 2.7 hours and then back to 95 ° C. for 1 hour.

The product is washed and sulfonated.

The properties of the resins are in Table 1.

Example 4

According to the process of Example 1, 491.7 g of styrene, 85.5 g of divinylbenzene, 8.8 g of methyl acrylate, 0.51 g of methylcyclopentadiene dimer and 1.90 g of t-butylperoctoate are charged to the reactor.

The liquid phase is 510.0 g of water, 20.1 g of poly (diallyldimethylammonium chloride), 1.6 g of gelatin protective colloid, 0.83 g of boric acid, and a 50% caustic soda solution to maintain a pH between 10.0-10.5. It is composed.

The reaction mixture is heated to 75 ° C. for 4 hours and then to 95 ° C. for 1 hour.

The product is washed and sulfonated.

The properties of the resins are in Table 1.

Example 5

According to the process of Example 1, 491.7 g of styrene, 85.5 g of divinylbenzene, 8.8 g of methyl acrylate, 0.5 g of methylcyclopentadiene dimer and 1.90 g of t-butylperoctoate were added to the reactor. Fill it.

The liquid phase is 510.0 g of water, 20.1 g of poly (diallyldimethyl ammonium chloride), 1.6 g of gelatin protective colloid, 0.88 g of boric acid, and 50% caustic soda solution in sufficient amount to maintain a pH between 10.0-10.5. It is composed.

The reaction mixture is heated to 75 ° C. for 4 hours and then to 95 ° C. for 1 hour.

The product is washed and sulfonated.

The properties of the resins are in Table 1.

Example 6

In accordance with the process of Example 5, a resin having the properties shown in Table 1 was prepared using the same organic phase and liquid phase.

Example 7

-메틸스티렌 이합체(0.59g)과 개시제 t-부틸 퍼옥토에이트(1.9g)을 사용하면 표 1에 있는 성질을 갖는 수지가 마련된다.Reaction regulator according to the process of Example 1

Use of methyl styrene dimer (0.59 g) and initiator t-butyl peroctoate (1.9 g) provides a resin having the properties shown in Table 1.

Example 8

Following the process of Example 1, using 30 g of methyl acrylate, 1.5 g of t-butylperoctoate and 0.3 g of cycloheptatriene (reaction modifier) provides a resin having the properties shown in Table 1.

Example 9

Following the general procedure of Example 1 and using 3.0 g of methyl acrylate, 1.5 g of t-butylperoctoate and 0.3 g of norbornin (reaction modifier), a resin having the properties shown in Table 1 was prepared.

[Example 10]

Following the general procedure of Example 1 and using 3.0 g of methyl acrylate, 1.5 g of t-butylperoctoate and 0.3 g of dicyclopentadiene (reaction modifier), a resin having the properties shown in Table 1 was prepared. .

Example 11

According to the general procedure of Example 1, 8.8 g of methyl acrylate, 0.29 g of methylcyclopentadiene dimer (reaction modifier and 2.64 g of di- (4-t-butylcyclohexyl) -peroxydicarbonate (Percadox 16- TM) provides a resin with the properties listed in Table 1. A blanket with 8% oxygen in nitrogen should swept the reaction mixture within 30 minutes, and 0.59 in the liquid phase to prevent polymerization in the liquid phase. g sodium nitrite is used (also in Examples 12 and 13).

Example 12

According to the general procedure of Example 1, 8.8 g of methyl acrylate, 0.29 g of methylcyclotadiene dimer (reaction modifier and 2.64 g of di- (4-t-butylcyclohexyl) -peroxydicarbonate (initiator) The initial polymerization reaction is carried out 57% for 7 hours, after which the temperature rises to 95% for 1 hour.

The properties of this resin are shown in Table 1.

Example 13

Following the general procedure of Example 1, 8.8 g methyl acrylate, 2.64 g di- (4-t-butylcyclohexyl) -peroxydicarbonate (but not reaction control) and 56 ° C. for 7 hours, 75 for 2 hours Use of a reaction temperature of < RTI ID = 0.0 >

Example 14

Following the general procedure of Example 1, using 1.9 g of 2.5-dimethyl-2.5-bis (2-ethylhexanoylperoxy) -hexyne (initiator) and a reaction temperature of 70 ° C. for 4 hours and then 90 ° C. for 1 hour. The resin having the properties shown in Table 1 is provided.

Example 15

Following the general procedure of Example 1, using 1.12 g of t-butylperoxyneodecanoate (starting material) and an initial reaction temperature of 53-54 ° C. for 4.5 hours, and a reaction temperature of 75 ° C. for 1 hour Resin having the property of 1 is provided.

The following examples illustrate the provisions and products from existing technologies.

[Example 16]

According to the general procedure of Example 1, using 2.20 g of benzoyl chloride (initiator) and 75 ° C. for 4 hours as the initial reaction temperature and 95 ° C. for 1 hour as the final reaction temperature provides a resin having the properties shown in Table 1.

[Examples 17 and 18]

Example 16 is repeated twice to give the product having the properties of Table 1.

The resins produced by the above examples were examined to determine the following.

(1) Total Bead Count% (% WB)

(2) Complete Bead Count% (% PB)

(3) Grinding strength of beads (catylone test)

(4) Percentage reduction of complete beads after repeated circulation in acid and base solutions (accelerated test)

All tests were performed after the resin was sulfonated.

TABLE 1

Instead of the sulfonation method shown above, weak and strong base resins with improved properties can also be prepared by the present invention using well-known methods of functionalizing the copolymer resin later to produce weak or strong anion exchange groups.

Preferred methods known in the art for functionalizing anion exchange groups include chloromethylation followed by amination.

Example 19-20

Two styrene / divinylbenzene strong base resins are prepared by the general method of Example 1 and by using conventional chloromethylation / amination processes to functionalize the copolymer. The copolymer of Example 19 uses terpinolene as the reaction regulator and 2,6-dimethyl-2,4,6-octatriene in Example 20. Both copolymers use t-butyloctoate as an initiator.

Standard specimens of commercially available strong base resins produced without reaction modifiers were prepared using conventional prior art initiators and compared to the above resins. The properties of each resin are shown in Table 2.

TABLE 2

The acid / base cycle test used here and in the claims that follow is 100 cycles of 1N HC1 and 0.5N NaOH at room temperature at a rate of about 2 cycles per hour.

Claims (1)

To prepare hard and segmented crosslinked copolymer beads by free radical polymerization in an aqueous dispersion medium of a monomer mixture comprising a monovinyl monomer as a main component and a crosslinking monomer having at least two active vinyl groups as a secondary component. A process according to claim 1, wherein the polymerization is carried out in the presence of a peroxy catalyst of the formula (I) or (II) as follows.

Wherein R ₁ is a branched alkyl group having a secondary or tertiary carbon linked to a carbonyl group (C ₃ -C ₁₂ ) X is 1 or 2: When X is 1, R ₂ is a branched alkyl group containing a tertiary carbon attached to oxygen, When X is 2, R ₂ is an alkylene group or an allalkylene group, In each case it terminates as tertiary carbon attached to oxygen.

Wherein Y and Z are each independently selected from lower alkyl, cycloalkyl, alkyl-substituted cycloalkyl, and alalkyl groups.