Hybrid copolymers

Abstract

Hybrid copolymers are prepared by at least partially filling the macropores of a macroreticular copolymer with a guest crosslinked copolymer of either the same monomers or a copolymer of different type monomers. The hybrid copolymers can be readily converted into ion exchange resins. Such resins have markedly improved physical and chemical properties, including improved ion exchange properties.

Description

This invention relates to novel hybrid copolymers prepared, for example, by adding a polymerizable monomer, a cross-linking agent, and a free radical initiator to a stirred mixture of a macroreticular copolymer and water. The macroreticular copolymer absorbs or imbibes the monomer mixture and polymerization can be achieved thermally.

As is well known, ion exchange resins or copolymers are generally divided into two classes:

(1) THOSE WHICH ARE ESSENTIALLY NON-POROUS AND WHICH ARE GENERALLY KNOWN AS GEL COPOLYMERS, AND

(2) THOSE WHICH ARE POROUS OR MACRORETICULAR.

Each class of copolymers when converted to or prepared in the form of ion exchange resins, that is by the introduction of or in situ formation of suitable functionality offers certain distinct advantages. For example, strong base resins prepared from macroreticular copolymers generally show an increase in physical stability and exchange kinetics relative to resins prepared from similar gel copolymers which generally exhibit a higher column capacity.

According to the invention there is provided a hydrophobic hybrid copolymer comprising a crosslinked macroreticular porous host or base copolymer having a surface area of at least 5 sq. meters per gram and pores larger than about 15-20 A units, of a polyunsaturated monomer and a monoethylenically unsaturated monomer the polyunsaturated monomer being selected from the group (a) consisting of divinylbenzene, divinyltoluene, divinylnaphthalene, diallylphthalate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, neopentyl glycol dimethacrylate, bis-phenol-A-dimethacrylate, divinyl xylene, divinylsulfone, divinylketone, divinylsulfide, allylacrylate, diallylmaleate and other diallyl esters, trivinylbenzene, and trivinylnaphthalene, and the monoethylenically unsaturated monomer being selected from the group (b) consisting of esters of acrylic acid, esters of methacrylic acid, styrene, vinyl naphthalene and vinyl toluene, said macroreticular copolymer being at least partially filled with a crosslinked gelular or porous guest polymer of a polyunsaturated monomer and a monoethylenically unsaturated monomer of the groups (a) and (b) mentioned above, the guest copolymer being present in the amount of about 10-200 parts by weight per hundred parts by weight of macroreticular host polymer or phase.

There are numerous techniques that can be used to prepare the hybrid copolymers and hybrid resins, which term incidentally has been coined to distinguish the novel copolymers of the present invention from the gel and macroreticular copolymers and resins of the prior art. The "hybrid" terminology indicates that the resins have some of the characteristics and/or properties of both gel and macroreticular copolymers and resins but, more importantly, they represent a new and novel class of materials having distinct properties of their own. One general approach for preparing these copolymers is to at least partially fill the macropores of macroreticular copolymer or resin with gel copolymer utilizing varying percentages of crosslinking agent and introducing such gel copolymer or gel copolymer forming components, in varying amounts. Alternatively, the hybrid copolymers can be prepared by filling the macropores of a macroreticular copolymer with additional macroreticular copolymers in varying amounts and with varying cross-linker contents or percentages or by varying the amount of phase extender. It is also possible to prepare the hybrid resins by filling the hybrid resins or copolymers with functionalized copolymers, e.g., by using a monomer such as 2-vinylpyridine-4-vinylpyridine, acrylic acid, methacrylic acid, etc.

The base or host copolymer possesses a special porous structure which is referred to herein as macroreticular. Macroretocular copolymers possess a network of microscopic channels extending through the mass and while these microscopic channels are obviously very small, they are large in comparison with the pores in conventional homogeneous cross-linked gels, pores of the latter type not being visible in electron photomicrographs and, as is well known, not being true pores at all (vide Kunin, "Ion Exchange Resins" page 45, et. seq. John Wiley & Sons, Inc. 1958). Typically, macroreticular polymers have a surface area of at least 1 sq. meter per gram, and more generally at least 5 sq. meters per gram and hae macropores larger than about 15 to 20 A Units. It is conventional to produce these macroreticular polymers in bead form, usually in an overall particle size of about 10 to 900 microns. Further information on the preparation and structure of macroreticular polymers, which are known materials, may be obtained by referring to British Pat. Nos. 932,125 and 932,126 and U.S. Pat. Nos. 3,275,548 and 3,357,158.

The macroreticular and gel type copolymers and resins, per se, and the resins containing ion exchange functional groups have been described in the prior art. In general, similar types of monomeric materials are used in preparing the macroreticular, and gel type resins, while the preparation process is varied to impart different characteristics, especially different porosity, to the different types of resins. When macroreticular or gel type components are used in the preparation of the hybrid copolymers and hybrid resins of the present invention, the nature of the polymer which comprises the backbone of the resin in relatively unimportant, the only requirement being that the resin for ion exchange ultimately contain suitable functional groups. However, in general, the backbone of these resins and thus the backbone of the hybrid resin as well, will be a hydrophobic cross-linked copolymer of (1) a polyunsaturated monomer, containing a plurality of non-conjugated CH.sub.2 .dbd.C< groups, which acts as a cross-linking agent and (2) a monoethylenically unsaturated monomer, either aromatic or aliphatic. If desired, the polymer can comprise essentially all of (1):

Suitable polyunsaturated cross-linking agents include divinylbenzene, divinyltoluenes, divinylnaphthalenes, diallyl phthalate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, neopentyl glycol dimethacrylate, bis-phenol A dimethacrylate, pentaerythritol tetra- and trimethacrylates, divinylxylene, divinylethylbenzene, divinylsulfone, divinylketone, divinylsulfide, allyl acrylate, diallyl maleate, diallyl fumarate, diallyl succinte, diallyl carbonate, diallyl malonate, diallyl oxalate, diallyl adipate, diallyl sebacate, divinyl sebacate, diallyl tartrate, diallyl silicate, triallyl tricarballylate, triallyl aconitate, triallyl citrate, triallyl phosphate, N,N'-methylenediacrylamide, N,N'-methylene dimethacrylamide, N,N'-ethylenediacrylamide, trivinylbenzene, trivinylnaphthalene, polyvinylanthracenes and the polyallyl and polyvinyl ethers of glycol, glycerol, pentacrythritol, resorcinol and the monothio or dithio derivatives of glycols.

Preferred hydrophobic cross-linking monomers for both the macroreticular phase or base copolymer and the guest fill include polyvinyl aromatic hydrocarbons, such as divinylbenzene and trivinylbenzene, glycol dimethacrylates and polymethacrylates, such as ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and polyvinyl ethers of polyhydric alcohols, such as divinoxyethane and trivinoxypropane. The amount of cross linking agent or monomer can be varied widely. In the case of anion-exchange resins the total utilizable capacity of the final resin as an anion-exchange resin generally decreases with an increase in the amount of cross-linking agent, and an amount of about 1/2% to about 30%, and preferably about 3 to 10%, on a weight basis is usually adequate. However, for other purposes and for cation exchange resins the cross-linking level can be significantly higher, i.e., up to about 50% by weight or even higher based on the total weight of the monomers. In general, therefore, the total amount of cross-linker level may rage from 1/2% to 50% by weight of hybrid copolymer, although preferred cross-linking levels would be from 1/2% to 30% or more, preferably from 3% to 20 % by weight of total hybrid copolymer.

Suitable monoethylenically unsaturated monomers for both the macroreticular base or host addition copolymer and addition guest copolymer fill include esters of acrylic acid, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, tertbutyl acrylate, ethylhexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, phenyl acrylate, alkylphenyl acrylate, ethoxymethyl acrylate, ethoxyethyl acrylate, ethoxypropyl acrylate, propoxymethyl acrylate, propoxyethyl acrylate, propoxypropyl acrylate, ethoxyphenyl acrylate, ethoxybenzyl acrylate, ethoxycyclohexyl acrylate, the corresponding esters of methacrylic acid, styrene, o-, m- and p-methyl styrenes, and o-, m-, and p-ethyl styrenes, vinyl naphthalene, vinyl toluene, ethylvinyl benzene, vinylbenzyl chloride, dimethyl itaconate and vinylnaphthalene. A class of monomers of particular interest consists of vinyl aromatic monomers such as styrene and the esters of acrylic and methacrylic acid with a C.sub.1 -C.sub.10 aliphatic alcohol.

The polymerization reaction is generally carried out in the presence of a catalyst. Suitable catalysts which provide free radicals to function as reaction initiators include benzoyl peroxide, t-butyl hydroperoxide, lauroyl peroxide, cumene hydroperoxide, tetralin peroxide, acetyl peroxide, caproyl peroxide, t-butyl perbenzoate, t-butyl diperphthalate, methyl ethyl ketone peroxide.

The amount of peroxide catalyst required is roughly proportional to the concentration of the mixture of monomers. The usual range is 0.01% to 5% by weight of catalyst with reference to the weight of the monomer mixture. The optimum amount of catalyst is determined in large part by the nature of the particular monomers selected, including the nature of the impurities which may accompany the monomers.

Another suitable class of free-radical generating compounds which can be used as catalysts are the azo catalysts, including for example, azodiiosbutyronitrile, azodiisobutyramide, azobis(.alpha.,.alpha.-dimethylvaleronitrile), azobis(.alpha.-methylbutyronitrile) dimethyl, diethyl, or dibutyl azobis(methylvalerate). These and other similar azo compounds, which serve as free radical initiators, contain an --N.dbd.N-- group attached to aliphatic carbon atoms, at least one of which is tertiary. An amount of 0.01% to 2% of the weight of monomer or monomers is usually sufficient.

In making gel and macroreticular type copolymers and resins and hybrid copolymers and resins containing the guest copolymers and resins, a wide variety of polymerization conditions and processes well known in the art can be used. However, the preferred method is suspension polymerization in a liquid, such as water, which is not a solvent for the monomeric material. This method produces the polymer directly in the form of small spheroids or beads, the size of which can be regulated and controlled. By adjustments in the composition of the suspending medium and in the rate of agitation during polymerization, the suspension polymerization process can be made to produce spheriods or beads of a wide range of effective particle sizes.

In preparing the base macroreticular copolymer or resin, and likewise in preparing a hybrid copolymer or resin which may contain a macroreticular fill of lesser cross-linkage content, the polymerization reaction is carried out in the presence of a precipitant which is a liquid (a) which acts as a solvent for the monomer mixture and is chemically inert under the polymerization conditions and (b) which is present in such amount and which exerts so little solvating action on the product cross-linked copolymer that phase separation of the product copolymer takes place as evidenced by the fact that the product copolymer is no more than semi-transparent and is preferably opaque when associated with a fluid having a different refractive index.

The determination of the most effective precipitant and the amounts required for the formation of a particular copolymer may vary from case to case because of the numerous factors involved. However, although there is no "universal" or single class of precipitants applicable to all cases, it is not too difficult to determine which precipitants will be effective in a given situation. The requirements of solubility with the monomer mixture and low solvating action on the product copolymer can be tested empirically and the solubilities of many monomers and copolymers are well known from publications and textbooks. A swelling type solvent can be used, however, provided that the cross-linker level is sufficiently high.

As a further guide in the selection of a suitable precipitant, reference may be made to scientific literature, for instance, as discussed in Hildebrand and Scott, Solubility of Non-Electrolytes, 3d., N.Y., 1950. In general, it may be stated that sufficiently wide differences in the solubility parameters of copolymer and solvent, respectively, must exist for the precipitant to be effective and that, once an effective precipitant has been located, the behaviour of many other liquids can be predicted from the relative position of the reference polymer and precipitant in published tables, within the accuracy of such published information. Furthermore, if the solubility parameter of a given polymer occupies an intermediate position in these tables, solvents with both higher or lower parameters may become effective.

A minimum concentration of any particular precipitant is required to effect phase separation. This is comparable to the observation that many liquid systems containing two or more components are homogeneous when some components are present in only minor amounts; but, if the critical concentration is exceeded, separation into more than one liquid phase will occur. The minimum concentration of the precipitant in the polymerizing mixture will have to be in excess of the critical concentration. The amounts in excess of such critical concentration can be varied and they will influence to some extent the properties of the product so formed.

Too high a concentration of the precipitant may be undesirable for practical reasons since the rate of copolymerization may decrease and the space-time yields become low. In many cases, the amount of precipitant employed may be between 25 percent and 60 percent by weight of the total weight of the monomer mixture and the precipitant.

The amount of precipitant liquid required to effect phase separation varies inversely with the degree of cross-linking of the copolymer so thaat the greater the cross-linker content the lesser is the amount of precipitant employed.

As stated above, the chemical character of the precipitant may vary appreciably, depending on the monomer mixture which is used. When employing aromatic hydrocarbon type monomers, such as, for instance, styrene and divinylbenzene, alkanols with a carbon atom content of from 4 to 10 will, if sufficient cross-linker is used, effect the desired phase separation when used in amounts of from about 30% to 50% of the total weight of monomers and precipitant.

Saturated aliphatic hydrocarbons containing at least 7 carbon atoms, such as heptane and isooctane, may be employed as precipitants for aromatic hydrocarbon systems, such as styrene and divinylbenzene. Also, cyclohexane may be employed. The amounts employed can be varied, depending on the degree of cross-linkage, and may be from 30% to 50% of the total weight of the monomers and precipitant.

When employing acrylic esters as the monounsaturated monomers, alkyl esters can be effectively employed as precipitants. Typical esters include n-hexyl acetate, 2-ethylhexyl acetate, methyl oleate, dibutyl sebacate, dibutyl adipate and dibutyl carbonate. The esters must have a carbon atom content of at least 7. The concentrations required will vary somewhat with the ester being used and with the amount of cross-linking monomer but from 30% to 50% by weight based on the combined weight of the monomers and the precipitant will generally cause the desired phase separation and the formation of a macroreticular structure within the polymerized mass.

Higher aliphatic hydrocarbons containing at least 7 carbon atoms, such as heptane and isooctane, may be employed as precipitants when employing acrylic esters as the monoethylenically unsaturated monomers. The amounts employed can be varied from 25% to 50% based on the combined weight of monomers and precipitant.

Many polymerization methods can be used in preparing the macroreticular resins and the hybrid resins as well. The preferred method, however, is suspension polymerization. In this case, an additional factor must be considered, namely, the solubility, i.e., miscibility. of the precipitant in the suspending medium. Since suspension polymerization of most ethylenically unsaturated monomers is generally conducted in aqueous media, most frequently it is the water-solubility of the precipitant which must be considered. While precipitants with water-solubilities as high as 20 grams per 100 grams of water can be employed, a low water-solubility is preferred because of handling ease, ease of recovery, and processing economies. As is well known, however, it is possible to decrease the water-solubilities of compounds by adding salts to the aqueous phase and this method also may be employed to decrease the water-solubilities of a precipitant liquid. The general position is that, when suspension polymerization is used, the precipitant must be either immiscible or only partially miscible with the suspending medium.

Other suitable methods for preparation of the macroreticular resins are disclosed in U.S. Pat. Nos. 3,275,548 and 3,357,158.

As noted hereinabove the terms "hybrid copolymers" or "hybrid resins" have been coined to denote materials obtained by a multi-stage polymerization technique. In general, the term hybrid copolymers refers to the novel materials of this invention before the introduction or creation of any significant amount or quality of ion-exchange functional groups. The term hybrid resins or hybrid ion-exchange resins generally refers to the hybrid copolymers in their converted or functionalized form, i.e., after treatment of the hybrid copolymers to introduce suitable ion-exchange functional groups or after incorporating functionalized monomers. The same materials, catalysts, proportions and polymerization techniques, particularly the suspension polymerization technique, referred to above with reference to the macroreticular copolymers and the gel-type copolymers are used in making the finished hybrid copolymers or hybrid resins. The hybrid ion-exchange resins of the present invention, in which the pores of the macroreticular copolymer are filled with a lightly cross-linked gel copolymer, do in fact combine the high capacity of the gel resin with the stability of the macroreticular resin. The hybrid copolymer is prepared by adding fresh monomer such as, for example, styrene, catalyst, and a suitable cross-linking agent such as divinylbenzene to a suspension of a macroreticular copolymer and water. The monomer is adsorbed or imbibed into the pores of the macroreticular copolymer, and the imbibed monomer is polymerized within the macroreticular copolymer beads by heating the mixture and thereafter ion exchange functional groups are introduced to the polymer complex thus formed. Not only do the resulting resins show a greater combination of capacity and stability than one obtains with a macroreticular resin and a gel resin, but also there are significant improvements in leakage and pressure drop over the corresponding macroreticular and gel type resins. While there has undoubtedly been prior work involving multistage polymerization copolymers and resinous materials include materials designed as ion exchange resins, the present polymer systems differ from anything known or disclosed in the prior art in the following respects: the first-stage polymer or the precursor macroreticular copolymer can furnish, if desired, substantial ion exchange properties in its own right in contrast to the inert inorganic carriers or porous polymers (PVC, PE) of the prior art, thus leading to superior total capacity in the final product. Also, the base macroreticular copolymer can be converted in whole or in part to an ion exchange resin by the introduction of suitable functional groups before the gel polymer or differently cross-linked macroreticular copolymer is added to the pores of the base or first stage polymer. The monomer which is to be sorbed or imbibed into the base macroreticular copolymer, herein designated as the second-stage monomer merely for ease of reference, is deposited within the macropores of the substrate and no interaction with the substrate is sought although some interaction would not necessarily be harmful or undesirable. In any event, the final compositions are still heterogeneous. Thus, while some swelling on the polymer body cannot be excluded, no groups or treatments promoting grafting efficiency are generally provided or even deemed necessary. At higher levels of cross-linking in the first-stage polymer, imbibing is probably therefore due to capillary effects and the products are not interpenetrating net works as described in parts of the prior art. The hybrid resin may, therefore, be considered heterogeneous products characterized by two relatively independent phases which cooperate in providing superior ion exchange capacity, particle stability, improved leakage characteristics, and other advantageous factors.

Other advantageous factors include, unexpectedly good hydraulic and good pressure drop characteristics, particularly, (1) for hybrid resins which contain a gel phase which may be lightly cross-linked, e.g., with as little as 1/2% cross-linker, and still have excellent properties, for example, in sugar decolorization, see Example 12, and Table IV infra, or (2) for hybrid resins which contain a lightly cross-linked macroreticular phase and which still have outstanding leakage characteristics, see, for example, Example II, and Table III, infra. This is rather surprising since lightly cross-linked resins are sometimes very soft and virtually unusable in many industrial applications.

The relative amounts of guest phase polymer and macroreticular host or base copolymer can be varied over a wide range. It is desirable, however, to use at least 5 parts by weight of guest forming components (guest copolymer) per 100 parts by weight of macroreticular base or host polymer, with the maximum amount being dictated by that amount which can be imbibed or retained or on the macroreticular base structure. This maximum will ordinarily be about 300 parts by weight of guest copolymer per 100 parts by weight of base polymer, although higher amounts can also be used. Preferably, the amounts of guest copolymer to macroreticular base will be in the range of about 10 to 200 parts of guest copolymer per 100 parts of macroreticular polymer, and more preferably, about 25 to 100 parts of guest copolymer per 100 parts of macroreticular host base polymer, all parts being on a weight basis.

The following examples will further illustrate the invention but are not intended to limit it. In the examples, as well as in the other parts of the specification and claims, parts and percentages are by weight unless otherwise stated. Mesh measurements are U.S. Standard Sieve unless otherwise stated. All chemicals used are of good commercial quality. In the case of divinylbenzene (DVB) a good commercial grade is used which contains about 56% active material, i.e., pure DVB, the balance being essentially all ethyl vinyl benzene. The copolymers set forth below are in bead form and are prepared by suspension or pearl polymerization techniques. Porosity is reported as percent porosity or as the volume of pores per dry volume of resin, usually as milliliter per milliliter (ml./ml.). Percent porosity can be obtained by multiplying this value by 100. All temperatures given in the examples are in .degree. C. unless otherwise stated.

EXAMPLE 1

(a) Preparation of Starting Copolymer (Macroreticular)

To a three-liter, three-necked flask equipped with stirrer, a thermometer, and a reflux condenser is added 1.15 g. of sodium chloride, 1.5 g. of purified gelatin in 50 ml. of water, 10 g. of sodium polyacrylate (12.5% solids) in 100 ml. of water, and 500 ml. of water with stirring. The stirring speed is adjusted to .about.145 rpm and after solution was achieved the stirrer was stopped and 400 g. of a 3% DVB*-styrene solution. 261.2 g. of methylisobutylcarbinol (MIBC) and 5.0 g. of benzoyl peroxide are added. The mixture is stirred at 145 rpm until a suitable dispersion is achieved and is heated at 80.degree. for 11 hrs. The MIBC is removed by distillation while maintaining a constant fluid level by the gradual addition of water. The mixture is cooled to room temperature, and the copolymer is isolated and washed on a Buchner funnel. The resulting copolymer product is dried at 125.degree. for 8 hrs. to give a 70% yield of -20 +70 mesh beads and is identified as Resin A in Table I below. The copolymer product has a porosity of 0.56 ml./ml. and a cross-linker level of 3% DVB. After chloromethylation and amination the copolymer is converted into a strongly basic anion exchange resin with a column capacity of 9 Kgr./ft..sup.3, as CaCO.sub.3, and a porosity of 0.2 to 0.4

*DVB=divinylbenzene

(b) Strong Base Gel Type Resin

A strong base gel type anion exchange resin, having a styrene-DVB matrix, is prepared in conventional manner. The gel resin has a column capacity of 12.0 Kgr./ft..sup.3 as CaCO.sub.3, a porosity of 0.0 and a DVB cross-linker level of 2%. The product is identified as Resin B in Table I.

EXAMPLE 2

(a) Preparation of Hybrid Copolymer

In a one-liter, three-necked flask equipped with an efficient stirrer, a condenser, and a thermometer is placed 52 g. of a 3% divinylbenzene (DVB, 58.9% active)-styrene macroreticular copolymer (0.71 porosity, 30-60 mesh) and 400 ml. of tap water. To this mixture is added 50 g. of a 0.5% DVB-styrene solution in which is dissolved 0.5 g. of benzoyl peroxide. The resulting mixture is stirred rapidly at room temperature for one hour and at 80.degree. for a total reaction time of 20 hours. The mixture is allowed to cool to room temperature and the resulting beads are isolated by filtration, washed with 600 ml. of methanol, and dried to a constant weight in a steam oven (75.degree.). The hybrid copolymer is used directly in the following chloromethylation procedure. The yield of hybrid copolymer is 99.4 g. (97.5%).

(b) Chloromethylation of Hybrid Copolymer

In a one-liter, three-necked flask equipped with a mechanical stirrer, a condenser with a drying tube attached, a thermometer, and a dropping funnel is placed 52 g. of the above hybrid copolymer and 240 ml. of 1,2-dichloroethane (EDC). The mixture is stirred slowly for 30 min. allowing the beads to swell. To the swollen beads is added 95 g. of chloromethyl methyl ether (CME) in one portion. The reaction mixture is cooled to 0.degree. by means of an ice bath and 26.8 g. of aluminum chloride dissolved in 26 g. of CME is added dropwise over a one hour time period while maintaining the temperature below 5.degree.. The mixture which resulted is heated at 40.degree. for 16 hours and is cooled to -10.degree. with the use of an ice-methanol bath. The cooled slurry is poured into 600 ml. of anhydrous methanol while maintaining the temperature below 10.degree.. The mixture is stirred for 30 min., the liquid layer is removed with a filter stick, and the resulting beads are given two 30 min. washes with 600 ml. portions of absolute methanol to give the product as tan uncracked beads which are used directly in the following aminolysis.

(c) Aminolysis of the Chloromethylated Intermediate

In a one-liter, three-necked flask equipped with a mechanical stirrer, a thermometer, and a gas diffusion tube are placed the chloromethylated intermediate prepared as described above. Methanol (250 ml.) is added and the mixture is brought to pH 8 with 10% sodium carbonate. To the basic mixture is added 40 g. of trimethylamine (TMA) by means of a gas diffusion tube while maintaining the temperature below 15.degree. with an ice bath. After the addition is complete the reaction is stirred at room temperature overnight. The unreacted TMA and the methanol are removed by distillation while maintaining a constant fluid level by the gradual addition of water. The reaction mixture is cooled and the product is backwashed to neutrality and isolated by filtration. The product had an average DVB content of 2.02%; solids--42.3%; anion exchange capacity--4.22 meq./g. of dry resin; reversible swelling--17.8%; column capacity at a 5 gal./ft..sup.3 /min. flow rate--10.2 kgr./ft..sup.3 ; whole bead content after two acid-base cycles with 1 N HCl and 1 N NaOH--98%; cracked bead content--7%.

EXAMPLE 3

(a) Preparation of Hybrid Copolymer

In a one-liter, three-necked flask equipped with an efficient stirrer, a condenser, and a thermometer is placed 52 g. of a 3% divinylbenzene (DVB, 58.9% active)-styrene macroreticular copolymer (30-60 mesh, 0.71 porosity) and 400 ml. of tap water. To this mixture is added with rapid stirring 100 g. of a 0.5% DVB-styrene solution in which is dissolved 1.0 g of benzoyl peroxide. The mixture is stirred rapidly for one hour during which time the added monomer mixture is absorbed by the initial preformed porous copolymer. The reaction mixture is then heated for 20 hours at 80.degree.. The mixture is cooled, and the copolymer is isolated by filtration, washed with 600 ml. of methanol, and dried in a steam oven (75.degree.) until a constant weight of copolymer is achieved to give 150 g. (98.7%) of product.

(b) Chloromethylation of Hybrid Copolymer

In a one-liter, three-necked flask equipped with a mechanical stirrer, a condenser to which is attached a drying tube, a dropping funnel, and a thermometer is placed 52 g. of the hybrid copolymer described above. The beads are swollen in 300 ml. of 1,2-dichloroethane (EDC) for 30 min. and 95 g. of chloromethyl methylether (CME) is added. The mixture is cooled below 10.degree. with an ice bath and 26.8 g. of aluminum chloride in 26 g. of CME is added dropwise over a one hour period. The mixture is warmed between 35.degree.-40.degree. overnight and is cooled to 0.degree. by means of an ice-methanol bath. The resulting beads are washed once with 600 ml. of EDC and three times with 600 ml. portions of methanol. The resulting chloromethylated product is used directly in the following aminolysis.

(c) Aminolysis of the Chloromethylated Intermediate

In a one-liter, three-necked flask equipped with an efficient stirrer, a thermometer, a condenser, and a gas diffusion tube is placed the chloromethylated intermediate described above. Methanol (300 ml.) is added and the mixture is brought to pH 8 with 10% aqueous sodium carbonate. Trimethylamine (TMA) 40 g.) is added below the surface of the liquid by means of the gas diffusion tube over a period of two hours. The reaction mixture is heated to 35.degree.-40.degree. overnight and the unreacted TMA and methanol are removed by distillation while maintaining a constant liquid level in the flask by the gradual addition of tap water. The resulting product is backwashed to neutrality and is isolated by filtration. The product has an average DVB content of 1.35%; solids 41.1%; anion exchange capacity--4.33 meq./g. of dry resin; reversible swelling 17.0%; column capacity at a 2 gal.ft..sup.3 /min. flow rate--10.6 kgr./ft..sup.3 ; whole bead content after two acid-base cycles with 1 N HCl and 1 N NaOH--100%; cracked bead content--5%.

EXAMPLE 4

(a) Preparation of Hybrid Copolymer

A 3% divinylbenzene (DVB)-styrene macroreticular copolymer (107.7 g.) having a porosity of 0.56 is suspended in 800 ml. of tap water in a two-liter, three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer. To the rapidly stirred mixture is added in one portion a 0.5% DVB-styrene solution (30 g.) containing benzoyl peroxide (1.37 g.). The resulting mixture is stirred at room temperature for 55 minutes and is heated at 80.degree. for a total reaction time of 22 hours. The reaction mixture is cooled and the product is isolated by filtration, rinsed with methanol, and dried in a steam oven (75.degree.) to a constant weight to give 134.1 g. (97.8%) of white opaque beads. Effective size: before, 0.322; after, 0.346.

(b) Chloromethylation of Hybrid Copolymer

In a two-liter, three-necked flask equipped with a mechanical stirrer, thermometer, and a condenser to which is attached a drying tube was placed 107 g. of the hybrid copolymer prepared as described above and 350 ml. of 1,2-dichloroethane (EDC). The mixture is stirred for 5 min. 241.5 g. of chloromethyl methyl ether was added, and the resulting mixture is cooled to 0.degree. by means of an ice bath. Aluminum chloride is added over a two hour period while maintaining the reaction temperature at 0.degree.. Upon completion of the addition the reaction mixture is heated at 35.degree. for 24 hours. The mixture is cooled and the liquid phase is removed by means of a filter stick. The crude product is washed with 600 ml. of EDC for 30 min. followed by 3.times.600 ml. washes with methanol. This material is used directly without further purification in the aminolysis described below. Calculated % Cl: 22.96; Found: 20.4.

(c) Aminolysis of the Chloromethylated Intermediate

To the chloromethylated intermediate described above is added 250 ml. of anhydrous methanol and enough 20% sodium carbonate (.about.10 ml.) to bring the mixture to pH 8. To the basic slurry is added 75 g. of anhydrous trimethylamine by means of a gas diffusion tube placed below the surface of the liquid while maintaining the reaction temperature between 5.degree.-10.degree.. Upon completion of the addition the mixture was warmed to 35.degree. for three hours. Excess TMA and methanol are removed by means of distillation using a Barrett trap while maintaining a constant volume by the addition of water. When the temperature of the reaction mixture reached 100.degree. the reaction mixture is allowed to cool to room temperature. The resulting product is backwash to neutrality with tap water. The final product has an average DVB content of 2.45%, solids--38.5%; anion exchange capacity--4.25 meq./gm. of dry resin; density--0.64 g./ml.; porosity--0.044; reversible swelling--20.8%; column capacity at a 5 gal./ft..sup.3 /min. flow rate--11.0 kgr./ft..sup.3 ; whole bead content after two acid-base cycles with 1 N HCl and 1 N NaOH--100%; cracked bead content--1%.

EXAMPLE 5

(a) Preparation of Hybrid Copolymer

In a two-liter, three-necked flask equipped with a mechanical stirrer, reflux condenser, and a thermometer is placed 800 ml. of water and 107.6 g. of preformed macroreticular bead copolymer (-20 +60 mesh) having a porosity of 0.56. To the resulting mixture is added 60 g. of a 0.5% divinylbenzenestyrene solution containing 1.67 g. of benzoyl peroxide while rapid stirring is maintained. After 55 min. the reaction mixture is heated to 80.degree. for a total reaction time of 22 hours. The reaction mixture is cooled to room temperature and filtered. The product is washed with 40 ml. of methanol and is dried in a steam oven for 4 hours to give 166.1 g. (99.1%) of white opaque beads. Effective size before polymerization, 0.322; after, 0.382.

(b) Chloromethylation of Hybrid Copolymer

In a two-liter, three-necked flask equipped with a mechanical stirrer, thermometer, and a condenser to which is attached a drying tube is placed 107 g. of dry copolymer prepared as described above and 350 ml. of a 1,2-dichloroethane (EDC). The mixture is stirred slowly for 15 min. to allow the copolymer to swell. To the swollen copolymer is added 241.5 g. of chloromethyl methyl ether (CME) in one portion. The resulting mixture is cooled to 0.degree. by means of an ice bath and 53.4 g. of aluminum chloride was added over a two hour period while maintaining the temperature at 0.degree.. The reaction mixture is heated to 35.degree. for 24 hours and the liquid layer is removed by means of a filter stick. The resulting beads were washed with 600 ml. portions of anhydrous methanol. Calculated % Cl: 21.3; Found: 21.0.

(c) Aminolysis of the Chloromethylated Intermediate

The copolymer prepared in the mannner described above is placed in a two-liter, three-necked flask equipped with a mechanical stirrer, condenser, and gas inlet tube. The copolymer is slurried in 250 ml. of absolute methanol and brought to pH 8 with 20% aqueous sodium carbonate. The mixture is cooled to 5.degree.-10.degree. by means of an ice bath and 75 g. of trimethylamine (TMA) is added below the surface of the liquid in the flask. After addition the reaction mixture is heated to 35.degree. for a period of 24 hours. The methanol and excess TMA are removed by distillation while maintaining a constant liquid level in the flask by the gradual addition of tap water. When the temperature in the reaction pot reaches 100.degree. distillation is discontinued and the mixture is cooled to room temperature and backwashed to neutrality with tap water. The product has an average DVB content of 2.11%; solids--38.5%; anion exchange capacity 4.43 meq./gm. of dry resin; density--0.645 g./ml.; reversible swelling--13.7%; column capacity at a 5 gal./ft..sup.3 /min. flow rate--11.3 kgr./ft..sup.3 ; whole bead content after two acid-base cycles with 1 N HCl and 1 N NaOH--98%; cracked bead content--13%.

EXAMPLE 6

(a) Copolymer (Macroreticular)

A 3% divinylbenzene (DVB)-styrene macroreticular copolymer having a porosity of 0.56 which was used in the preparation of Example 5 and Example 4 is used directly without hybridization in the chloromethylation step described below.

(b) Chloromethylation of Copolymer

In a two-liter, three-necked flask equipped with a mechanical stirrer, a condenser to which is attached a drying tube, and a thermometer is placed 107.6 g. of the copolymer described above and 650 ml. of 1,2-dichloroethane (EDC). The mixture is stirred for 5 min. and 241.5 g. of chloromethyl methyl ether was added and the resulting mixture is cooled to 5.degree.-10.degree. over a 25 min. period by means of an ice bath. Aluminum chloride (53.4 g.) is added over a two hour period while maintaining the temperature between 5.degree.-10.degree.. The reaction mixture is heated at 35.degree. for 24 hours and the liquid phase is removed with a filter stick. Half hour washes with one 600 ml. portion of EDC and 3.times.600 ml. portions of absolute methanol were used to purify the crude reaction product. Calculated % Cl: 23.1; Found 20.1.

(c) Aminolysis of The Chloromethylated Intermediate

In a two-liter, three-necked flask equipped with a mechanical stirrer, a condenser, a gas diffusion tube, and a thermometer is placed the chloromethylated resin described above. Methanol (300 ml.) was added and the slurry was brought to pH 8 with 10% aqueous carbonate. The resulting mixture was cooled to 0.degree.-10.degree. and 75 g. of trimethylamine (TMA) is added below the liquid surface through the gas diffusion tube. Upon completion of the addition the reaction mixture is heated at 35.degree. for three hours and is stirred at room temperature for 16 hours. The excess TMA and methanol are removed by distillation while maintaining a constant liquid level by the gradual addition of water. When the temperature reaches 100.degree. distillation is discontinued, the reaction mixture is allowed to cool, and the product is backwashed to neutrality. The product has an average DVB content of 3.0%; solids--38.5%; anion exchange capacity--4.25 meq./gm. of dry resin; density--0.65 g./ml.; reversible swelling--20%; column capacity at a 5 gal./ft..sup.3 /min. flow rate--9.65 kgr./ft..sup.3 ; whole bead content after two acid-base cycles with 1 N HCl and 1 N NaOH--100%; cracked bead content--1.5%.

EXAMPLE 7

(a) A strongly acidic, macroreticular cation exchange resin, having a styrene-DVB matrix, is prepared in a conventional manner. This resin has a column capacity of 12.0 kgr./ft..sup.3 as CaCO.sub.3, a porosity of 0.3-0.36 and a DVB cross-linker level of 20%. This product is identified as Resin C in Table II below.

(b) A strongly acidic, gel type cation exchange resin, having a stryene-DVB matrix is prepared in conventional manner. This resin has a column capacity of 22 kgr./ft..sup.3 as CaCO.sub.3, a porosity of zero (0) and a DVB cross-linker level of 12%. This resin is identified in Table II below as Resin D. Neither Resin C nor Resin D has any imbibed monomer.

EXAMPLE 8

(a) Preparation of macroreticular base or host copolymer

In a two-liter, three-necked flask equipped with a mechanical stirrer, condenser, thermometer, and a positive nitrogen flow is placed 500 g. of water and 1.5 g. of sodium. To this mixture is added 1.33 g. of gelatin dissolved in 30 ml. of water and 4.4 g. of sodium polyacrylate in 50 ml. of water. The mixture is stirred for 10 min. The stirring is stopped and a solution containing 350 g. of 20% divinylbenzene-styrene, 290 g. of methylisobutylcarbinol (MIBC) and 3.5 g. of benzoylperoxide is added in one portion. The mixture is heated and stirred for 16 hours at 80.degree.. The MIBC is removed by distillation while maintaining a constant liquid level by the gradual addition of water. Upon completion of the distillation the reaction mixture is cooled and the product is isolated by filtration, washed with methanol and dried at 75.degree. to a constant weight to give 336 g. (96%) of cross-linked macroreticular product having a porosity of about 0.54 ml./ml.

(b) Control Sulfonation

In a one-liter, three-necked flask equipped with a stirrer, a thermometer and a Barrett trap to which is attached a condenser with a drying tube is added 52 g. of a 20% divinylbenzene (DVB)-styrene macroreticular copolymer, from Example 8(a) above 16 g. of 1,2-dichloroethane, and 260 g. of 98% sulfuric acid in that order with stirring. The mixture is stirred at room temperature for 30 min., heated at 60.degree. for the one hour (at this point 180 g. of additional sulfuric acid is added to maintain fulidity), and at 110.degree. for three hours. While heating, approximately 7 ml. of EDC is collected in the trap. The product is quenched over a period of one hour while maintaining the temperature between 90.degree. and 110.degree.. The acid washings are siphoned to the top of the bead layer and the resulting beads are washed with successive 400 ml. portions of water until the washings are less than 3% sulfuric acid (5 washes). The beads are neutralized with a 25% excess of 10% sodium hydroxide (21.75 g. of NaOH) while maintaining the temperature below 30.degree.. The basic beads are backwashed to neutrality with tap water. It is observed that relative to hybrid resins (Example 9 and Example 10, below) the beads are more highly fragmented. Initial whole bead content--5%; fragmented--95%; 100% fragmented after one wet-dry cycle.

EXAMPLE 9

(a) Preparation of Hybrid Copolymer

In a one-liter, three-necked flask equipped with a mechanical stirrer, thermometer, and condenser is placed 52 g. of a 20% divinylbenzene (DVB)-styrene macroreticular copolymer from Example 8(a) above and 400 ml. of tap water. To this mixture is added with rapid stirring 30 g. of a 4% DVB-styrene solution in which is dissolved 0.3 g. of benzoyl peroxide. The mixture is stirred for one hour during which time the preformed copolymer absorbed the added monomer mixture. The mixture is heated at 80.degree. for 16 hours and the product is isolated by filtration, washed with 600 ml. of methanol and dried in a steam oven (75.degree.) to a constant weight to give 81 g. (98.9%) of opaque white beads.

(b) Sulfonation of Hybrid Copolymer

To 50 g. of hybrid copolymer, prepared as described above, in a one-liter, three-necked flask equipped with a stirrer, thermometer, and a Barrett trap to which is attached a condenser with a drying tube is added 16 g. of 1,2-dichloroethane and 260 g. of sulfuric acid in that order. The reaction mixture is stirred at room temperature for 30 min., at 60.degree. for one hour, and at 110.degree. for three hours. During this time ca. 8 ml. of EDC distilled into the Barrett trap. The reaction mixture is cooled to 90.degree. and 300 ml. of water is added over a period of 30 min. while maintaining the temperature below 110.degree.. The aqueous phase is removed to the bead surface by means of a filter stick and 300 ml. of water is added in one portion. The product is washed with 3.times.400 ml. portions of water and is neutralized with 10% aqueous sodium hydroxide. The excess caustic is removed by backwashing the sample to neutrality. The product containing 98% whole uncracked beads. After one wet-dry cycle the product contained 98% whole beads and 5% cracked beads; salt splitting cation capacity--4.25 meq./gm. of dry resin; solids--52.2%; reversible swelling--4.5%; column capacity at a 2 gal./ft..sup.3 /min. flow rate--22.1 kgr./ft..sup.3 ; porosity--0.43; average % DVB--14.1

EXAMPLE 10

(a) Preparation of Hybrid Copolymer

In a one-liter, three-necked flask equipped with a mechanical stirrer, thermometer, and condenser is placed 52 g. of a 20% DVB-styrene macroreticular copolymer and 400 g. of tap water. To this mixture is added 60 g. of a 4% DVB-styrene solution in which was dissolved 0.6 g. of benzoyl peroxide. The resulting mixture is stirred rapidly for 30 min. and the temperature is brought to 80.degree., and held there for 20 hours. The product is isolated by filtration, washed with methanol, and dried to a constant weight in a steam oven (75.degree.) overnight to give 107.5 g. (96%) of material.

(b) Sulfonation of Hybrid Copolymer

In a one-liter, three-necked flask equipped with a mechanical stirrer, a Barrett trap to which is attached a reflux condenser, and a thermometer is placed 50 g. of the hybrid copolymer prepared in the manner described above. To the copolymer is added 16 g. of 1,2-dichloroethane (EDC) and 260 g. of 99% sulfuric acid. The mixture is stirred for 30 min. at room temperature, for one hour at 60.degree., and for 3 hours at 110.degree.. During this time 7.8 ml. of EDC is collected. The reaction mixture is cooled to 90.degree. and 300 ml. of water is added over a period of 30 min. while maintaining the temperature below 110.degree.. The liquid is siphoned to the bead level and 400 ml. of water is added in one portion. The mixture is stirred for 15 min. and the process is repeated three times. The resulting product is made basic with excess 10% sodium hydroxide while keeping the temperature below 50.degree. and the excess base is removed by backwashing. The product contained 99% whole and uncracked beads; appearance after one wet-dry cycle--99% whole beads, 28% cracked beads; salt splitting cation capacity--4.15 meq./g. of dry resin; solids--55.1%; reverisble swelling--20.7%; porosity--0.13; average % DVB--11.4.

TABLE I__________________________________________________________________________PROPERTIES OF STRONG BASE ION EXCHANGE RESINS Column*** Capacity Kilograins (Kgr.) as Imbibed CaCO.sub.3 perResin Copolymer Monomer ft. 3 of Appearance** TotalSample (host or control) gms. % DVB resin Porosity Before After % DVB__________________________________________________________________________Resin A styrene-DVB (3%) -- -- 9 0.2-0.4 100/0/0 98/0/2 3 cross-linked MR* copolymer with porosity of 0.56 ml./ml.Resin B styrene-DVB (2%) -- -- 12.0 0 100/0/0 2/98/0 2 gel copolymerHybrid ResinsExample 2 styrene-DVB (3%) 50 1/2 10.2 0.02 99.5/0/.5 99.5/0/.5 1.8 cross-linked MR copolymer with porosity of 0.71 ml./ml.Example 3 " 100 1/2 10.6 0.00 100/0/0 99.8/0.2/0 1.4Example 4 styrene-DVB (3%) 30 1/2 11.0 0.04 100/0/0 99/1/0 2.5 cross-linked MR copolymer with porosity of 0.56 ml./ml.Example 5 " 60 1/2 11.3 0.01 97/1.5/1.5 85/13/2 2.1Example 6 " -- 9.6 0.15 -- -- 3.0__________________________________________________________________________ *MR - macroreticular **Appearance - represents untouched whole beads, cracked beads, and fragmented beads in that order both before and after acid base cycling. I acid base cycling the resin is contacted with 1N HCl for 1/2 hour, rinsed with water, then contacted with 1N NaOH for 1/2 hour and rinsed with wate for one complete cycle. A 20-30 mesh cut is used. ***Column Capacity - reported at a regeneration level of 4 lbs. NaOH/cu.ft. of resin. Regeneration with 1N NaOH and a flow rate of 1 gal./cu.ft./minute. Exhaustion with 500 ppm HCl at a flow rate of 2 gal./cu.ft./minute. TABLE II__________________________________________________________________________PROPERTIES OF STRONG ACID ION EXCHANGE RESINS Column*** Capacity Kgr. as Imbibed CaCO.sub.3 perResin Copolymer Monomer ft. 3 of Appearance** Total %Sample (host or control) gms. % DVB resin Porosity Before After DVB__________________________________________________________________________Resin C styrene-DVB (20%) cross-linked MR* copolymer with porosity of 0.35- 0.4 ml./ml. -- -- 12.0 0.3-0.36 100/0/0 99/1/0 20Resin D styrene-DVB (12%) -- -- 22.0 0 77/19/4 56/22/22 12 gel copolymer with zero porosityHybrid ResinsExample 8 styrene-DVB (20%) cross-linked MR copolymer with porosity of 0.54 -- -- 0.5 5/0/95 0/0/100 20Example 9 " 30 1/2 22.1 0.34 98/0/2 93/5/2 14.1Example 10 " 60 1/2 20.7 0.13 99/0/1 71/28/1 11.4__________________________________________________________________________ *MR - macroreticular **Appearance - represents untouched whole beads, cracked beads, and fragmented beads in that order both before and after wet-dry cycling. In wet-dry cycling the beads are dried in an oven at 125.degree. C. and then re-wet rapidly ***Column Capacity - reported at a regeneration level of 10 lbs. NaCl/cu.ft. of resin. Regeneration with 10% NaCl at a flow rate of 1 gal./cu.ft./min. Exhaustion with 500 ppm of CaCl.sub.2 at a flow rate of gal./cu.ft./min.?

In Table I, above, the properties of representative strong base hybrid ion exchange resins are compared with a similar macroreticular strong base resin (Resin A) and with a similar strong base gel resin (Resin B). It can be seen that the physical stability of the hybrid resins, i.e., the resins of Examples 2, 3, 4 and 5, as judged by the appearance before and after acid base cycling, is greatly improved relative to the gel resin, i.e., Resin B, and is at least as good in most instances, and in some instances better than the related macroreticular resin, i.e., Resin A. In addition, the column capacities of the hybrid ion exchange resins are significantly greater when compared with the macroreticular control, Resin A.

Table II illustrates a similar improvement in properties namely physical stability and column capacity for hybrid strong acid (cation) ion exchange resins when compared with a similar gel type resin, Resin D, and a similar macroreticular resin, Resin C. It is particularly striking that the column capacities of the hybrid resins, e.g., resins of Examples 9 and 10 are almost double that of the counterpart macroreticular resin (Resin C) and in the case of Example 9 is even greater than a corresponding gel resin, e.g., Resin D.

EXAMPLE 11

(a) Preparation of Hybrid Copolymer

In a one-liter, three-necked flask equipped with an efficient stirrer, a reflux condenser, and a drying tube is placed 100 g. of a 3% divinylbenzene (DVB)-styrene crosslinked macroreticular copolymer having a porosity of 0.56 and 300 ml. of tap water. The mixture is heated to 80.degree. and a solution consisting of 100 g. of 8% DVB (55.9% active)-styrene monomer and 1 g. of benzoyl peroxide is added in one portion. The resulting mixture is stirred rapidly at 80.degree. for three hours and at 95.degree. for two hours. The beads are filtered, washed with methanol, and dried at 75.degree. overnight to give 198.2 g. (99%) of product.

(b) Sulfonation of Hybrid Copolymer

A two-liter, three-necked flask is equipped with a mechanical stirrer, thermometer, Barrett trap, and a condenser is charged with 100 g. of the hybrid copolymer described above in Example 11(a), 30 g. of 1,2-dichloroethane (EDC), and 600 g. of 99% sulfuric acid. The mixture is stirred at room temperature for 30 min., 60.degree. for one hour, and 110.degree. for three hours. During this time 16.2 ml. of EDC distilled into the Barrett trap. Water (300 ml.) is added over a three hour time period and 3000 ml. over an additional three hour (with periodic removal of excess washings) period. At the end of the quenchsiphon, the liquid is removed to the bead level and the beads are neturalized with 3.times.500 ml. portions of 5% sodium hydroxide. The product is backwashed to neutrality and is isolated by filtration. The resin exhibits a sodium leakage of 6.34% measured at 10 ppm above the lowest sodium leakage point (11.52 ppm); rinse requirements--18.7 gal./ft..sup.3 ; solids--43.8%; salt splitting cation capacity--4.61 meq./g. of dry resin. The overall cross-linker level is 5.5%.

(c) Preparation of Hybrid Copolymer

In a one-liter, three-necked flask equipped with an efficient stirrer, a reflux condenser, and a drying tube is placed 100 g. of a 3% divinylbenzene (DVB)-styrene macroreticular copolymer, porosity 0.56, and 270 ml. of tap water. The mixture is heated to 80.degree. and a solution consisting of 80 g. of 8% DVB (55.9% active)-styrene monomer and 0.8 g. of benzoyl peroxide is added in one portion. The resulting mixture is stirred rapidly at 80.degree. for three hours and at 95.degree. for two hours. The beads are filtered, washed with methanol, and dried at 75.degree. overnight to give 178 g. of product.

(d) Sulfonation of Hybrid Copolymer

A two-liter, three-necked flask equipped with a mechanical stirrer, thermometer, Barrett trap, and a condenser is charged with 100 g. of the hydrid copolymer (-20+70 mesh), 30 g. of ethylene dichloride (EDC), and 603 g. of 96% sulfuric acid. The mixture is stirred at room temperature for 30 min., 60.degree. for one hour, and 110.degree. for three hours. 13.6 ml. of EDC is collected in the Barrett trap while heating to 110.degree.. The reaction is quenched at 100.degree.-110.degree. using the following schedule: 2 ml./min. for 80 ml., 4 ml./min. for 200 ml., 8 ml./min. for 200 ml., and 10 ml./min. for 720 ml. The liquid is removed to the top of the bead layer by means of a filter stick and the beads are washed with 6.times.600 ml. portions of water. To the resulting product is added 500 g. of 10% sodium hydroxide while keeping the temperature below 35.degree.. The resin in the sodium form is stirred for 30 min. and is backwashed to neutrality. The resin exhibits a sodium leakage of 4.15% with an end point taken at 10 ppm above the lowest sodium leakage point (5.65 ppm): rinse requirements--12.1 gal./ft.sup.3 ; solids--42.0%; salt splitting cation capacity--4.60 meq./g. of dry resin.

(e) Preparation of Hybrid Copolymer

In a one-liter, three-necked flask equipped with an efficient stirrer, a reflux condenser, and a drying tube is placed 100 g. of a 2% divinylbenzene (DVB)-styrene macroreticular copolymer (porosity--0.56) and 240 ml. of tap water. The mixture is heated to 80.degree. and a solution consisting of 60 g. of 8% DVB (55.9% active)-styrene monomer and 0.6 g. of benzoylperoxide is added on one portion. The resulting mixture is stirred rapdily at 80.degree. for three hours and at 95.degree. for two hours. The product is isolated by filtration, washed with methanol, and dried at 75.degree. to a constant weight to give 154.8 g. of beads.

(f) Sulfonation of Hybrid Copolymer

The procedure followed was the same as that for 11(d). The resin exhibited a sodium leakage of 2.15% with an end point taken at 10 ppm above the lowest sodium leakage point (1.85 ppm); rinse requirements--20.3 gal./ft.sup.3 ; solids--40.1%; salt splitting cation capacity--4.61 meq./g. of dry resin.

(g) Another cation exchange resin, commercially available, having a small amount of porosity believed to be achieved by solvent leaching linear polymer from an intermediate gel material. The sodium leakage is 7.45%; solids 44.6%; SSCC--4.67 meq./gm. of dry resin; lowest sodium leakage point--14.78 ppm; rinse requirements--80.9 gal./ft..sup.3. This product is manufactured by Diamond-Shamrock Company and is available under the tradename Duloite C-25D (Duloite Data Leaflet No. 25A lists the rinse requirements for C-25D as 20-30 gal./ft..sup.3).

(h) A standard, commercially available, gel type strongly acidic exchange resin having a cross-linker level of 8% DVB shows a representative 12.84% sodium leakage when measured at 10 ppm above the lowest sodium leakage point.

The Table below, Table III, compares % sodium leakage for the various resins described in Example 11.

TABLE III______________________________________Sodium LeakageWith Cation Exchange Resins.sup.1Resin Cross-Linker % Sodium.sup.2 Rinse Require-Sample Level, % Leakage ments gal/ft.sup.3______________________________________Example 11 b 5.5 6.34 18.7Example 11 d 5.2 4.15 12.1Example 11 f 4.9 2.15 20.3Example 11 g 6 7.45 80.9Example 11 h 8 12.84 88.7______________________________________ .sup.1 The data represent the average of two runs and are expressed in terms of equivalent calcium carbonate .sup.2 Measured at 10 ppm above the lowest sodium leakage point

Sodium leakage is determined, after placing the resin in the hydrogen ion form, by exhausting with a 500 ppm NaCL solution to a flow rate of 2 gal./min./cu.ft. of resin for the influent. The regenerant is H.sub.2 SO.sub.4, 10 lbs. of regenerant/cu.ft. at a 1 gal./min. flow rate per cu. ft. of resin. Low sodium leakage is very desirable in ion exchange resins, particularly resins useful in water-treating applications. As is shown in Table III above, the ion exchange resins of the present invention, e.g., 11b, 11d, and 11f, show a significant and distinct improvement in % sodium leakage value, as compared with a porous resin of the prior art, 11g, and a gel type resin of the prior art, i.e., 11h. Also, it should be noted that the rinse requirements are much less with resins of the present invention, 11b, 11d, and 11f, than they are with the resins of the prior art, i.e., 11g and 11h.

EXAMPLE 12

(a) Preparation of Hybrid Copolymer

In a two-liter, three-necked flask equipped with an effective stirrer, a condenser, and a thermometer is placed 107.6 g. of a 3% divinylbenzene (DVB) (55% active)-styrene macroreticular copolymer (-30 +60 mesh. Porosity 0.56) and 800 ml. of tap water. To this mixture is added 110 grams of a 0.5% DVB-styrene solution in which is dissolved 2.17 g. of benzoyl peroxide. The resulting mixture is stirred rapidly at room temperature for one hour and at 80.degree. for a total reaction time of 22 hours. The mixture is allowed to cool to room temperature and the resulting beads are isolated by filtration, wahsed with 600 ml. of methanol and dried to a constant weight in a steam oven (75.degree.). The hybrid copolymer is used directly in the following chloromethylation procedure. The yield of hybrid copolymer is 214.70 g. (98.5).

(b) Chloromethylation of Hybrid Copolymer

In a two-liter, three-necked flask equipped with a mechanical stirrer, a condenser with a drying tube attached and a thermometer was placed 106.03 g. of the above hybrid copolymer and 350 ml. of 1,2-dichloroethane (EDC). The mixture is stirred slowly for 10 minutes allowing the beads to swell. To the swollen beads is added 241.5 g. of chloromethyl ether (CME) in one portion. The reaction mixture is cooked to 0.degree. by means of an ice bath and 53.36 g. of aluminum chloride was added over a two hour time period, while maintaining the temperature below 5.degree.. The mixture which resulted is heated at 40.degree. for 16 hours. The resulting beads are washed once with 600 ml. of EDC and three times with 600 ml. portions of anhydrous methane. The resulting chloromethylated product was used directly in the following aminolysis.

(c) Aminolysis of the Chloromethylated Intermediate

In a two-liter, three-necked flask equipped with a mechanical stirrer, a thermometer, and a gas diffusion tube is placed the chloromethylated intermediate prepared as described above. Methanol (250 ml.) is added and the mixture is brought to pH 8 with 10% sodium carbonate. To the basic mixture is added 75 g. of trimethylamine (TMA) by means of a gas diffusion tube while maintaining the reaction temperature below 15.degree. with an ice bath. After the addition is completed the reaction is stirred at room temperature overnight. The unreacted TMA and the methanol are removed by distillation while maintaining a constant fluid level by the gradual addition of water. The reaction mixture is cooled and the product is backwashed to neutrality and isolated by filtration. The product has an average DVB-content of 1.6 g.; solids--52.43, anion exchange capacity 4.51 meq./g. of dry resin; reversible swelling--14.5%; column capacity at a 5 gal./ft..sup.3 /min. Flow rate--10.5 Kgr./ft.sup.3.

The following table, Table IV, shows the improvement in sugar decolorization that can be obtained with the novel hybrid ion exchange resins of the present invention.

TABLE IV______________________________________Sugar Decolorization with Hybrid Resins % Sorp. % Sorp. Weight of of Color Stability Capa- Color Bodies from Thur- (afterResin city Bodies Resin put cycling)Sample (milli- equiva- lents quat. ammonium function- ality per gm. of dry resin)______________________________________Resin E.sup.1 4.25 84.4 79.9 235 98/2/0Resin F.sup.2 4.18 81.9 76.6 269 84/15/1Resin G.sup.3 3.7 86.5 56.1 168 0/99/1Resin H.sup.4 4.20 85.9 70.8 190 95/4/1______________________________________ .sup.1 hybrid resin 30 g. of 0.5% DVB - 99.5% styrene/mole of 0.56 porosity macroreticular base having quat. ammonium functionality prepared according to teachings of Example 4, above. .sup.2 hybrid resin 60 g. of 0.5% DVB - 99.5% styrene/mole of 0.56 porosity macroreticular base having quat. ammonium functionality prepared according to teachings of Example 12, above. .sup.3 gel-type quat. ammonium resin commercially available, styrene-DVB (1%) cross-linked matrix. .sup.4 macroreticular quat. ammonium resin commercially available styrene-DVB (3%) cross-linked matrix.

The above data show the unexpected improvement in the ability of the hybrid resin to decolorize sugar solutions. In particular, the hybrid resins E and F lasted for 235 and 269 bed volumes, respectively, (to a given endpoint) while related gel and macroreticular resins lasted only for 168 and 190 bed volumes, respectively, to the same endpoint. The decolorization data is obtained as follows:

The color is monitored colorometrically at 420 m.mu.. The influent sugar is light cane (approx. 55 Brix) off of activated carbon beds at Sucrest Sugar Co. The conditions of the column runs are as follows:

Treatment temperature--70.degree. C.

Treatment flow rate--1.25 gal/ft.sup.3 /min

Bed size--30 mls.

Mesh size--20-40 standard screen

Endpoint--40% color leakage

Regeneration temperature--70.degree. C.

Regeneration flow rate--0.25 gal/ft.sup.3 /min

Regeneration level--60 lb/ft.sup.3 of NaCl (10%)

EXAMPLE 13

(a) Preparation--Acrylic Hybrid Copolymer

In a one-liter, three-necked flask equipped with a mechanical stirrer, a condenser and a thermo-watch-thermometer combination is placed 114.13 g. of a 20% divinylbenzene-(DVB)-styrene macroreticular copolymer (-30 +70 mesh) and 216.64 g. of tap water. To this is added with rapid stirring 30 g. of a 10% DVB-methylacrylate solution in which is dissolved 1.44 g. of benzoyl peroxide. The reaction mixture is stirred rapdily and heated at 80.degree. C. for 3 hours and the temperature increased to 95.degree. C. for 2 hours. The mixture is cooled and the copolymer is isolated by filtration, washed with 600 ml. of methanol and dried in a steam oven (75.degree. C.) until a constant weight of hybrid copolymer is achieved to give 133.40 g. (92.55%) of product.

(b) Acrylic Hybrid Copolymer Hydrolysis

In a two-liter, three-necked flask equipped with a mechanical stirrer, a condenser to which is attached a drying tube, an addition funnel, distillation head, and thermometer is added 111.40 g. of the hybrid copolymer described above and 305.65 g. of a 55.21% sulfuric acid solution. The solution is distilled for 15 hours with concurrent addition of make-up water. A non-ionic wetting agent is added as necessary to control foaming. When the distillation is complete, the hydrolyzed copolymer is back-washed until the effluent is neutral. The copolymer is isolated by filtration, washed with 600 ml. of methanol, and dried in a steam oven (75.degree.) until a constant weight of copolymer is achieved.

(c) Sulfonation of the Styrene Acrylic Hybrid Copolymer

To 100 g. of the hydrolyzed copolymer (KT1492) in a three-liter, three-necked flask equipped with a stirrer, thermometer, and a Barrett-trap to which is connected a condenser with a drying tube was added 600 ml. of 97% sulfuric acid. The mixture is stirred until thoroughly mixed and is heated at 120.degree. for 6 hours. The mixture is cooled to 50.degree. C. with the aid of an ice bath and water is added dropwise at such a rate as to maintain the temperature at 70.degree.. When 500 ml. of water had been added one half of the liquid layer is drained by means of a filter stick. The washing procedure is repeated three times and the product is backwashed to neutrality.

EXAMPLE 14

(a) Preparation of a Vinyl Pyridine Hybrid Copolymer

In a one-liter, three-necked flask equipped with a mechanical stirrer, a condenser, and a thermometer is placed 107.6 g. of a 3% DVB-styrene macroreticular copolymer (-30, +70 mesh, 0.56 porosity) and 206 g. of water. To this mixture is added with rapid stirring 30 g. of a 3% DVB-2-vinylpyridine solution in which is dissolved 1.37 g. of benzoyl peroxide. The reaction mixture is stirred rapidly at 80.degree. for 3 hr. and at 95.degree. C. for 2 hr. The resulting mixture is cooled and the copolymer is isolated by filtration, washed with 600 ml. of methanol and dried to a constant weight at 75.degree. to give 133.7 g. (97.1%) of product.

EXAMPLE 15

1. Preparation of Styrene/Divinyl Benzene (DVB) Hybrid Copolymer Containing Dimethyl Itaconate (DMI)

The hybrid copolymer is prepared by the following procedure. Styrene/DVB (100 g.) and 400 g. tap water are introduced into a 1 liter, 3-necked flask fitted with mechanical stirrer, reflux condenser, N.sub.2 inlet tube, thermometer, heating mantle, and thermowatch assembly. To the flask is added a premixed solution of 173.96 g. (DMI), 7.62 g. DVB (53.9% assay), 1.31 g. diethylene glycol divinyl ether (DEGDVE), 20.27 g. diisobutyl ketone (DIBK), and 3.6 g. lauroyl peroxide over a period of 1/2 hour with stirring. The stirring is continued for an additional 1/2 hour followed by heating the mixture to 60.degree. C. for 20 hours. After azeotropic distillation of the DIBK, the copolymer is isolated, washed with water, and oven dried, yield is 243.6 g. (86.2%).

2. Chloromethylation Procedure

The hybrid copolymer is chloromethylated in a 2 liter, 3-necked flask equipped with mechanical stirrer, reflux condenser, thermometer, and external cooling bath. The hybrid copolymer (143.6 g.), 999 ml ethylene dichloride (EDC), and 746 g. of chloromethyl ether (CME) are stirred in the flask for 2 hours, cooled to 0.degree.-5.degree. C., and 332 g. of AlCl.sub.3 added incrementally over a two hour period while maintaining the temperature at 0.degree.-10.degree. C. Upon completion of the AlCl.sub.3 addition, the temperature is raised to 25.degree. C. and held for 3 hours. The reaction is quenched by pouring into 1 liter of chilled methanol while maintaining the temperature below 35.degree. C. The mixture is stirred 15 minutes, stick filtered, and the resin washed with 1 liter of methanol. Removal of the methanol from the resin is followed by the addition of 1 liter of DI water and addition of 50% NaOH to make the solution basic. After heating to 100.degree. C. for 15-20 minutes, the solution is cooled and stick filtered. An analytical sample of the resin contains 14.78% Cl.

3. Aminolysis-Hydrolysis of the Chloromethylated Hybrid Copolymer

The entire chloromethylated hybrid copolymer sample is placed in a 2 liter, 3-necked flask fitted with mechanical stirrer, thermometer, dry ice condenser, and heating mantel. To the flask is added 120 g. cracked ice, 120 g. of 50% NaOH, and 338 g. of 40% dimethylamine (DMA). The mixture is stirred at ambient temperature for 1 hour, then heated to reflux for 4 hours and finally to .about.100.degree. C. for 2 hours to remove the excess DMA (dry ice condenser is replaced with water cooled condenser for this last step). The product is isolated, washed with water, and stored wet. Analysis gives 9.9% Cl and 4.5% N. General properties of the resin are measured as 49.41% solids, 3.10 meq/g. total anion exchange capacity (TAEC), and 1.52 meq/g. cation exchange capacity (CEC). Thermal salt capacities (mg NaCl/15 cc.) are measured at pH 6-8 using a 540 ppm NaCl solution. Measured values are 46.61 (pH 6), 77.81 (pH 7), and 43.95 (pH 8).

EXAMPLE 16

PREPARATION OF A MACROPOROUS HYBRID COPOLYMER

In a one-liter, three necked flask equipped with a mechanical stirrer, thermometer, and condenser is placed 100 g. of an 8% divinylbenzene (DVB)-methyl acrylate macroreticular copolymer and 400 ml. of tap water. To this mixture is added with rapid stirring 137 g. of a 1% DVB, 40% methylisobutylketone (MIBC)-VBC solution in which is dissolved 0.8 g. of benzoyl peroxide. The mixture is stirred for two hours during which time the preformed copolymer absorbed the added monomer mixture. The mixture is heated at 65.degree. C. for 16 hours to insure complete polymerization. The temperature is increased to 100.degree. C. and held for 3 hours while distilling out the MIBC. The product is isolated by filtration an dried at 75.degree. C. to a constant weight to give 179 g. (98.7%) of opaque white beads.

Amination of the above hybrid copolymer with dimethylamine, followed by caustic hydrolysis, yields an amphoteric resin having 2.5 MEQ/gram anion exchange capacity and 5.0 MEQ/gram cation exchange capacity. Additionally the resin has a thermal salt capacity of 0.195 MEQ NaCl/ml. at 500 ppm NaCl load at 25.degree. C. and 500 ppm NaCl regeneration at 95.degree. C.

The above-detailed description has been given for clearness of understanding only. No unnecessary limitations should be understood therefrom, as modifications will be obvious to those skilled in the art. While the examples given hereinabove deal with addition type polymers, the present invention also embracxes other types of polymers which may form one or more of the components of the hybrid copolymers and/or resins. Thus, condensation polymers, or mixtures of condensation polymers and addition polymers, may be used as the host polymer or phase or as the guest fill or guest phase.

Claims

1. A hydrophobic, heterogeneous hybrid copolymer having two relatively independent phases comprising a crosslinked macroreticular porous host or base copolymer phase having a surface area of at least 5 sq. meters per gram and macropores larger than about 15-20 A units, of a polyunsaturated monomer and a monoethylenically unsaturated monomer, the polyunsaturated monomer being selected from the group

(a) consisting of divinylbenzene, divinytoluene, divinylnaphthalene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethyacrylate, neopentyl glycol dimethacrylate, bis-phenol-A-dimethacrylate, divinyl xylene, divinylsulfone, divinylketone, divinylsulfide, allylacrylate, trivinylbenzene, trivinylnaphthalene, and diallyl esters,

and the monoethylenically unsaturated monomer being selected from the group

(b) consisting of esters of acrylic acid, esters of methacrylic acid, styrene, vinyl naphthalene, dimethyl itaconate, vinyl toluene, ethylvinyl benzene and vinylbenzyl chloride,

said macroreticular copolymer having its macropores at least partially filled with a crosslinked guest polymer phase of a polyunsaturated monomer and a monoethylenically unsaturated monomer of the groups (a) and (b) mentioned above, the guest copolymer being present in the amount of about 10-200 parts by weight per hundred parts by weight of macroreticular host polymer or phase.

2. A hydrophobic, heterogeneous hybrid copolymer according to claim 1 in which the polyunsaturated monomer is divinylbenzene and the monoethylenically unsaturated monomer is styrene.

3. A hydrophobic, heterogeneous hybrid copolymer according to claim 1 in which the amount of the crosslinker or polyunsaturated monomer in the copolymer is present in an amount about 1/2% to about 20%.

4. A hydrophobic heterogeneous hybrid copolymer according to claim 1 wherein polyethylenically unsaturated monomer is divinylbenzene and the monoethylenically unsaturated monomer is styrene in the host phase of the hybrid copolymer, said divinylbenzene being present in the host phase in an amount of up to about 20% by weight and where in the guest phase the polyethylenically unsaturated monomer is divinylbenzene and the ethylenically unsaturated monomer is methyl acrylate, the divinylbenzene in the guest phase being present in an amount of up to about 10% by weight and the total polyethylenically unsaturated crosslinker level in the overall hybrid copolymer being present in an amount of up to about 18% by weight.

5. A hydrophobic, heterogeneous hybrid copolymer according to claim 1 wherein the guest copolymer or phase is present in the amount of about 5-300 parts by weight per 100 parts by weight of macroreticular host polymer or phase.

6. A hydrophobic, heterogeneous hybrid copolymer according to claim 1 wherein the guest copolymer or phase is present in the amount of about 25-100 parts by weight per hundred parts by weight of macroreticular host copolymer or phase and wherein the crosslinking density of the guest phase is less than that of the macroreticular copolymer or phase.

7. A hydrophobic, heterogeneous hybrid copolymer according to claim 1 wherein the guest copolymer is gellular.

8. A hydrophobic, heterogeneous hybrid copolymer according to claim 1 wherein the guest copolymer is macroreticular.

9. A process for making a hydrophobic, heterogeneous hybrid copolymer in particulate form having two relatively independent phases consisting of a macroreticular host phase having its macropores at least partially filled with a second crosslinked copolymer guest phase which comprises adding to an aqueous suspension of macroreticular particles or beads of an essentially hydrophobic copolymer having a significant degree of porosity, a surface area of at least 5 sq. meters per gram, and macropores larger than about 15-20 A units, a liquid mixture comprising a monomer which is a (1) monoethylenically unsaturated monomer selected from the group consisting of esters of acrylic acid, esters of methacrylic acid, styrene, vinylnaphthalene, dimethyl itaconate, vinyltoluene, ethylvinyl benzene and vinylbenzyl chloride and (2) a polyethenically unsaturated monomer selected from the group consisting of divinylbenzene, divinyltoluene, divinylnaphthalene, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, neopentyl glycol dimethacrylate, bis-phenol-A-dimethacrylate, divinyl xylene, divinylsulfone, divinylketone, divinylsulfide, allylacrylate, trivinylbenzene, trivinylnaphthalene, and diallyl esters, imbibing said monomer liquid mixture into the macropores or particles of the macroreticular copolymer, the monomer liquid being present in an amount of about 5-300 parts by weight per 100 parts by weight of macroreticular copolymer, and thereafter heating the suspension containing the imbibed liquid monomer to polymerize the mixture within the macroreticular copolymer to cause the macropores to become at least partially filled with a second crosslinked copolymer guest phase.

10. A process according to claim 9 in which the amount of the polyethylenically unsaturated crosslinking monomer in the hybrid copolymer is present in an amount of about 1/2% to about 10% by weight.

11. A process according to claim 10 in which the polyethylenically unsaturated crosslinking monomer is divinylbenzene and the monoethylenically unsaturated monomer is styrene.