JPS62257903A - Insoluble solid crosslinked composition and treatment of paper or fabric - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel solid polymer compositions, their preparation and crosslinking and their uses.

A well-established method for improving the physical properties and solvent resistance of linear polymers is crosslinking, in which each polymer chain is joined at many points to form a continuous network. ing. Is the cross-linking 71? However, the covalent casing or chemically crosslinked structure has high strength, high resistance to hydrolysis, and a wide range of applications. is wide.

The most common way to perform covalent crosslinking is to use polyfunctional monomers in the polymerization reaction itself (eg when using divinylbenzene with styrene). Cross-linked polymers cannot be dissolved, melted or cast;
Polymerization must be carried out to achieve the desired final physical form. Problems often arise in the manufacture of films and membrane materials when catalysts must be introduced or when inhibitors such as oxygen must be removed from the polymerization reaction. Furthermore, the monomers themselves are often too toxic, too volatile, or too fluid to be conveniently processed in this manner. All of these factors make the manufacturing process difficult and expensive.

It is therefore preferred in many cases to prepare a linear polymer or a polymer dissolved in a suitable solvent, spray or cast into the desired final shape, and then simply crosslink. A well-known example of such post-crosslinking is the vulcanization of rubber, in which linear polyisogrene is mixed with sulfur, shaped, and then heat cured. Another example is the crosslinking of various unsaturated polymers by light; this technique has been utilized to make photolithography plates.

Although many polymers form loosely crosslinked glues upon heating, the mechanism is largely unclear and crosslinking is therefore difficult to predict or control. The present invention provides a post-crosslinking method with a unique mechanism,
The practical applications of polymers to which this method can be applied are wide-ranging.

To form new ester bonds between polymer chains,
It is possible to alcohol-rinse the side chain amide group or ester group on the polymer with a hydroxyl group, or to form a new amide bond between the polymer chains, the side chain amide group or ester group on the polymer It is thought to be able to amide (or amitorise) with an amino group, or to form a new ester bond or amide bond, it is possible to react the side chain calyiζ xyl group of the polymer with a hydroxyl group. .

Depending on the nature of the reaction and residual groups, acid or base catalysts may be used to obtain optimal crosslinking, or no catalyst may be used at all.

Alcohol rinsing of amides and esters is a well-known reaction in small molecule organic chemistry, where alcoholysis is generally carried out in solution at reflux temperature with a strong acid or base medium. Kope sec (Kopec @
One of the several mechanisms deduced by Panoropa (K) and Panoropa (Baz) explains the unusually high molecular weights obtained in the solution polymerization of N-(2-hydroxypropyl) methacrylamide [ European Polymer Journal
Polymer Journal), Volume 9, p. 10
~11 (1973)). These authors only consider the possibility of dimerization; actual crosslinking is not discussed, nor do they report that insolubilization occurs.

A feature of the alcohol rinse, amithrisis and transamination reactions described in the present invention is that a solid state is obtained in the absence of a solvent, and such a phenomenon is completely unexpected1 and hitherto unconventional. has not been reported.

Similarly, the amitolysis of amides and esters is a well-known reaction in small molecule organic chemistry, where the amitolysis is usually carried out at elevated temperatures and, depending on the nature of the solvent and the residual groups, sometimes in the presence of a basic melting medium. It is also sometimes carried out in the presence of an acid catalyst or even without the use of a catalyst at all. The novel post-crosslinking technique taught in this invention has many unique advantages, particularly in the production of synthetic membranes.

Conventional membranes for reverse osmosis (RO) and ultrafiltration (UF) are made of polymers that are insoluble in the fluid (most often water) being treated by the membrane. Typically, linear polyamides, polysulfones or cellulose acetates are removed from organic solvents and coagulated in water. Such membranes are hard;
Although it is physically strong, it is hydrophobic and prone to fouling due to adsorption of hydrophobic particles and solutes in the feed stream.

Such fouling is a major problem in industrial use of membranes, which often requires cleaning or expensive pretreatments.

Strongly hydrophilic polymers prevent such adsorption contamination.
It has been clarified that υ, and such hydrophilic polymers include those in which at least 80% of the constituent units have high polarity to increase the water solubility of the linear polymer, and those in which each unit has a fixing agent. There are those that have a charge or a negative charge, as well as those that are uncharged, such as acrylamide, which have an equally high affinity for water. However, they either dissolve in water or form soft cells with little crosslinking. Useful membranes can be made from such polymers with only a high degree of crosslinking, so that such membranes swell by a factor of up to 3 to 5 when immersed in water. Since the porous structure of such membranes is usually created by coagulation, and since the monomers are inherently non-coagulable, it is the best practical option to post-crosslink the coagulated linear polymer. It's a method. Using the techniques taught by the present invention, highly cross-linked U with controlled porosity
F membranes can be cast from highly hydrophilic polymers. The complex porous structure of these coagulated films is maintained by solid-state post-crosslinking. Furthermore, charged functionalities such as sulfonate or quaternary ammonium can be incorporated and Grego (Gr
(US Pat. No. 3,808,305). In this case, the fixed charge rejects the formation of charged colloidal particles and produces only slightly soluble salts of the solder.

A typical commonly used hydrophilic support medium is cross-linked polyacrylamide (PAM) beads of different sizes and varying degrees of cross-linking, which act to control porosity size. . PAM contains a carbon skeleton to which is attached a side chain amide carbunyl group, which contains an amide ammonia nitrogen and can be easily substituted with other nitrogen compounds, thus creating several derivatives with useful properties. can be formed. Inman and Dintz
is) [Biochemistry (Blochs+rnistry), Vol. 8, p. 4,
074-4,082 (1969)], commercially available beads made from a crosslinked copolymer of acrylamide and N,N'-methylenebisacrylamide were reverse-treated by several different reactions and It has been shown to produce useful products. The above authors directly aminoethylated the beads and added hydranod; trinitrophenyl: 2,
A number of derivatives from these beads were generated including 4-nonitroliphenylaminoethyl; succinylhydrazide:sulfonithyl; and p-hydroxyphenethyl. The above authors also found that it is possible to carry out cy-primary aminocaggling by the general acylat method. In this case, a hydrazide derivative was used.

Additionally, the above authors have performed force on proteins such as serum albumin by an acyl azide reaction, f-ring, and coupling to trizocine by treatment of the hydranode derivative with room temperature nitrous acid and subsequent treatment with an appropriate solution of trinosine. Furthermore, the above author p-
Conversion of the aminoethyl derivative of PAM using nitrobenzoyl azide followed by triethylamine and DM
Washing with F produced a p-nitrobenzamidoethyl derivative, which was then converted to a p-aminobenzamidoethyl derivative. The above p-aminobenzamidoethyl derivative is
After treatment with nitrous acid, it was used to couple bovine serum albumin via a noazonium intermediate. The authors further used some of these derivatives as immobilized enzymes and immunoadsorbents.

The materials that can be produced according to the teachings of the present invention constitute particularly useful and effective materials for modern biochemical and molecular biology techniques. The production of such materials often requires continuous and laborious laboratory processing, usually carried out over several days. A primary raw material is first provided and this raw material is immediately diluted to produce a dilute solution containing only small amounts of the desired components. Conventional biochemical techniques, which involve salt precipitation, desalting and sequential column chromatography, often determining the final concentration by freeze-drying and subsequent processing, are extremely laborious and time-consuming, and the entire process The materials intended as the final product are usually lost or denatured.

As a typical example, large columns are commonly used in the first place in the isolation of transcriptional response factors. In this column, heparin,
α-hydroxyapetite or phosphocellulose is crosslinked. Note that the above DNA-binding protein has an affinity for this column. In the next step, the active substances are usually eluted using different salt gradients and each eluted fraction is tested for specific activation. Once the active fraction has been isolated, the fraction is separated using dull permeation chromatography to determine the amount and approximate molecular weight of the proteins in this fraction, which ultimately constitute transcriptional response factors. A predetermined band containing a large amount of active protein is isolated. A final purification step is necessary because these preliminary treatments will not produce the desired single V kund of purified protein under virtually all circumstances. In this purification step, antibodies against the desired protein are grown and these antibodies are used in an affinity chromatography system to ultimately obtain the pure protein.

Since the desired component is a low molecular weight substance, such as a polypeptide that exists in a group of homologous polypeptides, purification presents a particularly difficult problem.

All of these processes have the disadvantages mentioned above, since in most cases they involve hydrophobic materials or surfaces that adsorb or lose the desired protein.

According to the present invention, the inventor has discovered the following.

That is, the substantially improved cross-linked glues in the form of films, coatings, and molded materials have at least 80% of the polymer units containing pendant amide carbs. It can be prepared by crosslinking from a solution of one or more linear polymers containing nyl or pendant ((/danto)oxycarbonyl groups).

The crosslinking is influenced by side chain hydroxyl groups extending from the polymer or hydroxyl groups present as low molecular weight polyols; or by side chain amine groups extending from the polymer or amino groups present as low molecular weight noamines or polyamines. When a catalyst is required or beneficial, such catalyst is generally strongly acidic and has a low molecular weight or is a side chain extending from the polymer. After removing the solvent by drying or coagulation,
Curing is carried out at high temperature and some of the amidocarbyl or oxycarbonyl groups are treated with alcohol to form ester or amide bonds. The ester bond crosslinks and insolubilizes the glue, and the amide bond similarly crosslinks and insolubilizes the glue. The present invention can produce membranes, films, and solid glues with superior strength, controlled pore size, and controlled swelling properties, and furthermore, these products possess a wide range of fixed charges and other functionalities. be able to. - As mentioned above, the crosslinking reaction according to the invention involves the presence of the following functional groups: side chain amides or esters, alcohols, amines and (in most cases) strong acids. The alcohol or amine may itself be a polymer (e.g. hydroxyhexyl acrylamide copolymer) with side chain functional groups, or a low molecular weight polyol (e.g. glycerol or pentaerythritol),
or a diamine or polyamine. The alcohol group must be secondary, nonvolatile, and not easily decomposed under high temperature curing conditions. The hydroxyl group can also be present in an initial form such as hydroxyl. Although it is of course possible to carry out the reverse reaction of crosslinking polymers with side chain alcohol groups using low molecular weight bisamides or bisesters, it is not convenient and the hydrolytic capacity of the resulting resin is tend to be smaller than those produced from crosslinking reactions. In cases involving crosslinking of diamines/polyamines, the amine group is preferably a primary amine, but may also be a tertiary amine. However, tertiary amines cannot be used. The amine must also have low volatility;
Or it must be non-volatile and not easily decomposed at high temperatures.

Although the reaction is greatly accelerated by acid catalysis, some polymers such as polyacrylamide crosslink well in the absence of catalyst. The acid must be strong, volatile, and non-oxidizing. The acid may also have side chains, as in poly(3-sulfonolobyl acrylate), or may be a discrete low molecular weight molecule. Methanesulfonic acid is ideal for this purpose, but similar strong mineral or organic acids can be used. At least 0.1 per molecule of crosslinked alcohol functional group
mol of acid catalyst should be used; if the ratio exceeds 1:1 no beneficial effect will be obtained. If the acid catalyst is [F] with a side chain functionality on the polymer, excellent crosslinking is achieved when additional low molecular weight acids are used as well. This is probably because the catalytic ability is concentrated at the reaction site.@As long as long chain molecules with side chain amidocarpyl or oxycarbonyl groups are stable under the conditions of high temperature curing, the present invention suitable for cross-linking. The most common and practical of these are N-substituted polyacrylamides and polymethacrylamides, esters of polyacrylic acid and polymethac+)kW, or homologs of the acids themselves and the following polymers; (2) Each R is the same or different, hydrogen, or an alkyl group having up to 10 carbon atoms, or an aryl group having up to 10 carbon atoms, and R' is an alkylene group having up to 10 carbon atoms. or an arylene group having up to 10 carbon atoms, R〃 is an alkyl group having up to 10 carbon atoms or an aryl group having 10 carbon atoms, and this R''
may have substituents that impart desired functionality to the R'' group, such as carboxyl, sulfonic acid, amine, ammonium or other functional groups.

Alkyl substituents on the polymer backbone are therefore mandatory (e.g. polyethacrylamide or poly(2-
propyl acrylate)), and the amidocarbyl or oxycarbonyl group may also be extended from the polymer backbone by one or more methylene units, as in the amide or ester of poly(3-butenoic acid). Since the solid state crosslinking reaction of the present invention is highly susceptible to steric hindrance, substituents near the crosslinking site should be avoided as much as possible.

Various functional groups may be present on the alkyl N-substituent of the polyacrylamide or the alcohol moiety of the polyacrylate ester.

The polyacrylamide may have one or two N-substituents or may be free of such substituents. Amidocal in N-substituted polyacrylamide? A positive charge must be present near the nyl group. Since a positive charge is likely generated at this location during the reaction (ultimately appearing on the positively charged amine by-product), a second positive charge fixed nearby inhibits cross-linking of such polymers. For the corresponding polyacrylate ester,
The by-product is a neutral alcohol, and such polymers are effectively crosslinked. Of note, the hydrophobic physical properties are influenced by substituting side chain functional groups with polyhydroxyl alcohols such as glycerol or pentaerythritol. In fact, non-functional alcohols are bound onto the polymer according to the present invention to produce linear polymers of varying solubility.

The main advantage of the new crosslinking method is that the crosslinking takes place in the solid state in the absence of solvents. The polymer chains intertwine in close proximity during crosslinking, thus forming a tightly bonded network that exhibits little swelling in solvents. Consequently, it is necessary to have good compatibility in the solid state at the molecular level of all polymers and low molecular weight substances. If the catalyst or crosslinker is removed from the polymer during drying, the reaction will not be satisfactory. If the matrix polymer undergoes phase separation, the polymer will not be able to increase its strength and its natural swellability will be reduced. The speed and method of drying affects the tightness of the chains. Polymers dried in the expanded state (eg lyophilized) do not undergo satisfactory crosslinking. The molecular weight of the polymer is not very important since the crosslinking reaction actually joins the polymer chains into a single molecule. Very low molecular weight polymers ((50,000) tend not to entangle well in the solid state, thus producing highly swollen, less tight glues.

Other factors also affect the tightness of the crosslinks for this invention. The crosslinking agent added and the number of crosslinkable side chain amide groups or ester groups in the copolymer are very important. The crosslinking agent or crosslinking component is 0.1 molt (1
With a small amount of force (relative to the monomer content of the coalescence), the polymer will be insolubilized as an extremely loose and loose glue.
On the other hand, when the amount exceeds 50 mol, hardly any reactive sites are found in the polymer. In order to achieve the desired amount of primary groups in the chain and a high degree of crosslinking, at least 80 units and at most 100 units of the chain must serve as reactive sites. The higher the temperature, the longer the curing will take place and the more effective the crosslinking will be. Curing times of more than 3 hours at 150°C do not produce any beneficial effects; in fact, the cure time is 1 hour at 120°C, but it is possible to insolubilize for a longer time at lower temperatures. The techniques of the invention can be applied to produce membranes of many types of polymers. For example, conventional RO membranes are often swollen in compression over a period of time, making them susceptible to biochemical and chemical attack (particularly chlorination). The tight cross-linking made possible by the technology of the present invention increases the physical strength and reduces the effects of polymer chain scission, which makes the RO membrane selective under various conditions of use. can be used. Furthermore, the ability to fabricate RO membranes with clean hydrophilic coatings reduces the need to pre-treat the feed stream.

Conventional electrodialysis (ED) membranes contain small amounts of charged groups fixed within the pores of a hydrophobic polymer matrix. Using the technology of the present invention, EDpA with very high fixed charge density, tight porosity structure and low swelling
can be manufactured at low cost. Membrane permeability (MP)
Alternatively, if complete evaporation is required, an extremely thin membrane is required that selectively absorbs one component of the feed stream without irreversible swelling or shrinkage.

According to the technique of the present invention, a wide range of polymers with different chemical affinities can be incorporated into the film, the swellability of which is determined by the degree of crosslinking. Solvent extraction membranes must also not swell excessively and have controlled porosity, and these techniques are also adaptable. After all, the wide range of functional groups compatible with post-crosslinking methods provides extraordinary versatility in the production of porous coagulated membranes for enzymatic coupling.

The technique of the present invention allows for the production of a wide variety of new and highly useful adhesive coatings. Although cross-linked coatings have long been known to exhibit superior strength and solvent resistance, the production of these cross-linked coatings typically involves photocuring (as in the case of paints) or harmful chemical additives (epoxies).
(as in ). In the present invention, a viscous solution of a polymer and a relatively non-toxic crosslinking agent (incorporated into the polymer) is applied to a surface and cured by heat in a relatively short period of time. 4-lyacrylamide and its congeners can be cast into thin films suitable for electrophoresis. Coatings containing highly sulfonated polymers are susceptible to contamination,
Prevents clot formation and microbial adhesion. These coatings are therefore useful for coating heat exchangers, artificial heart valves, ship bottoms, and screens for removing suspended solids.

Solid glues of the present invention can also be produced that have high moisture content, high physical strength, biocompatibility, and resistance to biological contamination due to optical clarity, and these solid glues can be used in long-term abrasion resistant contact lenses and It is ideal for other devices used in eye protection.

According to other techniques of the invention, paper and/or textiles can be treated to effect surface crosslinking and/or modification of the surface properties of the paper or textile to achieve desired effects. The polymers of this invention can be used to modify the physical properties and surface charge of paper, thereby improving the appearance, ink ride or hand of the paper. When the polymer of the present invention is applied to textiles, the dye coverage, wrinkle resistance and texture are improved.

An important advantage of the polymers of the present invention is that no soluble catalyst or co-reactant needs to be present in the crosslinking process. This advantageously avoids the flow contamination problems caused by surface treatments in most cases.

The fact that crosslinking can be carried out to a high degree without producing toxic gases is also a major advantage. A crosslinking reaction that can avoid the generation of formaldehyde, for example, is also a major advantage.

Furthermore, the polymers of the invention can also be used as barrier films in the production of microelectronic circuits and chips, in which case the crosslinking properties and ease of adhesion of these Paris 1'-films! This is an important advantage. These polymers are likewise useful in lithographic printing, where the polymers can impart different adsorption properties to the printing plate surface, or even no adsorption properties at all.

In particular, the technology of the invention can be used for special purposes, namely in the production of adsorbents, especially biochemical adsorbents.

Although the nature of biochemical sorbents is completely hydrophilic to minimize nonspecific absorption of proteins, most of the carriers commonly used for these purposes contain significant toxic Performs non-specific adsorption of approximately Additionally, most of the useful carrier materials cannot be formed into sheets, films, coatings or membranes with controlled porosity in a manner that produces a wide range of hydrophilic materials upon post-crosslinking in accordance with the teachings of the present invention. Can not.

The present invention is advantageous in many ways. First, the present invention provides a dialysis or ultrafiltration system that does not denature the protein, ie, does not lose active desired protein during the purification step. Furthermore, ultrafiltration is a suitable technique for easily and rapidly removing large amounts of salts or other low molecular weight impurities from protein solutions. For proteins that are extremely susceptible to denaturation, denaturation can be minimized or avoided by coating the tubes and cells according to the present invention. The polymers of the present invention are highly suitable for large-scale as well as small-scale ultrafiltration operations. Ultrafiltration using the polymers of the invention can be carried out at high speeds using simple equipment. In the examples below, we describe a very thin glue electrophoresis system suitable for analyzing very small sample volumes.

The following examples include monomer production, homotogane, copolymerization,
Consists of crosslinking of polymer films and resins, and casting and testing of membranes. The polymerizations carried out in the examples yield polymers of nearly the same molecular weight and comonomer composition as required in the crosslinking and membrane examples.

In case of differences, the polymerization method can be easily modified according to principles well known to those skilled in the art.

For example, molecular weight can be increased by reducing the amount of catalyst, or can be decreased by adding a suitable chain transfer agent such as inolonol. Since the reactivity ratios in almost all copolymers are comparable, the composition of the comonomers can be varied by appropriately adjusting the initial amounts of each monomer. If molecular weights are given, they are determined by viscometry or glue permeation chromatography. In the absence of a reference molecular weight, an estimate is made based on the viscosity or cell permeation capacity of similar known polymers. The difference between weight average molecular weight and number average molecular weight is of no significance since molecular weight is altered by at least two factors without changing the results.

All solutions of polymers are prepared on a weight/volume basis;
Concentrations of total solutes are given in % by weight. The relative proportions of solutes in the ridges are expressed in parts by weight. The concentration of low molecular value compounds is expressed in moles relative to the monomer units of the polymer in solution. All solvents are of experimental quality, but in many cases it is possible to substitute practical or industrial versions. All water used as a solvent or reagent in these examples is distilled water. All ethanol used was of standard strength 200.

Swelling index is the ratio of the weight it or volume of the resin swollen with solvent to the resin in the dry state by standard measurements. All resins and membranes containing polyelectrolytes are soaked in saturated sodium chloride solution after soaking in distilled water and before heat curing to minimize osmotic shock.

All of the membranes described below are manufactured by using similar basic techniques well known to those skilled in the art. Unless otherwise specified, all membranes mentioned in these examples are manufactured by Hollytx.
1, i.e., rolled polyester nonwoven fabric [Eaton-Dlks+man
Co-)). The casting solution is filtered through a coarse glass frit, after which bubbles are removed by centrifugation or vacuum application. A viscous liquid polymeric film can be used in a hand-operated knife with a fixed or adjustable opening. Gardnar Laboratoriss
), or motorized roller-type equipment used privately in the paper and paint industry [Targeys Engineering Corporation (T.
alboy+s Engineering Corp.
), Emaraon N.
Commercially available from J.

Highly preferred are completely clear casting solutions prepared using solvents or solvent mixtures. The polymer in the above solvent or solvent mixture has a high viscosity or approximately the maximum viscosity at a given solid content.

Casting and/or coating is carried out by immersing the surface part or the support material in a casting solution, this method is often preferred when particularly thin coatings or films are desired, and This method allows the use of dilute casting solutions.

The pure water 7 lux of the membrane is measured as follows.

That is, the membrane was placed in a standard ultrafiltration cell (Getman) filled with prefiltered distilled water;
This is done by applying a nitrogen pressure of 0 to 100 psi and measuring the permeation capacity per unit time.

The flux is expressed in μ@a, i.e. microns/sec atmospheric pressure,
The above flux is completely unaffected by applied pressure. The approximate highest magnitude is obtained by measuring the percentage rejection of the red dye erythrosine from a 15 ppm feed solution. The concentration of the dye (MW836) is measured photometrically.

A type 80 membrane is tested in which a high pressure (400-800 pat) is applied across the membrane and the percentage of salt rejected is determined by conductivity.

Membrane porosity varies according to many factors, and these factors must be carefully varied and controlled to obtain the desired porosity value. Relative to an uncoagulated film, the higher the solids content in the casting solution and the larger the dart opening of the casting knife, the greater the amount of deposited polymer.

And the flux value becomes low. Slow evaporation of the solvent and high degree of cross-linking produce a non-porous glue with little swelling and low flux values.

The 7 lux of the coagulated membrane depends on the fineness of the pore structure, which in turn depends on the paper size of this pore structure and on the rate of coagulation. Hollytex
When a highly porous support such as 3329 is used, the cast film is rapidly attacked from both sides, forming large pores. Membranes cast on tight supports such as Holitex 3323, glass or mirror (MYLAR) tend to have lower fluxes. If the porous support is infiltrated with a coagulation solvent, coagulation will occur immediately upon casting and the flux will ultimately be high.

The higher the temperature of the coagulation bath, the higher the flux;
If coagulation is slow, by increasing the residence time,
The casting solvent can be completely extracted. Partial drying of the cast film before solidification results in a significantly finer porous structure and lower flux. Once the cohesive epidermis is formed, Roe
A low flux film of the b-8ourlrajan) type is obtained.

The most reliable way to control porosity is to increase or decrease the solids content in the casting solution. Films with high solids content solidify slowly and form a dense porous structure.

The higher the molecular weight of the polymer, the lower the solids content without increasing the viscosity and the higher the potential flux. Generally the smallest molecule! (MW) and a maximum molecular weight; below the minimum molecular weight, coagulation will be insufficient, and above the maximum molecular weight, the solids content will be too low and a cohesive film structure will form. The polydispersity of the polymer must not be too high, otherwise the polymer with the lowest molecular weight will cause abnormal coagulation. Tightly crosslinking a hydrophilic coagulated membrane prevents the pores from becoming too small due to swelling when the membrane is immersed in water, thus improving flux.

In the examples described herein, only a small fraction of the monomers are used, which monomers are polymerized to produce materials that are crosslinked in accordance with the techniques of the present invention.

For a particular application, the most suitable material can be selected from a large number of monomers described in the literature and/or commercially available. For example, acrylic acid and methacrylic acid can be used to form esters or amides with a wide range of substituents attached to oxygen or nitrogen atoms, respectively. These include alkyl groups and aryl groups to which a wide variety of ionic or nonionic groups are attached. One of the important advantages of the invention is that a very wide range of compounds with a large number of special uses can be used as postcrosslinkable polymers according to the invention.

Similarly, the physical properties of the final product can be modified by the nature of the crosslinker used and the reaction utilized.

Crosslinkers with long chains between each reactive group generally produce a doughy glue, whereas those with short distances between the two reactive sites produce materials with a low degree of swelling in the solvent. do. Note that the uncrosslinked polymer dissolves in the above solvent. One of the particular advantages of the present invention is the fact that the difunctional crosslinking agent has a large number of crosslinking reaction sites on the reactive polymer, whereby a particularly high degree of crosslinking is achieved.

When producing many of the films, coatings, membranes and other materials described in this invention, the bottom surface is usually Appropriate infiltration is essential. It is advantageous to modify conventional polymers to use manifold polymers and solvents useful for purposes of the present invention. For example, many aqueous solutions cannot be easily cast onto a UF-type PAN support membrane;
5:1 copolymer p (AN-AMPS) or P
It is advantageous to use (AN-MAPTAC).

The following abbreviations are used in the examples described below.

DES t-j Noethylsuccinate from EI Pa5o Products Co.

DMAC is dimethylacetamide from Aldrich.

Intestine σ is Fi 5her dimethylformamide.

TCEH is Fischer's symmetrical tetrachloroethane.

Tl (F is Fisher's tetrahydrofuran.

TMP is celanese trimethylolpropane.

A number of heptads are listed below, and these are indicated by abbreviations in the examples.

Some of the hepaticas are commercially available; others have their preparation and physical properties described in the examples.

AM is acrylamide from Polysciences.

AMPS HARTZ IJ/-LE CORPORATION (L
Ubrizol Corp, ), Special Reaction, 7-Grade (Spatial Reaction
grade) 2-acrylamido-2-methylglononosulfonic acid.

DMAM is N,N-diomethylacrylamide from Polyscience.

DMB AM is N,N-di-n-butylacrylamide as mentioned in the Examples.

HEA is Pfaltzite and Bauer hydroxyethyl acrylate.

HPA is Palatinate and Power's hydroxyglobyl acrylate.

1 (RAM is N-(6-hydroxyhexylacrylamide) as described in the Examples.

MAPTAC is Texaco Chemistry (Texac).

Chem, ) methylacrylamidopropyltrimethylammonium chloride.

NBAM is N-n-butyl acrylamide as mentioned in the Examples; O NBMAM is N-n-butyl methacrylamide as mentioned in the Examples.

NMAM is Polycye/Sys N-methylacrylamide.

SEM is Dow Chemical's 2-
It is sul7oethyl methacrylate.

5PA(Na) is the sodium salt of 3-sulfoglobyl acrylate mentioned in the examples.

5SA(K) is the K salt of styrene sulfonic acid mentioned in the examples.

TMEAC is a monomer-polymer.
-Polymar) trimethylaminoethyl acrylate chloride.

Some of the polymers used in the practice of this invention are:
Prepared as described in the following examples, these polymers are abbreviated by placing P before the literal monomer designation. Others are commercially available raw materials from the manufacturers mentioned below.

[KYNARJ i'i Polyvinylidene Fluoride from Pennwalt Corp. 5, MW 375,000 and grade 301].

PAM stands for American Cyanamid (AmericanC).
yanamid) polyacrylamide resin, trade name cyanamar, P-250, frost s,
o o o, o o o, and unless otherwise specified, PAM represents this substance.

'PAN is DuPont polyacrylonitrile, neutral modified type A and MW 150,00
If it is 0, unless otherwise specified, PAN represents this substance.

PSSA is the National Search and Chemistry
, ) polystyrene sulfonic acid with a molecular weight of 70,
000 is adjusted in this embodiment.

Additionally, several other commercially available materials were used: AIB
N is Eastman azobisisobutylnitrile.

DNPD is N from Gfalz & Pauer.

N--)-2-+phthyl-p-phenylenediamine.

EPON 1031 is manufactured by Shell Chemistry (She
It is a tetrafunctional epoxide resin from llChem, ).

Molecular sieves are manufactured by Goupyson Division Op Grace Chemical A/ (Davison Division).
ofGrace Chemical) with small pores of 3 or 4 angstroms.

MSA is Fisher's methanesulfonic acid.

Witkamid 511 is Liteco Chemistry (W
It is an emulsifier from itco Chem, ).

EDA is ethylenediamine, DAH is noaminohexane, and DAO is noaminooctane, which are commercially available from Aldrich.

Next, the present invention will be explained according to the following examples. Note that these Examples do not limit the present invention.

〔Example〕

Example 1 In two three-necked flasks, 1291 (1 mol)
No(n-glythyl)amine [Fisher 5 scientific]
] and 0.51 of dry toluene were mixed and cooled to 5°C. 46.9 (0.5 mol) of acryloyl tn, dissolved in 50 ml of toluene, were added so as to keep the temperature below 10°C. After addition, warm the flask to 25°C.
The precipitate was removed by filtration. Add 1g of DNPD,
After concentrating in a rotary evaporator.

The product was distilled at 20 Torr and 61-63°C.

Yield was 77g (84%).

Example 2 150 g of 6-aminehexanol (7'Falz & Pauer) was distilled, ground and dried under vacuum overnight. Add 11 dry THF at 40°C,
The solution was cooled with lO'C'l and partially precipitated. 1
Acryloyl chloride of 52d (57,9!I) was added dropwise over 2.5 hours while stirring at 0 to 15°C, and after 2 hours, 2
00-T)LF was further added.

The white precipitate of amine hexanol hydrochloride produced was filtered, washed with THF of IQQmj, and then
- was stirred while adding THF. The main solution was prepared by filtering 300 d of THF, treating with 5 g of 7 licaglu, and filtering again. The hydroquinone of 11 was then added and the THF solution was evaporated under vacuum to prepare an oil. 5
79.00- by recrystallization from ethyl acetate.
41 white crystalline product was produced. Evaporate the mother liquor, 75
Recrystallized from 1 Lt of ethyl acetate to give m-p-57,5
An additional 4.0 g of product was produced at ~58.5°C.

Example 3 Preparation of N-n-butylacrylamide (NBAM) In 21 three-necked flasks equipped with an iced acetone bath, a stirrer, a thermometer, and an addition funnel, 146I of n-butylamine (dried over 4A molecular sieves) was added. 11 in toluene (dried over calcium hydroxide). The solution was stirred and cooled to 0°C. 90.5.9 dissolved in 100 d of dry toluene such that the temperature does not rise to 10 °C
of distilled acryloyl chloride was slowly added. After addition, the temperature of the solution was brought to room temperature and then covered with medium porosity 7 paper. Then 1.51 non-volatile inhibitor DNP
D was added and the solution was concentrated on a rotary evaporator.

By distillation at 0.05 Torr and 85°C, 115
g of product with a yield of 90.5%.

Example 4 In 11 three-necked flasks, 400 d of dry TH
F and 4Qml of distilled n-butylamine (0,405 mol) were mixed. After cooling to 5°C in a water bath, 2 Qrnl (0,205 mol) of methacrylic chloride was slowly added, making sure to keep the temperature below 10°C. The precipitate was removed by filtration, and the F solution was concentrated using a rotary evaporator. 1
f1 DNPD was added and the oil was distilled at 76-78°C and 20 torr.

The yield was 24.3.9 (84 pieces).

Example 5 19 g of sodium acrylate, 7.51 g of acrylic acid, 60 g of tert-butanol and 0.1 g of p-methoxylphenol were heated to reflux in a 5QQmJ three-neck flask. 2511 propane sultone (Aldrich) was added dropwise over a period of 2 hours and further tertiary butanol was added, stirring as necessary. The precipitate was collected by t-filtration and dried under vacuum. This gave 409 products.

Example 6 Preparation of potassium salt 5SA(K) of styrene sulfonate 372 g (2.0 mol) in 31 four-bottle flasks
of 2-bromoethylbenzene (R8A Corporation) and 1350 m/m of 1,2-dichloroethane were mixed. Note that the above two raw materials were previously dried using a 4A molecular sieve. The flask was warmed to 60°C and flushed with nitrogen. 240 g (2.07 mol) of chlorosulfonic acid (Eastman) was dissolved in 1,2-dichloroethane and added dropwise with vigorous stirring. 60 minutes until no hydrogen chloride is generated.
Continue stirring at °C. As a partial vacuum, residual HC
11 and cooled the flask to 10'C.

A chilled solution of 13511 KOH in 750 g of distilled water was added and the flask was chilled to 0°C. The precipitate was collected using a Puchner funnel cooled with ice water and then dried under vacuum to give 440 g of coarse powder. of product was produced. 959
The above product was dissolved in a solution of 86 T KOH aqueous solution and 750 rItl of distilled water, warmed to 65° C. and filtered through a heated Buchner funnel. The Fi was slowly cooled to 5° C. and the precipitate collected and dried as described above. The yield was >30011C67%.

Example 7 Sog of AMPS was dissolved in 100 g of distilled water and then flushed with nitrogen for 30 minutes at ambient temperature.

3,2119 potassium peroxysulfate dissolved in 1 xi of water was added, continuously purged for 10 minutes, and the vessel was sealed and left at 40° C. for 16 hours. The polymer was isolated by dilution to less than 10% solids and lyophilization Example 8 where 50% (w/v) of iooy MAP
The aqueous TAC solution was warmed with 21 activated charcoal, stirred, and filtered. The solution was flushed with nitrogen for 15 minutes and warmed to 40°C under nitrogen. A solution of 100 to 100% ammonium peroxide sulfate in 100 liters of water was added, followed by a solution of 10 rR9 of sodium metabisulfite in 11 liters of water. The solution was stirred under nitrogen at 40°C until the viscosity increased sufficiently, then it was covered and placed in an oven at 60°C for 1 hour. The polymer was isolated by drying in a vacuum og/or diluted with 500 rILt of water and lyophilized. Its inherent viscosity is 0 at 25°C.
．． Example 9 Distilled NBAM was extracted with 0.1N sulfur, washed with saturated sodium sulfate, dried over anhydrous sodium sulfate, and filtered. This solution was then mixed with degassed distilled water and 1.2 g of Rau IJ) and sulfuric acid).
l) rum to produce a mixture of P) 14.0. The mixture was heated at 4QCl without stirring and nitrogen was bubbled through for 30 minutes. Next, 50 μm of ammonium peroxide sulfate was added to 1 d of water and dissolved. Latex formed within 10 minutes and polymerization continued overnight. Ethanol is added to the latex to coagulate the polymer, then this polymer is
00- in ethanol, precipitated in distilled water in a blender, and dried under high vacuum overnight to yield 32.2 g.
of polymer was produced. 1 (-F extra UNBNA
The polymerization of M proceeded in exactly the same manner as for PNRAM, except that N-butylmethacrylamide monomer was used, and the reaction was carried out at 50°C.

Example 10 751 DNBAM monomer in 375-g distilled water, 8 g
of sodium lauryl sulfate and 100 μl of ammonium peroxide disulfate, and the - was adjusted to 4.0 with phosphoric acid. The solution was stirred at 60° C. for 18 hours by bubbling nitrogen. The resulting polymer was coagulated with methanol and mixed with water to remove the detergent and harden the polymer. The polymer was further dried under vacuum to obtain 64 g of product.

Example 11 A 30% aqueous solution of SEM monomer was heated with nitrogen bubbles, 0.2 w/w% (based on the monomer) of ammonium peroxide and sulfate was added, and the mixture was polymerized at 50°C for 16 hours. Apply this solution to a weak base ion exchange column [ROHM &+].
/S (Rohm & Haaa)) to remove residual monomers, then lyophilized and fc
The molecular weight was determined to be 100.000 by the zero viscosity method in comparison to similar known polymers.

Example 12 10.9 of 5PA (
Na) was added with stirring. The solution was warmed to 50°C, 1.01R9 ammonium peroxide dihydric acid was added, the solution was covered and left overnight at 50°C. The solution was diluted until the solids content was 5%, lyophilized, redissolved until the concentration of solids in water was 5%, and loaded onto a strong acid ion exchange column [Amberlite].
It was made acidic by passing it through 200 J, Rohm & Is-K. Freeze-dry the diluted solution to recover the polymer.

Example 13 In a three-neck flask of 500 rILl, 18°J
Xylev, 209 Witkamide 511 and 401
n9 AIBN was mixed and warmed to 55° C. under nitrogen. The stirring state was maintained at 450 rpm using a stirring blade that occupied most of the inside of the flask. 30 g of potassium styrene sulfate monomer was added dropwise (0.5R 61 minutes) to 90 g of water, and the reaction was continued for 72 hours. The obtained emulsion was added to 11 acetone and separated. Remove the precipitate, mix with 11 acetone, filter and dry to 31
．． 6 g of product was obtained. This was dissolved in 600ml of water and precipitated into 1,31% absolute ethanol in the formulation. The supernatant solvent was discarded and replaced with 1.51% absolute ethanol and stirred until a finely ground material was obtained.

This was filtered and dried to give 21.9 product. The molecular weight of this product was determined to be approximately 200% by comparison to a standard sulfonated polystyrene using permeation chromatography.
I decided on 10,000. The above polymer was dissolved in water until the solids content was 5%, and the polymer was added to a strong acid ion exchange column (Amarite 2).
00. (Rohm & Haas) and then lyophilized.

Example 14 A 40% TMEAC aqueous solution of 20.9
Treated for 0 minutes and filtered. Part F solution with nitrogen, 51
Ammonium peroxide diacid n9 was added and the resulting solution was left at 50° C. overnight. Precipitate the polymer with acetone,
Filter and dry 6. ! i' (75%) product was obtained.

Example 15 Preparation of a 9:1 copolymer of P(AMPS-HHAM) In a 500 μL polymerization kettle equipped with a heating mantle, cooling coil, thermometer, overhead stirrer and glass bubble generator, 67.5 J of AMPS, 6.149 of HHAM and 300d of water were mixed.

Nitrogen was bubbled into the solution for 1 hour while maintaining the temperature at 58°C. Next, 35rn9 of ammonium peroxide dihydrate and 15μ of sodium metabisulfite were each dissolved separately in 61111 degassed distilled water, and 2- of the peroxide dihydric acid salt solution was added to the reaction kettle. , and an additional 2 d of metabisulfite solution were added. The temperature was kept as close to 68°C as possible and from the table, aliquots of 2'ILl were added after 1.5 minutes and 5.5 minutes.

After 1 hour, 300°C of distilled water was added and the resulting viscous solution was freeze-dried at -20°C. The obtained polymer was 3 l
In NaC2, O,! When measured in l solution, 2
It had an inherent viscosity of 27111//l.

Example 16 Production of 9=1 copolymer of P(NBAM-HEA) 10 moles of copolymer were determined and 1.79.9% was added to 13 grams of water.
By dissolving (0,0154 mol) of HEA,
The inhibitor in the HEA monomer was removed. This is 4
04 methanol, 17.67 fi NBAM (0
, 139 mol) and 90 μm of AIBN. The polymer was isolated by mixing with water in a compounder, followed by filtration and further drying at 45° C. under vacuum.

Yield was 17.2 g (88 g).

Example 17 Preparation of 1:1 copolymer of P(AMPS-8SA) 22g
Sodium salt of AMPS and 24 Da of 5SA(K)
(Full power (ptuka)) 801! mixed with water,
zJ with nitrogen at 40℃? -I did. 3 parts of ammonium peroxide disulfate was added and purging was continued until polymerization started. The container was covered and left at 40°C for 18 hours. Glue permeation chromatography revealed that a significant amount of monomer remained. The solution was therefore dialyzed against distilled water and the polymer was isolated by lyophilization. Yield is 38
It was g.

Example 18 In a 500d three-necked flask, 130I of xylene and 13g of Whitcamide 511 were mixed with 15μ of A
Mixed with IBN and then stirred at 50° C. under nitrogen. 21.5 g styrene potassium sulfonate, 65
The aqueous phase was prepared by mixing d water and 2.8 g HEA with charcoal and filtering. 450-50 Orp
The aqueous phase was added dropwise (approximately 0.5 d/min) to the xylene phase under stirring of m. After 48 hours, the polymer was isolated by pouring into 11 ml of absolute ethanol in a blender, decanting the solvent, and remixing with 700 ml of ethanol. Yield was 15.4.9. According to gel permeation chromatography, its molecular weight was approximately 900,000.

Example 19 To prepare PAM with a molecular weight of 1 million, 100 J of AM, 2.5+aJ of 2-pronozonol (this 2-
If there is less or no propatool, the molecular weight will be higher; if there is more 2-propanol, the molecular weight will be lower).Water was added to the mixture to make the total amount 750 rlLl, and the mixture was purged with nitrogen gas. Add a solution of 50 to 50 ammonium peroxide sulfate in 1 ml of purged water, followed by a solution of 25 μl of sodium metabisulfite in 1 ml of purged water, then boil under nitrogen. The solution was stirred and stored in a 25°C water bath. As the reaction progressed, the temperature rose to 34° C. even though the bath was cooled, and the reaction proceeded for 3 hours. Water was then added and the viscous solution was thoroughly stirred and finally freeze-dried, mixed with 31 methanol in a blender, filtered and dried.

PNMAM and PDMAM were prepared by the same method, except that a somewhat higher temperature was required with increasing substitution to maintain miscibility, and no 2-propanol was added.
is expressed in v4. The reaction was carried out for 16 hours at 50° C. under nitrogen, and the product was recovered by diluting with excess water and lyophilization.

PAM is easily soluble in water, ethyl glycol and glycerol. With increasing substitution of methyl groups on nitrogen atoms, polymers can be used in many polar organic solvents (D-T
, phenol: becomes soluble in T(J, ethanol) and can be coagulated by organic solvents such as noethyl ether.

2.5 mol of glycerol was added to a 5% aqueous solution of PAkl having a molecular weight of 5 million. The resulting clear solution was heated to 60°C.
dried inside an aluminum pan, and further heated at 140°C for 3 hours.
Time cured. After soaking in water for several hours at 80°C, the glue swelled slightly and became completely hard. When the precipitation was repeated with 10 ml of glycerol, a hard and slippery glue was produced.

When using 50 moles of glycerol and 50 moles of MSA, the appearance of the resulting glue was no different from that produced with 10 moles of glycerol alone.

PAM% PNMAM and PDMAM could be crosslinked by the same reaction as all other nonionic substituted acrylamides. Films or membranes made from PAM appeared to be the most hydrophilic, those from PNMAM were only slightly less hydrophilic, and those from PDMAM were somewhat less hydrophilic, but at most bonding points. All of these had strong hydrophilic properties compared to most polymers containing alcohol or amino groups.

Example 20 1 in a solution containing 0.11 J glycerol and 0.34 dg MSA in 28.51 Lt absolute ethanol.
．． 50g of PNRAM was dissolved. The resulting viscous solution was poured onto an aluminum sheet to a thickness of 1 and heated at 60°C for 30 minutes.
It was dried for 0 minutes and further cured at 140°C for 3 hours. The resulting film was immersed in ethanol for one week. The weight swelling index was 45 in this solvent.

In another experiment, 0.121 R1 of glycerol and 0.3811 L1 in 13.5- of ethanol
1.50! in a solution containing MSA! 1 of PNBMAN was dissolved. The resulting solution was dried and cured as described above, giving it a weight swelling index in ethanol of 4.
A film of No. 5 was formed.

In a third experiment, three solutions of PNRAM were prepared in ethanol, each at a concentration of 8. 1st
The solution contains no crosslinker and the second solution contains glycerol and M
Each solution contained 3 moles of SA, and a third solution contained 20 moles each of glycerol and MSA. Retakal installed on the glass? Pour each solution onto a film of oxymethylcellulose to a thickness of 7 mils,
It was dried at 0°C and further cured at 140°C for 3 hours. After 7 days of immersion in distilled water, the water content was determined gravimetrically.

As a result, the moisture content was 12.9% for the non-crosslinked product, 12.5% for the 3% crosslinked product, and 20%0% for the 3% crosslinked product.
The cross-linked content was 30%.

Example 21 Crosslinking of PDNBAM: Comparison with PNBAM Phenol: To a 5% solution of PDNBAM in 1:1 TCE were added 40 moles each of MSA and glycerol. A similar surface solution was prepared from PNRAM. Each of the resulting clear solutions was poured into an aluminum dish and dried at 60°C.
It was further cured at 14° C. for 3 hours. Phenol: TCE
When a 1:1 ratio of solvent was added and the resulting dal was stirred at 50° C. overnight, the polymer did not dissolve. PNBAM
A cohesive and strong film structure was obtained in the case of P
The DNBAM film was much more swollen and had a dough-like structure.

Example 22 PA with glycerol from ethanol? 111PS
Crosslinking of 90d in ethanol with 101! 0.89 g of glycerol (
20 mol%) was added. The solution was cast to a thickness of 6 mils on a glass plate, dried at 60°C, and cured at 150°C for 3 hours. After a brief soak in saturated sodium sulfate, the film was soaked in distilled water overnight. The obtained resin was hard and highly hydrophilic, hardly swelled, and did not rise from the plate before being peeled off from the plate. Its swelling index was 31. When the glycerol was removed from the reaction mixture, the cured film completely dissolved and showed no crosslinking.

Example 23 Crosslinking DM of P AMP S with nool from DMF
Add 50 mol of M to each 5 mol of PAMP solution in F.
1°3-butanediol and 1,4-butanediol were each added separately along with SA.

Dry each solution at 60 °C in an aluminum dish, then 14
It was cured for 3 hours at 0°C. Water was added and each of the above dishes was heated at 60°C for 4 hours with stirring - in each case the resulting nine-glue had the same hardness as with the same amount of glycerol and was insoluble. , and has a cohesive property, and the swelling index is 3 when using 1.3 zool and 3 when using 1.4 diol, respectively.
．． They were 0 and 3.1.

Implementation gAJ24 Crosslinking of P(AMPS-HHAM) from water A 2001n9 sample of P(8jPS-)LHAM) copolymer with a 90:10 molar composition was dissolved in 2-distilled water and heated at 60°C.
After drying at and then heating at 150° C. for 1.5 hours = immersion in saturated sodium sulfate and then in water, a crosslinked resin was obtained. The volume swelling index of this resin in water was 5.0. The same method was repeated except that it was cured for 2 hours at 145°C. The swelling index at this time is 4.
It was 7.

Example 25 P (AMP S-) blended with PAN from DMAC
) IHAM) until the crosslinked solids content of
and a copolymer of 15 mol of HRAM was dissolved in DMACK. Five parts of this solution was added with PAN in DMAC.
1 part of the 10% solution was added. Transfer the final solution onto a glass
Cast to mil thickness.

After drying at 60°C for 30 minutes, the resulting film was
It was cured for 3 hours at 5°C. This film was immersed in saturated sodium sulfate and then in distilled water. Its lateral swelling degree is 125% and its volumetric swelling index is 2.
The above experiments were performed in the same manner, except that a copolymer of 0.20 molar HHAM was used. The resulting crosslinked film exhibited a degree of lateral swelling of 6 inches and a volumetric swelling index of 2.1.

An aqueous solution of the crosslinked PSPA of Example 26 (molecular weight approximately 1,000,000) was prepared. A sample of this solution was dried at 90°C and
The polymer remained completely dissolved in water when cured for 3 hours at 40°C. The polymer did not crosslink when 50 molt MSA was added, but when 50 molt MSA and 50 molt glycerol were added, the cured polymer became a stiff cohesive solid that could be removed in hot water. It softened slightly but did not swell appreciably.

Example 27 A 10% ethanol solution of PSEM containing 50 moles each of glycerol and MSA was prepared.

After drying at 60°C, it was cured at 140°C for 3 hours to produce a weakly crosslinked glue. If glycerol is omitted,
The cured polymer was dissolved in ethanol.

Example 28 To a 5% aqueous solution of PTMEAC was added 100 moles of glycerol and 100 moles of MSA. Drying and curing at 140° C. for 3 hours produced a resin with little swelling in water. The positive charges on the side chains of this acrylate did not clearly inhibit crosslinking.

5 of PMAPTAC in ethanol at room temperature
Phenol:TCE is 1:
A 5% solution of PMAPTAC of 1 was prepared, respectively. To each solution was added 50 moles of glycerol and 50 moles of MSA.

Each of these solutions was poured into an aluminum dish, dried at 60°C, and cured at 140°C for 3 hours. Water, ethanol, and the above 1:1 solvent were added to each sample of cured resin. In each case the polymer dissolved quickly. Presumably, the positive charge on the side chain of this N-substituted acrylamide suppressed the crosslinking reaction.

Example 29 Crosslinking of P(SSA-HEA) An aqueous solution of a copolymer having an SSA:HEA molar ratio of 4:1 and a molecular weight of about 1 million was prepared. This solution was divided into three portions. I didn't add anything to the first part.

In the second part, 0.5 moles of MSA were added per mole of HEA monomer, and in the third part, 0.5 moles per mole of HEA were added.
Molar MSA and 0.5 mole glycerol were added. Pour each sample into an aluminum dish and dry.
It was cured at 140°C for 3 hours. Water was then added to the six dishes and the samples were heated to 60°C. The unreacted copolymer swelled and formed a weak glue, but did not dissolve. M.S.A.
The copolymer treated with produced a somewhat stiffer glue.

Copolymers treated with MSA and glycerol produced very stiff glues that swelled very little.
Example 30 Crosslinking of PAM with diamine from water Crosslinking of PAM with molecular weights s, o o o, o o o was carried out as follows. An aqueous solution of this polymer was prepared.

Add to this solution 28% by weight of each of the three diamines (based on seven units) in an amount equal to 25 moles of PAM.
solution was added. The above three amines are EDA and DAH
and DAO. After combining the diamine with the polymer, these solutions remained completely clear. Pour each sample into each aluminum pan to a thickness of about 2 cods and heat at 70°C for 6 hours.
It was dried for hours to remove moisture, and then cured at 140° C. for 3 hours. The degree of swelling is 2.2 for EDA and 4.3 for DAH.
and 4.8 for DAO. Additionally, hydrazi/ was used for crosslinking. This formed extremely short crosslinks, which is advantageous when very low degrees of swelling are desired.

Example 31 Crosslinking of PAM with EDA and MSA from Water 5X
In a 3% aqueous solution of PAM with a molecular weight of 10', F
25 molar each of JDA and MSA (relative to PAM) were added as 20 molar aqueous solutions. This sample was poured into an aluminum dish to a depth of about two fins and dried at 70°C for 6 hours.
It was further cured at 140°C for 3 hours. The sample was cooled and water was added. The resulting resin swelled to form a cohesive film with a swelling index of 1.5.5. The experiment was repeated using 50 mol of MSA instead of 25 mol, yielding a cohesive film structure with a swelling index of 4.5 as well.

Example 32 Crosslinking of PMAPTAC with diamines from water PMAPTAC with a molecular weight of approximately 5 x 106 in a 5% aqueous solution
Crosslinking of AC was carried out with 113% of each of the three diamines, namely EDA, DAH and DAO.
The solution was added to the polymer solution in an amount equal to 20 moles of PMAPTAC units, producing a clear solution. These were poured into an aluminum pan to a thickness of about 2 gourds, dried at 70°C for 6 hours, and further cured at 140°C for 3 hours. The crosslinked resin of EDA was the strongest and most rigid, and the degree of swelling increased slightly with increasing methylene chain length of the diamine. The swelling index is 3 for EDA. It was 3.4 in the case of O, DAH and 3.5 in the case of DAO.

Example 33 Crosslinking of polyester with diamine from toluene (poly(methyl acrylate) (PMA) 4”i)
A solution with a solids content of 25 g in #, z 7.

A small amount of the solution was poured into an aluminum pan to a thickness of about 3 m.

Another part of this PMA solution is D, which is miscible with the PMA solution.
35 ml of EDA was added as a 20 ml solution in MF. This was similarly poured into an aluminum dish, P
To the third portion of the MA solution was added 35 mol of MSA. In this case 20 in EDA and MSA Atl-D
It was added as a solution. An insoluble salt was formed immediately and one phase remained unchanged so the sample was discarded.

Two aluminum pans containing samples of rIJ ester were dried at 70°C overnight and then cured at 140°C for 3 hours.

Toluene was added to the two dishes, which were then heated to 60° C. and stirred with a magnetic stirrer.

Samples of PMA and EDA produced a semi-rigid resin with a wetness index of 4.9 in toluene (wet weight of resin divided by its dry weight).

Example 34 Crosslinking of P(AN-HPA) by EDA from D-simulator 2
95 molt AN and 5 molt H
P (AN-HP
A) and PAN were compared. Each polymer was dissolved separately until the solids content in the solution was 14%,
It was then poured into an aluminum pan to a thickness of approximately 3 mists. A third solution was produced by adding 35 molty EDA (relative to the HPA content) to the appropriate amount of this copolymer solution, and this third solution was poured into an aluminum plate. °The three dishes were dried at 70°C for 5 hours and cured at 140°C for 3 hours.

Excess DMF was added to the 6 dishes and these were heated to 60"C and stirred with a magnetic stirrer for several hours. The PAN homopolymer was completely dissolved. Only the P(AN-HPA) copolymer swelled and It produces a soft gelatinous material with a swelling index of 8.3 in the intestinal σ, and those containing converted EDA retain a firm, cohesive film structure, which upon ablation has a swelling index of 3.0. Therefore, by using gDA, the degree of crosslinking was considerably increased. Perhaps due to the hydroxyl groups reacted with the oxycar-nyl groups of HPA, the P(AN-1(FA) copolymer itself could be crosslinked.

Example 35 Experimental crosslinking of PAMP S with diamine from water 3×
To three separate 5% aqueous solutions of PAMPS with a molecular weight of 10 were added 25 mol% each of EDA, DAH and DAO (as 20 wt% aqueous solutions). E
The DA-PAMPS sample precipitated immediately, and DAO and DAM-PAMPS became cloudy after 1 minute of stirring, but no precipitation occurred. The three samples were poured into an aluminum dish to a depth of approximately 2 cm, dried at 70°C for 6 hours, and then dried at 140°C for 3 hours.
Time cured. The swelling index in water is fluid! ' Le (7) 30 for EDA-PAMPS, D of weak rk
15 for AO-PAMPS, weak Ir A/DAH-
In the case of PAMPS, it was 10. The reason for the high degree of swelling and poor mechanical properties of these resins was thought to be probably due to ionic precipitation of the polymer by protonated amines having opposite charges.

Example 36 Experimental Crosslinking of Na PAMPS with EDA and Water To a 10% aqueous solution of the sodium salt of PAMPS was added a 20% solution of 25 mol of EDA to give a clear solution. The solution was poured into an aluminum pan to a depth of about 2 fi, dried at 70°C for 6 hours, and then cured at 140°C for 3 hours. The produced rk was very soft and fragment-like and had a swelling index of 50 or more.

Example 37 Experimental crosslinking of PMAPTAC with EDA and MSA from water
An attempt was made to crosslink the PMAPTAC present in the 5M aqueous solution by adding an amount of 20% aqueous solution equal to 5M. The resulting solution was clear and poured into an aluminum pan to a depth of approximately 2 m, dried at 70°C for 6 hours, and further cured at 140°C for 3 hours. Each sample was cooled and water was added to produce in each case a doughy rk, which had a swelling index of 20. When a similar experiment was performed except that 50 molty MSA was used, the resulting polymer dissolved and crosslinking appeared to be poor. It was hypothesized that the excess acid would produce a positively charged crosslinker, so that the positive polymer would repel this crosslinker and therefore no crosslinking would occur.

Example 38 PAMP on a composite RO membrane of a thin film of PAN
A 9-day solution of PAM was prepared by heating and stirring the polymer in SDMF at 60° C. for several hours.

After cooling to room temperature, the clear solution was cast onto a Holitex 3329 using a donor knife to a thickness of 7 mils. The film was immersed in water for 10 minutes to solidify and then dried at room temperature. The initial 7 lux of water is 50 ps
150μIl&.

1.0 part of PAMPS with a molecular weight of 5 million and grise o
- 7% methanol solution containing 0.13 parts of
It was cast onto an AN support membrane to a thickness of 7 mils, dried at 60°C and cured at 140°C for 3 hours. The obtained film was 400
When subjected to a feed solution of 0.02 N KCl at psi, it had a 7 lux of 0.22 μsa due to 76-salt rejection.

Example 39 PNBA on PAN thin film composite RO membrane
M P containing 10 mol each of glycerol and MSA
A 100% solution of NBAM and DMF was added at 1000 μsa.
The pure water flux was poured onto a PAN support membrane to a thickness of 8 mils. The film was air dried for 10 minutes, dried in an oven at 60°C for 3 hours, and cured at 140°C for 5 hours. The membrane was soaked in distilled water for 24 hours and then placed in an RO test cell (Gourmand) containing 30011 NaCt feed solution. At 200 psli, the initial flux is 8
It is 0.35μsa due to 7ch rejection, and 400 pal
It is 0.14 μsa due to 92-chi rejection, and 50
At 0 psi, 97% rejection was 0.1 μsa.

Example 40 UF Membrane of Polyacrylamide A 5% aqueous solution of PAM was prepared by slowly adding polymer granules to a blender containing water and stirring at high speed until the solution just started to boil (approximately 15 minutes). . When measured in water at 25°C and 0.005 cm, the above stirring increases the inherent viscosity from 3000 m4/ll to 2600 m4/ll.
Decreased in trench d79.

Holitex 3396 was prepared by adding 50 mol of glycerol to a stirred 5% solution and treating the resulting solution with a base.
(soaked in 3N NaOH for 3 days)
flowed into the mill. Dry the film at 90°C and then dry at 140°C.
It cured for 3 hours at 45 pal.
An initial water flux of 40 μam was obtained. A similar flux was observed when 50 mol of pentaerythritol was substituted for glycerol.

Example 41 UF membrane of PAMPS coagulated in DES Ruffenol PAMPS with TCE 1:1 (molecular weight 5 million)
Divide the 3% solution of 5.10.25 and 5 into 4 parts.
Added 0 mol of glycerol and MSA. After pouring the above solution to a thickness of 8 mils onto polytex with close porosity (3396) or medium porosity (3381), the DES was coagulated for 2 minutes at room temperature, dried, and further dried at 140 °C. It was cured for 3 hours. It was then immersed in water, whereby the membrane layer adhered strongly to the support and did not easily peel off even when rubbed. All membranes were hard, smooth, and highly hydrophilic.

In the case of crosslinking with different molti, the following pure water fluxes (in 2 μsm) were obtained: Potex 3381
In the above, if it is 5%, it is 482. If it is 10, it is 500.
In the case of 25%, it was 580. In the case of 50chi, it was 675 μS&. 58 for 5 inches on Polytex 3396.
In the case of 10 inches, it was 195 in the case of 58.25% and 385 μsa in the case of 50%.

Implementation fPJ42 Solidified PAMP S/kyn in DES
A 10% solids solution of ar) in UF membrane DMAC was prepared.

Note that this solution contains 5 parts of PAMPS (molecular weight 1 million),
1 part Quinar and 0.45 parts Epon 1
It consisted of 031. Pour the above solution to a thickness of 7 mils onto Polytex slightly warmed with DES, then
The PAMP S was solidified by dipping at 0°C for 20 seconds, then dried, and further cured at 140°C for 3 hours. The resulting membrane was 1.5 μsm with 93% dye rejection at 100 psi.
He had a fluff.

Below is a blank space Example 43 The UF membrane casting solution of Nur is 10'l in the DMAC solution and 5
p(AMPS-HHAM) copolymer (9:1
The same procedure as in Example 42 was repeated, except that the molar ratio, molecular weight (100,000 ml) and 1 part quinar.

DES t- was used for coagulation, and the flux was 1
υ2.1 μl with 90% dye rejection at 00 psi
Met. This membrane showed insufficient stability in base and disintegrated rapidly in P)+11 buffer.

It is speculated that the hydroxyhexyl groups of the polymer would react with the diethyl succinate coagulation solvent during curing to produce exposed ester bonds that are readily hydrolyzed.

°UF membrane of Example 44 3.25 parts of PSSA with a molecular weight of 1 million, 1 part of P(NBAM-HEA) with a molecular weight of 300,000 and 0.3 parts of glycerol in a molar ratio of 9:1 and 0.3 parts of MSA. 19
The casting solution was poured to a total thickness of 6 mm in DFviF, coagulating for 2 minutes at 25°C in DES, then dried and further cured at 140°C for 3 hours.

This membrane had a 7 lux of 30 μmm at 50 psi.

0.8 parts of the UF membrane P (SSA-AMPS) of Example 45 (molecular weight 250,000; containing 50 molar AMPS), PNBAM having an intrinsic viscosity of 6srttt7g in D temperature at 25°C
0.36 parts of glycerol and 0.36 parts of MSA.
Prepare a solution of Fj in DMF with a total solute concentration of 4.5 by mixing 38 parts of This solution was cast onto Polytex 3396 to a thickness of 5 mils and then immediately immersed in DES for 2 minutes. Next, heat for 20 minutes in an open air at 140°C containing DES steam,
Further, it was cured by heating at 140° C. for 3 hours in the open drying mode. The membrane was rinsed with draining water soaked in grit for 10 minutes. This membrane had a water flux of 200μ6m.

Example 46 Three membranes used for UF of primary sewage effluent at 50 psl were compared. The first membrane prisoner is [O8mo-nlca,
It is a commercially available polysulfone UF membrane made by Co., Ltd. (5EPA 20 KPS). 2 parts PMAPTAo, 1 part PNRAM, 0.3, consisting of 3.2 t solids with phenol + TCE 1 = 1
Membrane (B) was cast from a solution consisting of 6 parts glycerol and 0.15 parts MSA, and the membrane was coagulated in DES, dried and cured for 30 minutes at 140°C.

In the casting solution 1 part glycerol and 0.1
The membrane (Q is membrane C) except that 9 parts of MSA were used.
Same as B), total solids of membrane C was 3.7%.

The resulting membrane was placed in a rectangular cell. This process is 12
The effective area of In2 and 100,c across the surface of the membrane
It had a cross flow of rR/sec. After ultrafiltration under constant conditions for more than 11,100 days, the blacks of the three membranes at 50 pal were mixed with Membrane A.
is 1.0 μsm, film B is 2.8 μsm, and film C is 3.0 μsm.
Next time with 2μ■. Supply - Next Sewage Effluent Gold Chemical Oxygen Demand:
! 1 (cOD) 11001N; l/l,
That of the permeate was on average only 88 m9/l.

Example 47 The type of RO membrane that can withstand the heat treatment required for crosslinking reactions can be hydrophilic.

One example of such a RO membrane is the polymeric polybenzimidazole (FBI) (U.S. Pat. No. 3,699,30
No. 8, October 17, 1972). These films have high thermal stability. Additionally, these membranes are often amylized with organic liquids consisting of ethylene glycol and other diols.

Samples of PBT RO membranes were treated with two solutions using a dip coating method. Of the two solutions mentioned above, the first solution has a total solids concentration of 0.75 in ethylene glycol and is composed of 20 moles of EDA (per PAM unit) t-containing molecules [50 million molecules of PAM]. hole. The second annotation solution is PAM with f5 million molecules dissolved in the same solvent.
With a 1% solution of PS, 20% glycerol was added as a crosslinking agent.

The dried FBI membrane was dip coated with each of the two casting bath solutions, and the excess solution was drained off. First m! -90℃
It was dried for 4 hours. At this point both membranes appeared completely dry. After reading this, the film was cured by heating at 140° C. for 3 hours. The PUTllfi was kept under tension on a grate during the casting, drying and curing steps, but the membrane did not deform as a result of this process. Following curing, each membrane was immersed in distilled water and the surface examined. In both cases, a thin but cohesive and highly hydrophilic temporary membrane is completely broken &
When observed on the surface, those that did not change color by the dissolved Py and t-contamination test had thinned black band-like molasses.

EXAMPLE 48 A low cost ED membrane suitable for use in using ED to obtain electrical energy by mixing salt solutions of different concentrations could be produced according to the present invention. It is known that mixtures of normal salt chain solutions and dilute d-liquids, such as mixing river water with seawater or concentrated prine with seawater, can be used to generate electricity, such as in model batteries. Because the diffusion process controlling the speed of this power generation system is relatively slow, it is important to obtain low cost thin membranes. A particularly useful membrane can be formed using a highly porous support material and crimped on both sides. Porous crimp-bonded polyester can be used for this purpose as well as other support materials with other compositions. For ED use with
A PAMPS composition similar to Example 2 was applied to one side of the entire support sheet and then dried, after which the other side of the support sheet was coated with PM containing EDA of the type shown in Example 33.
It was treated with APTACm parabolite and further dried. This was followed by simultaneous curing of both sides to produce a porous support matrix. The matrix had a cation-permeable membrane on one side and a strongly basic anion-permeable membrane on the other side.

In the device itself, these membranes are made of conventional reticulated plastics, such as those used in conventional ED devices.
A dilute salt having a high ohmic resistance separated by a conductor passes through the interior of the support sheet and a concentrated salt solution passes through a reticulated plastic material separating one sheet from the next. The sheet Fi stack is oriented in such a way that a potential that produces a t-flow is generated by the diffusion of ions, and electrical energy is induced from the electrodes at both ends of the stack. The primary advantage of this system is its low cost and construction that takes advantage of the different ohmic resistances of the two salt solutions. The low cost of this device is a major factor in the commercial use of this type of power generation system.

Example 49 A bipolar ion exchange membrane has one side permeable to cations and the other side permeable to anions, and these two parts are arranged so that the resistance of the bipolar membrane is as small as possible and The parts are bonded together such that they are chemically cross-linked. Bipolar membranes are particularly described in Clamp et al. (U.S. Pat. No. 4,116,889) and Dege et al. (U.S. Pat. No. 4,253,900). These bipolar membranes are concerned with useful illustrations of the general concept. Using the methods of Examples 22 and 33 of the present invention,
A bipolar membrane was formed by pouring the PAMPS sulfonic acid membrane material shown in Example 22 onto a t-glass grate. However, in this case, the membrane material tl- was poured through the date opening so that the final membrane thickness in the dry state was 20 microns. After pouring and drying this membrane material, but not yet cured, quaternary ammonium anions were added using the formulation method of Example 33 and also to a dry membrane thickness of about 20 microns. A permeable membrane material was poured onto the top of the membrane. A film was formed by drying the upper surface and further curing the two-layer film at 140° C. for 3 hours. If a film with further mechanical strength is desired, each part of the above bipolar membrane can be poured using a woven fabric impregnation method and doctor plaid that have stable size, strength, and non-dissolving properties in the reducing solution. can do.

Installed in a typical power water separation cell between platinum electrodes? The final bipolar membrane can be converted into two product streams of sodium hydroxide and hydrochloric acid with a concentration of about 5% at a current efficiency of more than 85%. did it. The rate-limiting step in the operation of bipolar membranes is on the hydraulic osmosis competing with the water from the surrounding 'IB fluid' (i- water released from the center of the membrane by electroosmosis).
These membranes can conduct up to 10 Ω without decreasing current efficiency or increasing ohmic resistance over a period of 2 months.
It turns out that 07nR/ft2 can also withstand high currents.

Due to the low cost of these bipolar membranes, these applications are of particular interest.

Example 50 Solvent Extraction and Facilitated Transport
Membranes suitable for this purpose can be produced by using certain examples of the invention. For example, when performing solvent extraction using a thin water-soluble solvent film separating two aqueous solutions, Example 20
and 21 formulation methods can be used. A film was prepared by casting the PNBAM polymer onto a Holitex support using the formulation method of Example 20, with a solid composition and dart opening chosen such that the final dry film thickness was about 2 microns. form. In order to obtain particularly thin films, it is necessary to cast the membrane using the thin film composite of Example 39. The membrane was cast, dried and cured, followed by swelling in a suitable solvent. Among such membranes, decalin has been found to be useful in many solvent extraction processes because of its solvency, physical and chemical stability, water insolubility and very low vapor pressure.

The membrane was swollen to approximately 3 times its initial volume such that the volume fraction of polymer in the membrane was approximately 25%.

This membrane was then used in the extraction solvent step. In the solvent step with, the feed solvent was placed on one side of the membrane and the stripping solvent was placed on the opposite side of the membrane. In this case the feed solvent and stripping solvent did not dissolve the decalin appreciably.

The same membrane was used in the same manner as above for the purpose of facilitated transport as described by Kao and Gr@gor [C. G (5eparationSci
enc@T@chnology), Volume 18, No. 5, 4
21 pages, 1983]. A 25% solution of decalin was absorbed into the membrane to form a facilitated transport system using trioctylphosphine oxide Ha as a carrier. The membrane was then washed with water and used to extract acetic acid from a feed containing various solutes and acetic acid. The feed material was circulated on one side of the membrane. An aqueous alkaline solution on the other side of the membrane converted the acetic acid transported across the membrane to sodium acetate. Thus, extraction and concentration of the acid from the feed and separation of the salt in the stripping solvent was achieved.

Other facilitated transport agents such as liquid ion exchangers or IJX reagents can also be used in a similar manner. The above LTX reagent is used to selectively extract copper from a copper leach solution, and in this case, copper is extracted and concentrated in a stronger acid solution as a stripping solution.

Example 51 Protective Coatings Protective coatings can advantageously be prepared from blends of crosslinkable materials with particularly inert polymers that have the property of swelling in certain solvents, such as oils. Useful protective membrane breakers include some PNBA (
It can be prepared by dissolving 5 parts of quinar with a similar hydrophobic polymer and adding a crosslinking agent such as a short chain nol or a diamine such as hydrazine or EDA. Upon casting, drying and curing, it produces a film or rupture that swells slightly in mineral oil. This film or coating acts as an excellent protective layer under such circumstances.

Example 52 Pervaporation (p*rva) through which certain components of a solvent mixture permeate
poraHon ) (PV) membranes can be manufactured according to the teachings of the present invention by using very thin films used in TFC (thin film composite) compositions. The TFC compositions described above are cast from polymers that strongly absorb the components to be selectively evaporated, thus allowing selective transport of the components. In this case, a high degree of crosslinking is required so that the polymer permeable components interact favorably. This is because it is necessary to expand the pores by swelling to allow the mixed solvent to pass through.

The membrane was prepared by first casting and solidifying a PAN film to form a UF support on Polytex 3381. Then, until the total solids content is 0.5%,
Prepared by dissolving 5 parts PAMPS, 1 part PNRAM and 0.8 parts each of glycerol and MSA in total ethanol, soaking, casting and draining from the support membrane. After drying and curing (3 h at 140 °C), separate mixtures of water and alcohol were circulated in a chamber across the Holitex side of the membrane, and a vacuum of 1 m2 was maintained on the other side of the membrane. , each vapor was captured, collected, and analyzed. The ratio (by weight) of alcohol in the permeate divided by the alcohol in the feed is 0.5 and 0 of the alcohol in the liquid feed.
．． At weight fractions of 9, 5 and 20 for methanol-water, 5 and 20 for ethanol-water, and 12 and 40 for groun-nol-water. At 10 Tiptano-water in the feed, the ratio was 7, but at 95% in the feed, the ratio was about 400. For very thin, highly crosslinked Pv barrier membranes, these highly selective permeabilities can be maintained with high fluxes.

Example 53 Another advantage of the post-crosslinking process of the present invention is that a wide range of combinations as homopolymers or copolymer mixtures with other polymers are possible, making it possible to create materials suitable for special applications. It is to generate.

For example, a useful monomer is polyglycol methacrylamide (PGMAM), which has 1633
Polyglycolamine () I-163, Union Carbids] f1
0.01.9 of triethylamine, 60 (1) of ethanol and 0.2.9 of p-methoxyphenol (Fisher) were mixed, then 100.9 of methacryloyl chloride was slowly added and concentrated under nitrogen. It can be produced by reacting at 50°C.

The product is then filtered at -10°C, the resulting filtrate is passed through a strong base anion exchange resin in the hydroxide state, diluted with methanol and passed through a weak base anion exchange resin.
It was finally concentrated and dried.

A casting solution is prepared from DMF and this solution contains 1 part of PA.
MPS and 5 parts of P(AN-PGMAM) t-(P
for AMPS) 1 mol of glycerol and MS
It contained Ai. UF to process the diluted black belt molasses feed by pouring the film and then solidifying it in water.
It was used as a membrane. After 23 days of use with this very dark and dirty feed material, with the flux held constant, the cell was opened.

The membrane was still completely white and no trace of dirt was visible. In this formulation, an insoluble matrix polymer was used that contained polyol side charges that also crosslinked with highly hydrophilic polymers such as PAMPS.

When EDK useful cation exchange membranes are desired, PAMPS to P(AN-PGMAM) to provide various degrees of swelling and porosity useful for a variety of applications.
Various proportions of can be employed.

The same is true for P~fAPTAc anion exchange membranes. Polyelectrolytes can also be selected from a wide range of polymers, which do not crosslink themselves. One example is PSSA and P(AN-PNB
A)! Copolymers of PNBA or PNBA form highly crosslinked cage-cage membranes with useful properties.

EXAMPLE 54 This invention relates to the production of a particularly useful romatodalaffy system that can be used for analytical and Y4 production purposes. According to the invention, it is possible to form very thin films by means of certain casting methods, and it is possible to produce chromatography systems with particular utility. In addition, in the above casting method, the pore structure of the film can be controlled by the coagulation method or the degree of bridging, and the hydrophilicity of the film can also be increased. It can contain uncharged fixed charges.

In analysis, high throughput is of paramount importance, and this is achieved by making the process path of diffusion into and out of the pore or Vir Luglu constant phase very short. Although the use of the thin films of the present invention is particularly advantageous, the problem of flowing the mobile phase across the plane of the stationary phase must be solved so that the "front" of the fluid flow is not severely disrupted.

A stationary phase with a thickness of 2 or 3 microns is very elegant. This is because this stationary phase allows for high throughput of the chromatography system.

However, it is also desirable to be able to arbitrarily control the total volume of mobile phase relative to stationary phase and to maintain the driving pressure within a suitable range. The following formulation method has been found to be very useful. However, this method of formulation is not the only method that can be used.

First, coat a very smooth glass plate with a smooth film of paraffin and score parallel lines into the glass plate with an iron pen, preferably penetrating the glass at intervals of several tones to about 13. Painted. The flat surface of the glass plate was then treated with hydrofluoric acid or a paste of hydrofluoric acid and a suitable salt to etch the glass to a depth of 1 to several microns. The etched grid plate is usually formed into a rectangular or parallelogram shape from a practical standpoint so that the longitudinal and lateral flow of the mobile phase is uniform. At this point - the mother rough-in layer was dissolved, the grate was washed and a uniform layer of one of the formulations of the invention was cast onto the plate. Here, Examples 19, 22°23.26128, 30.31.
Formulations such as No. 32 could be used. By varying the casting conditions and the content of solids in the casting solution, films with different thicknesses can be prepared. By solidification, various porosity can be obtained which can also be controlled within a certain range. At this point the film was dried, cured, and water-wetted, resulting in a film with a grid metal on a surface made of exactly the same material.

To produce a chromatography device, it was sufficient to carefully bend the partially dried film into a cylindrical shape and place it on another, slightly larger cylinder. The membrane was mounted in an apparatus having suitable inlets and outlets for supplying the solvent and first it was wetted and allowed to swell appropriately. What is thus obtained can act as a perfect analytical chromatography system. The high throughput of this p-adography system is due to the extremely short diffusion path.

This structure is difficult to manufacture, uses very fine beads of uniform diameter, and also produces high pressures because it has channels running through and across the column. This system is significantly different from conventional HPLC equipment.
A system that does not require high pressure is obtained.

The advantage of the corrugated stationary phase is that this phase can have very fine wave spacing, its hydrophilicity is high, there is no need to use very fine fabrics etc., and the membrane is usually at least 5 A minimum thickness of microns is determined, and the phase thickness is usually several times that minimum value.

A similar general method can be used to make preparative chromatography columns, but larger sizes can also be made, in this case corrugated -! ! Alternatively, a membrane without waves W is bent around the cylinder, in which case a very fine cloth is used as the spacer material. However, since protein denaturation on almost all surfaces is a major problem in biochemistry and molecular biology, it is beneficial to use fine fabrics coated to increase hydrophilicity. . Alternatively, fibers can be spun and woven into textiles from the polymeric blends of various examples. Alternatively, the stationary phase may be a completely homogeneous fabric that can act as a reed, stationary phase, and speeder.

Because casting of membrane films is a highly developed technique that can be performed on a large scale with good control over various physical properties of the film, large scale preparative chromatography systems also benefit from the teachings of the present invention. It is clear that it can be easily manufactured by

Chromatographic systems that separate low molecular weight substances with fairly similar properties, such as polybegutides and oligomers of low molecular weight carbohydrates, as one example, would be particularly advantageous. These compounds are important substances in molecular biology. Also, the analysis of ions by ion exchange HPLC systems is used in a wide range of fields, and the materials mentioned above are also applicable.

Example 55 As one example, modern molecular biology techniques often utilize sheets of nitrocellulose. This is because this substance has a high affinity for small pieces of RNA or DNA for nucleic acids with a molecular weight of about 12,000. Nitrocellulose is commonly used to hold the polymer on its surface during reaction with the polymer. Recently, several synthetically treated nylons and other materials have been used for this purpose, such as DEAE cellulose paper, polylysine bonded paper, etc.

The teachings of the present invention are particularly concerned with the preparation of surfaces with special affinity groups that retain materials without causing modification. Advantageously, reactions can be carried out only with certain groups of nucleic acids selectively retained on the surface.

The present technique also provides for crosslinking nucleic acids to paper using typical post-crosslinking or conjugation reactions utilized for enzyme and protein immobilization. These reactions, when combined with the nondenaturing action of highly hydrophilic surfaces, provide researchers with an effective tool for the denaturation of nucleic acids.

Significant advantages are obtained in the absence of non-specific binding of proteins and similar molecules.

- Example 56 PAGE Polyacrylamide gel electrophoresis (PAGE) is a commonly used technique for the small scale determination of proteins in complex mixtures, usually using detergents such as SDS. is used to create rod-shaped molecules such that the protein moves at a speed that depends on its molecular weight. PAGE plates are usually very fragile and sometimes difficult to manufacture. If a particular component needs to be measured, removing a special slice of the grate is a time consuming and somewhat complicated process.

Very thin and very stable PAGE grates can be made from sheets of thin, strong plastic, such as oriented polyester or Miller (DuPont). These can be coated directly with polymers dissolved in organic solvents which moisten the glass and form bonds between the active substances of the PAGE film and the raw glass. Or, as an example, one side of the mirror sheet can be treated with a strong alkaline solution for a period of time, which hydrolyzes some of the diester bonds and renders the material readily wettable by water; and the chemical bonding is carried out by means of the casting formulation according to the invention.

These PAGE sheets can be prepared by pouring or dip-coating onto them one of the polymers appropriate for the desired separation and having an uncharged, negative or positive charge and a porosity set by coagulation. It is made by producing a thin r film with . The film is then dried and cured using standard methods. PAG having a thickness t of 1 to 2 microns or more
E-films are easily formed by this method. The dried and cured film can be stored in a dry state, and immersed in a buffer solution and placed the original film together with other glass plates on top of the glass plate to eliminate voids and achieve a uniform thickness. By imparting stiffness and stiffness, it can be applied to the PA (J method.The unknown sample is then used and separation is performed by passing an electric current through it.At this point the system is easily disassembled and stained.These PAGE
The barrels have vertical or wide holes and still have adequate mechanical strength for these manufacturing methods. After the dyeing was done, each section of the sheet was cut for subsequent purposes. The small thickness and nature of this PAGE system has implications for the isolation and identification in the case of extremely small samples of substances possessing similar properties, and therefore makes it useful for other methods such as sensitivity. Limitations are limiting factors.

Example 57 Desalting and Concentration of Protein Solutions By the use of selected materials such as hydrophilic UF membranes with a fixed charge of the same label as the protein or dangerously charged membranes preferably made from PAM, PNMAM or PDMAM.
Proteins are easily desalted and/or concentrated. Ultrafiltration is the preferred method of desalting and concentration. Because it is a quick process. Conventional dialysis can also be used, but it is a relatively slow process.

Membrane pore sizing can only be done reliably by experimental means, i.e. by creating membranes of different porosity and then determining the non-passage of the desired protein. Ta. Since proteins are usually highly denatured molecules, the method used is important. Low pressure is usually used to allow the protein to pass through the pores without denaturing. To keep the flux high and to minimize the formation of r/I/layers on the membrane, high velocity cross-flow or other means of minimizing concentration polarization are used. If protein loss by surface denaturation is desired, the walls of the UF cell can be coated with highly hydrophilic materials of the type described in other examples. The lumen of the connecting tube can be similarly treated.

The simple and rapid method described above is particularly useful when processing valuable materials that are easily denatured or deteriorate rapidly.

Example 58 Hydrophilic Microfiltration Screen A microfiltration screen with high mechanical strength and precision openings is prepared according to the invention by coating the screen itself with several formulations given as examples in the invention. It can be constructed by Common products include metal wire and ? Microscreens made from a number of polymers including lyolefins, polyesters and nylons, these products are typically made for screen printing or microfiltration purposes. however,
Hydrophobic and gelatinous materials adhere to the openings of these screens, clogging them and making them difficult to remove by backwashing. All conventional screens have such drawbacks.

The same is true for wide screens used for the dewatering of cakes and other semi-solid materials that usually contain water as a liquid.

It has been found that particularly useful microfilters can be formed by coating these fine screens with hydrophilic polymers. - In the case of polyester and nylon monofilament screens, the method described above is particularly simple and a wide range of coating formulations are available. In this case, for all solvents that rapidly attack the monofilament screen [7
Care must be taken to ensure that this does not occur. In the case of I-lyolefin screen, chromic acid immersion fJ! Alternatively, pre-treatment by one of the conventional methods, including the use of corona discharge, renders the surface susceptible to wetting and subsequent coating adhesion. Wire screens require a basecoat, which is one of the commercially available epoxy compounds commonly used as a basecoat. These are extremely thin and the adhesion to them by the formulations of the invention is excellent.

A typical application is a polyester screen commercially available from T*tko Ardsley, New York, which is first immersed in a casting solution and then cast. This is obtained by removing excess solution by passing the solution through a device for use. It is sometimes necessary to apply a moderate vacuum to the film to remove excess droplets of potting solution. This was followed by drying the film at -60°C for 2 hours and then for 14 hours.
It was cured for 3 hours at 0°C. Microscopic examination of the screen showed that after proper application of M, the screen was completely covered by the hydrophilic polymer. This was confirmed by using dyes that strongly dyed the screen material itself, but not the entire polymer coating. The application process is usually carried out by passing the screen over a roller under appropriate tension and passing it over the top of the entire Dr.Plaid screen. In this method, the loops between adjacent fibers are pulled tight and the potting solution not only coats the screen, but also acts as an adhesive to close the roof and seal them.

Following normal drying and curing steps, these screens have been found to be very effective for microfiltration of materials such as cell suspensions. The cell suspension results from the fermentation of beverage alcohol, primary and secondary sewage sludge, and raw materials requiring removal of cells and other suspended solids.

One particularly useful aspect of the present invention is the use of a screen mounted on the exterior of a rotating porous cylinder that is rotating within an annular region. In addition, in the annular region, the supplied W3 suspension is sucked and discharged under pressure through this region. A dual effect can be obtained by covering both the rotating and stationary porous surfaces with the same screen. This mechanical arrangement produces a very effective agitation of the surface of the screen, a phenomenon known as Taylor's swirl. Solids that are suspended under the influence of such swirls are collected in bands. This band, under the influence of the upflow and downflow of the feed material through the annular region, produces a "rope" of concentrated suspended solids that is discharged from the outlet so that a sufficient concentration of the material is achieved. can get.

Lower pressures are used. Sticking of suspended solids is not a problem in the present invention, and the use of the hydrophilic surface of the present invention allows
Low rotation speeds of 300-600 RPM were found to be curing. The preferred concentration of suspended solids in containers resulting from the production of beverage alcohol was set at 5-18%.

When the same hydrophilic material is used as a coating on a cylindrical or planar device under normal conditions of cross-flow, the velocity of cross-flow must be high. This is because the flow of permeate forces the suspended solids against the surface of the microfilter, slowing down the rate of filtration through the surface layer of the filter.

When wire screens or polymer screens that do not have strong hydrophilic properties are used in spinning equipment, rotational speeds of 2000-3'OOORPM or higher are required to provide sufficient shear stress so that the filtration process can be carried out at a satisfactory speed. It will be held in Therefore, the above effect is achieved by a combination of a Taylor-like spiral arrangement and a hydrophilic material, and the preparation of the hydrophilic material as taught by the present invention is particularly beneficial for the removal of suspended solids. be.

The same configuration can be applied to ultrafiltration methods when separating low molecular weight solids from solutions of proteins or in the case of highly porous membranes to separate proteins from each other. In many of these separations, the range of convection at the membrane or microfilter solution/suspension interface is stringent, and high flux rates result in a combination of hydrophilic and moving surfaces. .

Example 59 As is well known in the art, affinity adsorption and enzymatic conversion methods, enzymes, proteins, antibodies, etc. Insolubilizing polymers or copolymers containing substituents to which biological substances are attached have been utilized. This is noted in several Grsgor patents and the first Greco patent application (U.S. Pat. No. 618,652). All of these systems are hydrophobic or hydrophilic. Although it is based on a not strong polymer of
It has the advantage that adsorption is not specific. A co-pending application (U.S. Patent Application No. 618,652) describes a number of known coupling chemistries, such as those using arylamines, pyridines, hydroxyl-containing olefins such as N-hydroxy substituted acrylamides, and the like. These methods are similar to some of the rnman and Dlntlzla chemical bonding reactions mentioned above. The above co-pending application discloses that arylamine, pyridine or comonomer N-(5
-Hydroxy/I/-3-oxa-pentyl)acrylamide and N-(9-hydroxyl-4,7-zoxanonyl→methacrylamide) mention is made of the use of hydroxyl-containing substituents.

Therefore, under the teachings of the present invention, highly hydrophilic polymers can be obtained by substitution reactions on linear or cross-linked polymers containing pendant amidoca/L/M nyl groups or oxyca) L/gonyl groups suitable for crosslinking. Polymers can be converted into useful surfaces, microfilters, membranes, etc. Note that the above-mentioned highly hydrophilic polymer can be made insolubilized by the teachings of the present invention.

These surface layers, membranes and microfilters can be fabricated by those skilled in the art using citriclo- It can be activated by counter-illness.

Contains chymotrypsin, glucose isomerase, protein,
A very wide range of biopolymers can be coupled, including comb serum albumin and the like.

A method in which non-specific adsorption does not interfere and all of the soybean trypsin inhibitor adsorbed by the membrane can be desorbed by conventional techniques, including modification of -() and the use of Decalagling agents such as urea The above biocopolymer force-lag ring bonding system can be used for the separation and isolation of soybean trigsin inhibitor by coupling chymotrypsin.

Similarly, protein iA can be immobilized on a hydrophilic support material and then, if necessary, an antibody such as rga bound thereto can be conjugated by techniques known to those skilled in the art. Such immobilized antibodies can be used for analytical, separation and production purposes.

Similarly, a method of affinity adsorption involves the use of hydrophilic polymers to which the protein gelatin is bound.
It can be used to remove nsctln).

Another example is to immobilize protein *A'e, then anti-human (
ar[lhuman) binds to serum albumin rgG. Then antigen ISA in IgG binding buffer
1, washed to remove undesired substances, and eluted in pure, concentrated form.

As one example, it is well known that the microenvironment of an enzyme influences its catalytic activity. The teaching of the present invention is
It not only provides a highly hydrophilic environment, but also provides an environment in which the final positive or negative charge is located in the vicinity of the coupling group, thus providing an optimal microenvironment for the above method. be able to.

Example 60 The teachings of the present invention can be utilized in the surface treatment of cellulosic and non-cellulosic textiles and papers for a variety of purposes. Furthermore, according to the invention, the degree of hydrophilicity can be varied' and/-! Resistance to electrostatic charge build-up can be imparted through conductivity or conductivity, thus providing the material with resistance to creases and receptivity to fillers. Using the teachings of the present invention, other desirable properties such as receptivity to dyes and inks can also be obtained by surface modification. These surface treatments are relatively durable, as subsequent heat treatments can form chemical bonds between the polymer and the support paper or textile. It can also be removed by methods. Some of the materials according to the invention consist of single polymers that are soluble in common solvents, and this fact makes them particularly advantageous in their applications, minimizing the release of soluble products that normally cause fluid contamination. can be kept to a minimum.

Two washed fabrics, one made of IJ ester (DuPont's Dacron) and the other polyamide (DuPont's Zytsl)
0.5% of P(AMPS-HHAM) (Example 15)
Dip the fabric into an aqueous solution, discard the excess solution, and use the fabric at 60°C.
and then cured at 140° C. for 3 hours. They were then washed briefly with dilute sodium bicarbonate solution, further washed with water, and dried. The finished fabric is non-sticky,
Synthetic materials also have a softness like cotton, and also have water and adhesion properties like cellulose materials rather than synthetic materials, so the fabrics mentioned above have a different "stiffness". did it.

Example 61 The extent of crosslinking in a polymer can be determined in several different ways. A practical test is to measure the swelling index of the resin in a solvent in which the polymer is slightly dissolved. Quantitative experiments were performed to determine the amount of groups displaced from the polymer by the crosslinking reaction. Glycerol, TMP and pentaerythritol/L/ll in one series
- Dissolve PAM with a molecular weight of 3 x 10 in water in a closed flask while varying the number of polyols containing crosslinkers, and dry the resulting solution at -60°C and further at 140°C for 3 hours. Hardened. The flask is then cooled, the ammonia released by the cross-linking reaction is neutralized with an excess of standard hydrochloric acid, and an aliquot of this solution (including that used for rinsing insoluble stool fat) is added with 1- standard base. The released ammonia gold was determined by back titration. The molar ratio of released ammonia to polyol units or PAM units is calculated as a function of the moles of polyol to PAM, and from these data it can be concluded that the degree of crosslinking is approximately 4
It changed from 1 to 11. This method does not show mirror cross-linking between different PAM chains, but rather cross-links formed between two groups on the same mirror.

However, since a solvent in which PAM is easily dissolved (and stretched) is used, and the steric effect due to the specified polyol fully supports the crosslinking of mirror opening, the crosslinking between the polymers was ultimately dominant.

Similar experiments were performed using fully substituted C-glycerol (along with regular glycerol) and MSA catalyst in PAMPS and water. After drying and curing, the amount of radioactive absorption i in the washed resin was measured. The crosslinking was at a high level, and was judged to be 8 to 15 degrees based on the data.

We also conducted a number of experiments in which glycerol and MSA were added to ηMPS in islet σ and PAM in ethylene glycol;
The tit-changed. Dry at 80℃ for 5 days,
After curing for 3 hours at °C, the swelling index in water was measured. Under favorable conditions, the swelling index is 2.4-3.0 for PAMPS, PA! 2.1-3.0 for l/I, these results indicate that by employing the teachings of the present invention, a very high degree of crosslinking is achieved.

By choosing the solvent, the swelling index can be varied to a certain extent. PAMP S appears to be more highly crosslinked from water than from DNF.

This is probably because PAMS is well stretched in water.

It will be understood that the specification and examples are presented by way of example rather than limitation, and various changes and modifications may be made thereto without departing from the spirit and scope of the invention.

The following margin procedural amendment (method) August 1985, /LA Japan Patent Office Commissioner Black 1) Akira Who ■, Indication of the case 1988 Patent Application No. 99497 2, Name of the invention Insoluble solid crosslinked composition, and Processing Method for Gion or Fabrics 3, Relationship with the Amendment Case Patent Applicant Name: Barry Pea, Bregor 4, Agent Address: 8-10-6, Toranomon-chome, Minato-ku, Tokyo 105
Subject of amendment (1) Power of attorney (2) Specification 7, Contents of amendment (1) As attached (2) Engraving of specification (no change in content) 8, List of attached documents

Claims (1)

[Claims] 1. An insoluble solid crosslinked composition produced by crosslinking a linear polymer having at least 80% of polymer units containing oxycarbonyl groups and hydroxyl groups in solid form at an appropriate temperature. wherein the crosslinking is effected by (i) hydroxyl groups, which hydroxyl groups are present in the form of (a) hydroxyl groups extending from the polyol, (b) hydroxyl groups of low molecular weight polyols, and/or (c) epoxy-containing compounds. or the crosslinking is effected by (ii) an amino group, which is a pendant group from (a) the polymer or (b)
An insoluble solid crosslinking composition, present as a low molecular weight diamine or polyamine, characterized in that said composition swells only slightly in a solvent that dissolves the polymer before crosslinking. 2. The composition according to claim 1, wherein the molar ratio of the monomer units constituting the polymer to the total alcoholic groups is in the range of about 1:0.001 to 1:0.5. 3. The composition according to claim 1, wherein the hydroxyl group is present as a low molecular weight polyol. 4. The composition of claim 1, wherein said polymer molecule has an alcoholic group extending therefrom. 5. The composition according to claim 1, wherein the crosslinking is catalytically influenced by a strongly acidic moiety. 6. The composition according to claim 5, having a strongly acidic functional group extending from the polymer molecule. 7. The composition according to claim 5, which contains a strong acid independent of the polymer molecule. 8. The above polymer has the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, each R is the same or different, and one carbon atom is
an alkyl group having up to 0 carbon atoms or an aryl group having up to 10 carbon atoms; R′ is an alkylene group having up to 10 carbon atoms or an arylene group having up to 10 carbon atoms; an alkyl or aryl group having up to 10 units, to which a functional group selected from the group consisting of sulfonates, amines and quaternary ammoniums is attached. 9. The composition according to claim 1, wherein the polymer is composed of units of 2-acrylamido-2-methylpropanesulfonic acid, and the hydroxyl group is in the form of at least one of glycerol and pentaerythritol. 10. The composition of claim 9 further comprising an alkanesulfonic acid or a benzenesulfonic acid. 11. The composition of claim 9 further comprising an alkanesulfonic acid or a benzenesulfonic acid. 10,00
The composition of claim 1 in the form of a porous thin layer having a pure water flow rate of 0 microns/sec/atmosphere. 12. A composition according to claim 1, which is produced by coagulating a solution containing the substance before crosslinking. 13. The composition of claim 12, wherein the polymer consists of units of 2-acrylamide-methylpropanesulfonic acid, and the hydroxyl groups are present in the form of at least one of glycerol and pentaerythritol. 14. Claim 1, wherein the amine is a diamine.
Compositions as described in Section. 15. The composition according to claim 1, wherein the amine is a primary amine. 16. An insoluble solid crosslinked composition produced by crosslinking in solid form at a suitable temperature a linear polymer having at least 80% polymer units containing oxycarbonyl groups and hydroxyl groups, comprising: The crosslinking is effected by (i) hydroxyl groups, which hydroxyl groups are present in the form of (a) hydroxyl groups extending from the polyol, (b) hydroxyl groups of low molecular weight polyols, and/or (c) epoxy-containing compounds, or Crosslinking is effected by (ii) amino groups, which are (a) pendant groups from the polymer or (
b) applying to the surface of the paper or textile an effective amount of the insoluble solid crosslinking composition, present as a low molecular weight diamine or polyamine, which swells only slightly in the solvent in which the composition dissolves the polymer before crosslinking; A method for treating paper or textiles, characterized in that the surface thereof is crosslinked and/or its surface modified by: