JPS5893760A - Blended high polymer matrix film, manufacture and use - 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 a family of blended polymeric matrices and methods of making them.

Polymer layers suitable for use in ultrafiltration and reverse osmosis processes are typically prepared in the form of sheets, tubes, hollow fiber spirals, etc. from a casting solution containing the desired polymer. It is manufactured by casting or molding a membrane into the shape and shape of the membrane. Depending on the specific ultrafiltration or reverse osmosis process, polymeric layers can be prepared with positive or negative functional groups incorporated into the polymeric layer, or polymers with different monomer formulations. It is often used to create layers to impart interesting functional properties to the resulting polymeric membrane.

The selection of the desired solvent to be used in the casting solution is limited due to the many problems associated with the production of compounded polymer membranes. This means that the formation of monomers into solids against coalescence is inhibited,
In addition, when making a casting solution, this solution is used to gelatinize the casting solution, and 11! or may become impossible to spread or use due to further physical separation or other unsuitability. Other considerations involved in the manufacture of formulated polymeric membranes relate to the water solubility of some of the polymers used in the casting solution. For example, when a specific water-soluble homopolymer or copolymer is blended with other polymers in a casting solution to produce a blended polymer caster, this water-soluble polymer can be produced by ultrafiltration or L11 infiltration. will be leached from the formulated membrane when used in

In addition, other dilutions and casting solutions associated with the production of compounded polymer membranes can be treated with Iiii &! This occurs after forming a membrane from the casting solution. In the membrane thus formed, when testing the casting solution or after evaporation or diffusion of the casting solution, 1M
It is often seen that the heavy metal bodies that make up the metals become completely incompatible. For example, in solution, two or more polymers may be compatible, but in the solid, dry or half-dried state, these polymers may become incompatible, and upon drying, e.g. - Appears on the surface with macroscopically incompatible appearances such as ridges or cracks, or has non-macroscopic defects, or is exposed to ultraviolet osmosis or reverse osmosis. Incompatibilities in the dry formulation family, which may not form a suitable formulation suitable for use in the casting process, often result in the formation of a polymer that is the core of the casting solution. Separate micro-bonds between forms′
Compatible, water-insoluble, interpenetrating polymers blended in such a way as to separate the polymers into regions, prevent substantial leaching of water-soluble polymers, and result in the formation of compatible blended polymers. No network structure is formed.

It is easy, quick, and easy to create compounded polymer membranes that can be incorporated into matrix or supporting polymers and have the desired polymeric properties and functional groups.
It would be desirable to provide this in an effective and economical manner, yet without the difficulties associated with the production of conventional compounded polymeric membranes.

The present invention #i relates to a compounded polymer composition that has been used illegally as an ultraviolet filtration method and reverse 1V method, and an improved method of making and using the compounded polymer membrane. In particular, the present invention relates to a compounded polymer membrane in which the compounded membrane is composed of a matrix polymer compounded with a copolymer having positive, negative, or neutral and polar functional groups, a method for producing this membrane, and a membrane. It is about how to use.

Formulated polymeric compositions suitable for use in membrane processes such as reverse osmosis and ultrafiltration, for example, and in the case of homopolymers, DU! Copolymerizing monomers that are incompatible with Trix and, if the homopolymer is compatible, are water soluble and will largely leach from the matrix polymer after compounding. It has been found that it can be easily produced by

Appropriate used to produce copolymers; things! It has been found that desired functional properties can be imparted to a water-insoluble formulated membrane polymer containing a base matrix polymer by appropriate selection of - monomer positive, negative or #i It can have polar groups or other physical anchoring chemical groups and properties that are desired to be imparted to the compounded compatible polymeric membrane.

The blended polymer of the present invention is! This method avoids the troubles associated with the conversion of specific functional groups to a matrix polymer. The grafting process often has a detrimental effect on one or more properties of the matrix polymer and typically results in only a low level of grafting. Therefore, the present invention enables the production of compounded polymeric membranes by means of which the homopolymer becomes water-insoluble.
A water-insoluble blended film can be formed by copolymerizing the monopolymer with a second polymer that makes the homopolymer water-soluble, and furthermore, it is possible to form a water-insoluble composite film by copolymerizing the monopolymer with a second polymer that makes the homopolymer water-soluble. It is tolerant. . Thus, the formulated polymer membranes of the present invention provide polymers that are not soluble in water, but which form a transparent compatible spread when blended with a matrix polymer in solution, cast, and dried. .

That is, one combination that provides membrane support and strength to the resulting polymeric membrane and is typically inert to variations in UpH% temperature and cleaning conditions! tritutas polymer, typically a water-insoluble polymer, and a copolymer, typically a water-soluble, non-water-soluble copolymer, which is compatible with and intimately blended with and interleads with the matrix polymer. A blended polymer membrane consisting of a polymer is manufactured. A copolymer that is soluble in the casting solution containing the copolymer HIROMA SILIX I and that maintains compatibility with the matrix polymer even after being cast and processed,
Separately from the combined matrix 1, it is prepared by copolymerizing the lN1 monomer and the second monomer in the presence of various initiators in a solvent solution.

The first monomer is a water-insoluble and oil-soluble monomer, which, when combined alone, has mutual objectivity in the matrix polymer after one casting in the casting solution. This product of 81 monomers often contains no positive or negative groups, resulting in a homopolymer of 182 monomers, when homopolymerized in the casting solution or more typically A homopolymer that is incompatible with the matrix 1 of the material after casting, or a homopolymer that is water-soluble and compatible with the casting solution containing the matrix polymer after casting. It is a monomer that provides a homopolymer that is substantially leached from the matrix polymer formulation upon one use to form a receptive membrane.

The second monomer is water-soluble or alcohol-soluble and often contains positive or negative groups that are desirable to impart to the resulting formulated polymeric membrane, e.g. Alternatively, it is used in formulated polymeric membranes used in electrocoating operations to separate cationic or anionic aqueous theoretical compositions. Appropriate behavior of the Ill monomer to be copolymerized, the second monomer, and other monomers reduces the water solubility of the resulting comonomer, and improves both the phase with the matrix group. Improve compatibility. In this way, the resulting blended polymer MU has the desired properties with balanced hydrophilicity and hydrophobicity (Graph F
Overcome the mandate regarding the use of functional groups by chemical technology.

The matrix polymers to be selected include a wide range of ST polymers that provide the necessary support and strength to the resulting polymeric membrane. For example, when the polymer membrane undergoes changes in temperature and pH due to this polymerization, it tends to become inactive.
Strongly alkaline cleaning, consisting of a water-insoluble polymer that provides sufficient strength and chemical and abrasion resistance to clean agricultural surfaces, making it particularly desirable for use in food and dairy processing. lk liquid is used to polish the surface of the layer. For example, the matrix polymer may be a homopolymer or a copolymer, typically a sigenated heavy metal, such as, but not limited to, a homopolymer derived from vinylidene tetragenide, and a copolymer. Copolymers, such as polyfluoride, vinylidene fluoride, polyvinylidene fluoride, and copolymers with other fluorinated and fluorinated monomers, such as hexfluoropropylene or trifluoropropylene. Copolymers with p-ruethane or copolymers with other polytetraalkanes, as well as helegenated vinyl tetragenide polymers and copolymers, including vinyl chloride, especially chlorinated vinyl chloride. Matrix polymers typically include polymers such as those obtained by using in conjunction with other monomers:
The formulated polymeric membrane accounts for the majority of the weight percentage, while the copolymer with which it is co-compounded constitutes a minor proportion and is present in an amount sufficient to provide the desired product membrane properties.

The copolymer of the blended polymer membrane in the present invention contains at least two copolymers.
@ monomers, usually organic monomers or plebri! - is produced by copolymerizing.

However, it will be appreciated that small amounts of other monomers or monomer mixtures may be used to vary the physical and chemical properties of the copolymers used, if desired. The first monomer to be used is of such properties as to impart water insolubility and compatibility with Y) the lithium-rich polymer, and the homopolymer is present in the casting bath solution. Also suitable are a wide range of super fats that are of such a nature that they remain mostly or completely compatible after producing the final form of the composite film containing the matrix-enriched material. Monomers can be selected. However, monomers which produce water-insoluble copolymers and homopolymers and which provide or increase compatibility of the total copolymer with the matrix have been found to be particularly desirable. Monomers of this type include, but are not limited to, acrylate and methacrylate monomers,
For example monoarylates and monomethacrylates such as methyl methacrylate; cyclohexyl methacrylate; isodecyl acrylate; isodecyl methacrylate; lauryl acrylate; lauryl methacrylate; - butylmethacrylates include pyruvir methacrylate; perfluoroalkane methacrylate; tetrahydrofurfuryl acrylic-F; Includes dalicold dimethacrylate. Various diluting monomers, such as monomer diluents such as epoxies, such as allyl glycidyl ether and glycidyl methacrylate, can also be used if desired. The polymer is methyl methacrylate or alkyl methacrylate. This is because they tend to be more stable than the removal-compatible acrylates exposed to alkaline cleaning solutions. A monomer whose homopolymer is water-soluble and, due to phase separation, incompatible with the matrix polymer both in the casting solution and in the resulting final polymer film. Or they are mostly incompatible, or they are compatible both in the monomer casting solution and in the final molding solution, but the homopolymer is heritable or almost water-soluble. The monomer is such that it can be leached from the matrix polymer during use in reverse osmosis or ultra-permeability without forming an interpenetrating network within the matrix polymer.

This type of second monomer can vary compositionally, but is usually a monomer containing cationic or anionic groups, such as positive or negative groups, alone or in various combinations. When a compounded polymer membrane having negatively charged groups is used for the separation of water-in-oil engine or for use in the dairy industry, such as concentration of whey solution, it is necessary to use a compounded polymer membrane with a strongly charged group in the compounded polymer membrane. It is often desirable to use or have an optional saponyl group, usually a carboxylic acid group, especially a phosphonic acid group or a sulfonic acid group, as part of the second monomer.

If the resulting formulated polymer membrane is to be used, for example, for the concentration of aqueous and cationic electrocoating paint solutions, it is desirable that the formulated polymer membrane contain positively charged nitrogen atoms in the form of secondary or tertiary amino groups, especially quaternary ammonium groups. should contain. Quaternary amino groups can be introduced directly by using a suitable polymer, or by using monomers containing quaternary niaceno- or tertiary-amino groups and then in the casting solution. It is also possible to generate quaternized ammonium groups in the compounded film by treating the secondary or tertiary amonyl groups in the composition or after preparing the compounded layer.

That is, the second monomer useful for wrinkling the copolymer can be a wide variety of monomers, particularly monomers with positive or logical functional groups; Acrylate and methacrylate monomers containing sulfonic acid groups or amino groups or combinations thereof. - If a positively charged formulation^ molecular film is desired in the specific example, the second
The monomers can be acrylate monomers and methacrylate monomers, such as alkyl or L dialkylaminoethyl methacrylates and methacrylates, especially C1-C-alkyl or low dialkylaminoethyl methacrylates. Suitable secondary and tertiary amino monomers for use as the second monomer include, but are not limited to, dimethylaminoethyl methacrylate; dimethylaminoethyl methacrylate; dimethylaminoethyl acrylate; diethylaminoethyl arylate; 1
-butylaminoethyl methacrylate. Additionally, quaternary ammonium monomers may be used, or #i, niamino monomers M1+ and tertiary amino monomers may be cast, for example by use of well-known quaternizing agents such as dimethyl sulfate, methyl chloride. It can also be converted to the quaternary ammonium form by treatment in solution or in the final formulated membrane.

If the blended polymer membrane has a negative group as desired, the second
The monomers Fi can be, but are not particularly limited to, monomers having several sulfone groups, such as sulfonated monomers, especially acrylacetalkyl alkanes such as atarylaryl-domethylbutanpan (5MP8). A preferred cationic second monomer is MP8 and the first monomer is methyl methacrylate. A copolymer of MPI and methyl is particularly useful in water-in-oil applications when combined with a matrix polymer. The MP8 component, which may be a copolymer consisting of a copolymer with methacrylate, will impart hydrophilic sulnenic acid groups to the blended polymer. M
In the case of Pβ polymers, for example in the case of homopolymer reservoirs, matrix polymers such as PVD in solid form or in casting solution.
is incompatible with F and is water soluble and PVD
F! Leaches from the F littutus membrane. When Mu MP8 and methyl methacrylate are copolymerized, that is, the first monomer and the second monomer, the resulting copolymer is, for example, PVDF.
while being compatible with matrix polymers such as
It has been found that the resulting composition is stratified to reduce water solubility and the resulting copolymer does not leach from the membrane during use or when immersed in a public water leaching bath. Copper blend homopolymerization using a matrix polymer of vinylidene fluoride and a copolymer of MP8 and methyl methacrylate gave an experience with extremely high processing flux, i.e. 10
1 foot per day at ~20 psi low pressure6
00 gal and has a moderate response to pressure; also has a moderate flux of 300 to 400 gal/ft per day at pressures as low as 10 to 2 Dpmj and has a moderate response to higher pressures. It has a good response; it also gives a relatively low 7 lats or 7 lacs of 100 gains per foot per day at low pressure;
500-70 per foot per day at 50 pai
The 81 monomer of the copolymer exhibiting excellent response at higher pressures of 0 gam can include the use and addition of other monomers. For example, if the first monomer is a perfluorinated acrylate or methacrylate, in particular copolymers with MP8 or with tertiary aminoacrylates and methacrylates, such as polyfluoroalkyl methacrylates and acrylates, such as polyfluoroalkyl methacrylates and acrylates, such as It has been found that compounds such as octafluoropentyl methacrylate and other monomers result in polymeric membranes. For example, one preferred embodiment of the copolymer [11 using a methacrylate, especially a lower alkyl methatalyl, as monomer] and a sulfone-containing vinyl monomer such as tfAMP8 as the second monomer. In particular, monomers such as methylallyl, alkylarylsulfonate, and vinylsulfonic acid are used.

Typically, formulated polymeric membranes are prepared in a casting solution of about 8~! 15 weight attack, more realistic #i12~27 weight ≦
, with a total polymer content of e.g. 15-22 wt.
Typically Fi 11000-10 at 20°C (L OO
111 of the copolymer in the blended polymeric membrane to give a casting solution with Ocps (up to a weight of 10 to 35%, for example 15 to 25% by weight)
can be in the range of The first monomer of the copolymer and I
LtfL, tf2 can be enriched with I2 monomer, but
The range is from 0% to 80%, for example from 40% to 60%, for example d50:50-. Various other small amounts of polymers and additives may be added to the blended homogeneous polymer or casting solution, provided that these additives are compatible and do not affect the compatible and water-insoluble blended polymer. shall bring.

For copolymerization, @11 monomer and the second monomer are used in the organic solvent solution for the monomer, and a small but effective polymerization initiator is added, even if it is a U4-packed peroxide, e.g. It can be prepared separately by adding an organic or inorganic perhydride or azobis-isobutypnitrile or other azo initiator. Next, this copolymer! For example, if necessary, along with the Trix 凰 combination! Solvents such as dimethylacetamide for F lix polymers can be directly formulated into a suitable casting solution containing the solvent and diluent, and the resulting casting solution is then used to form thin films. , tubular or fibrous membranes can be formed.

The membrane can be supported or unsupported and is cast onto a fibrous support web, such as a woven or non-woven polyolefin, preester or its striated porous structure, and then at least After being partially evaporated, the partially evaporated and partially cured cast film is introduced into an aqueous leaching bath. Thin film thicknesses in forming thin films and tubular films can range, for example, from 1 to 50 cells, but are more typically from 5 to 15 mils, and film curing times from 11 to 15 mils.
In the range of 500 seconds, more typically in the range of 10-60 seconds, even 10-30 seconds. II! The public water bath is usually
The noodle skin ranges from about 6゛0 to 80A.

It has been found that some losses occur even during coleaching made from the first monomer and the second monomer. This is because the solvent carries some of the copolymer into the leaching bath during the coacervation process.

This typically occurs whenever a mixture of two hydrophobic polymers with different solubilities and molecular weights is coagulated. Lower molecular weight components will exhibit some tendency to leach. Therefore, it is practical to prepare a copolymer having a molecular weight as high as possible, for example, a molecular weight of 1 to 000 or more, preferably more than 1,000,000 or more. Additionally, most copolymers limit the range of comonomer distribution in the copolymer, resulting in the copolymer being almost completely water-soluble and being used during the leaching process. bring. Experiments have shown that losses during leaching are 50-40% under unfavorable conditions (low molecular weight, wide distribution).
After leaching, losses of more than 2 do not occur, even under severe conditions, although high levels can be reached.

In one example, the copolymer is a volatile organic solvent solvent! Acts as a solvent for Trix polymers as well as 2@ monomers. A polymerization initiator is added, stirred and heated, and left to stand to form a copolymer, and then! The solution containing the Trix polymer can be added directly to this polymerization solvent solution to create the desired casting solution, or as desired! The Trix polymer and additional solvents and diluents can also be added directly to the copolymerization solution to create a casting solution of the desired viscosity. The manufacturing method represents a considerable advance in membrane technology and enables the economical and rapid production of composite membranes with the desired functionality and parent properties, and moreover involves directly compounding a single agglomerate into a matrix-heavy material. Overcoming the difficulties associated with manufacturing compatible formulation membranes.

With regard to the description of the blended polymer family of the present invention and the method of manufacturing this membrane, the term "comparability" is used. The Trix polymer and the homopolymer of the second monomer undergo phase separation in the solvent used for the membrane casting solution, or the matrix polymer and the same homopolymer with which it is blended undergo solid phase separation. When copper is produced to form a polymer layer as a
When the solvent in the casting solution evaporates and diffuses, the appearance becomes non-uniform or a casting film is formed! Either the homopolymer in the matrix cannot function due to separation or microprecipitation, or it cannot produce a satisfactory membrane, or the homopolymer in the matrix becomes water-soluble! ) is used to mean a condition that substantially leaches from the substance. In the blended polymer family of the present invention, the copolymer is blended in intimate and interpenetrating manner with the polymer matrix and is not removed during leaching or during use, thus exhibiting parent wood properties and yields. The polymer group becomes water-insoluble.

The invention will now be described with reference to specific embodiments;
Therefore, those skilled in the art will recognize that changes and modifications may be made to the specific examples described, and all of these fall within the essence, spirit and scope of the present invention.

Production example of nitrogen-containing (cationic) copolymer 1 Dimethyl acetate (DMAc) 4801 and dimethylaminoethyl metatarylate (DMAEMA) 194
5j and methyl methacrylate (MMum) 12 & 5JF were mixed in a polyethylene container at ° room temperature. Azobisisobutyryl nitrile (IBN) initiator asso
II was dissolved in the mixture. High purity (oxygen-free) nitrogen was bubbled into the solution for 1 hour. The container was quickly sealed and placed in a 60°C oven for 4 days. At this point, it can be used for producing a copolymer liquid spreading solution. This formulation d, 50150, has a composition of 4% and a total solids content of 40%.

Example 2 40j of DMAc, 19.55JFf) VI and 2165F (F) MM were mixed in an Erlenmeyer flask, and α0111 of DMAc was dissolved in the mixture. The copolymerization was carried out as in Example 1.

Tuna production of anionic copolymer - Example 3 800071 DMAc, 2000j 2-acrylamido-2-methylpropanesulfone k (Mps) and 2
000j of MM and (14N of IBN) were mixed.

Preparation and copolymerization were carried out as in Example 1. This copolymer had a composition of 5 o/s o by weight.

Example 4 2401 DMA C and 10511 Mu MP8 (45.15% by weight of the resulting copolymer) and 4577 octafluoropentylmetatalyl (OFPMA).

270%) and 12jl of cyclohexyl methacrylate =)
(CHM, 7.7%), (L24JF glycidyl metatallylate (0M, α 15%) and α0169 IBN were mixed and copolymerized in the same manner as in Example 1.

Example 5 DMAEMA-MMA copolymer solution of 2 & 511 (DM
Total polymer concentration in AC 40% and comonomer distribution 5
0750 mol%) and 3481 PVDF and 1
4α61 N-methylvilleridone (NMP) was mixed until all components were dissolved. The material was cast to a thickness of 25 mils including the nonwoven substrate. The curing time was set to r&&]#'i for 5 seconds. The membrane was leached in pure water. These membranes gave 7 lats of 32 GFD on cationic paint and produced a clear permeate. The fouling rate was considerably slower for the experimental membranes, whereas conventional membranes would typically give 7 lux of 15-17 GFD for the same cationic paint. was treated with 14 WIt of methyl iodide to quaternize the N-containing components. The solution was heated at 80°C for a while. The ingredients were prepared as shown in Example 5. 7 Lux is 54GF for cationic paint.
D and was found to have much improved fouling rates.

Example 7 50150 mol of &O11 vinylimidazole/MM
Human copolymer (total solids in DMAC 40% αOII
of NMP and 2αOII of PVDF were mixed. The membrane was prepared as in Example 5. Similarly to the sand in Example 6, quaternization can be carried out as appropriate.

Film performance for cationic paints was similar to that in Examples 5 and 6.

Example 8 A solution of 2811 MUMP8/MM copolymer (copolymer 40% by weight, DMAc 60% by weight, having a monomer composition of 50150% by weight) was mixed with 2151 NMP.

After thorough mixing, 5711 PVDF was added with constant stirring, while atmospheric conditions were completely excluded. The solution was heated to 105° C. for 1 hour after all components had visibly decomposed.

The membrane was cast onto a nonwoven backing to give a thickness of 1 s mil on this face. After a 5 second curing time, the membrane was leached in pure water at room temperature.

jI! prepared by this method! Ha, synthetic oil industry! When tested on the Luji test, it showed 7 lats of 550 GFD at 10 psi and 7400 FD at 50 psi. The permeate Fi contained less than 20 ag/j of hydrocarbons. # after use contains less than α1-oil, whereas
The comparison contained about 35% more oil.

example ! A comparison layer containing PVDF (17) was prepared by dissolving 22.7 Nf) PVDFtt in 77.511 NMP.

After treating the casting solution and casting membrane in the same manner as above, the same circles as in Experiment B were produced! When using Luzi carbon, it showed 7 lux of 25 GFD at 10 psI and 70 GFD at 50 psi. The permeate is 20
It contained a large amount of hydrocarbons, about 0 to 11,000 pp. After use, MFi typically contains 30-50% oil.

MP8/cyclohexyl methacrylate (CHMA)
(60/40 Jusha-distribution) copolymer 247% and PVD
A membrane consisting of PZ & 3% was prepared in a manner similar to that described in Example 8. 7 observed for the same emulsion attack.
The flux was 110 GFD at 10 psi and 400 G1'D at 50 psm, resulting in a clear permeate.

Example 11 Copolymer of AMP8 and octafluoropentyl methacrylate (OFPMA) 2101 and P V D with a concentration of 40% in DMAc and a weight ratio of 4α81592
Mix F54.5.9 and DMAc122.5N,
Heated as in Example 8. The crotch was cast as shown in the example above. Synthetic engineer! 4000FD and 5
It showed 7x of $0.50 GFD at 0 psi, and all permeate fluids contained less than 20 pprn of hydrocarbon volume.

Example 12 (VFs-CTFI) copolymer (60 moles of AMP8 and 20 moles of OFP
MA and 199\mol CHMA and α1 mole ≦0M person, that is, glycidyl metatallyte F.

Membranes made from 6% 1a (consisting of ) 814 arc, a copolymer of vinylidene fluoride and siltrifluoroethylene, were prepared and tested as in Example 8. 7 lux is 400GFD and S at 10?81
Op weight was 6250 FD resulting in a clear permeate.

Example 13 Vinylidene fluoride removal pin in Example 12 #) Refluor I
Membranes were similarly tested using a copolymer of vinylidene fluoride and hexafluoropropane in place of the copolymer with ethylene, with similar results.

Example 14 #i primed PVC45N and AMP8/MMAJ) copolymer (weight ratio 60/40 and 40 whispers in DMAc droplet) 45
II and DMAc 2101 to form a casting solution.
II did it. One cast was made on a non-woven support bar to a thickness of 16 mils (including support) and a 10 second cure time was used.

7 lux tlj for synthetic emulsion 1: 10p
220GFD at S Todoroki and 1500GF at 50psi
It was D. The permeate was completely transparent. Example 15 Copolymer of vinylbenzyl chloride (WBC) and M-M (weight ratio 5 o, 5 o and 5 o in DMAC)
One solution was prepared using ay, PVDF4 (1) and DMAC52511.

This molten t100j was reacted with jetanol sulfide to produce a sulnenium ion-containing membrane.

The above ffi solution was reacted with another 100 II &) liphenyl phosphite to obtain a membrane containing phosphonium ions.

Furthermore, the sixth 1001 of the solution is added to the thiol fbfI! R
Processed with. The material prepared from this solution was then forged to obtain a component containing surnene.0 Procedural amendment January 14, 1980 Director General of the Patent Office Shima 1) Haruki Tono 11 indications 1982 Patent application No. 1 ! 3. Relation to the case of the person making the amendment Patent applicant name Abu Incorporated - Subject matter of assistant agent 1E - Axis - Specification ← Scope of claims 0" column Contents of the amendment We will amend the detailed statement submitted to the attached meeting.

t Correct the range field for 411FFllI as follows.

``Claim 2.411 (1)) A rounded water-insoluble matrix polymer that provides support and strength to the membrane, and -) compatible with and in situ blended with the matrix polymer. The copolymer consists of (1) a first monomer which, when homopolymerized, produces a water-insoluble homopolymer that is compatible with the matrix polymer of the membrane; a) a second monomer which is homopolymerized to form a homopolymer that is incompatible with the matrix polymer of the membrane, thereby forming a matrix polymer; A compounded polymer membrane characterized in that it imparts mutual incorporation of incompatible monomer functions therein.

(2) The membrane according to claim 1, wherein one of the monomers has a functional group with positive, negative, or uncharged polarity.

(3) The membrane according to claim 1, wherein one of the monomers has a positive nitrogen atom group.

(4) The membrane according to claim 1, wherein one of the monomers has a negative sulfone group or a human-xyl group.

(5) The membrane according to claim 1, wherein the matrix polymer comprises a hydrogenated organic polymer.

(6) The membrane according to claim 1, wherein the matrix polymer comprises a vinylidene fluoride polymer or copolymer.

(7) The membrane according to claim 1, wherein the matrix polymer is a chlorinated circularly cyclized vinyl polymer or a copolymer.

(8) The weight percent of the copolymer in the membrane polymer is about 10
55 weight≦Claim 1.

(9) The weight percent of one monomer in the copolymer is about 20 to SO
Membrane according to claim 1, having a weight range, preferably in the range from 40 to 40 weight.

2. The membrane according to claim 1, wherein the first monomer is a metatarylate or acrylate monomer.

(2) The membrane according to claim 10, wherein the first monomer is an alkyl methacrylate.

The membrane according to claim 1, wherein the second monomer comprises a monomer having a second or tertiary atom group.

13. The membrane according to claim 12, wherein the second monomer comprises alkyl secondary or tertiary azanoethyl methacrylate or acrylate.

(14) Claims in which the first monomer is a water-insoluble methacrylate or acrylate monomer, and the second monomer is a water-soluble sulfonated methacrylate or acrylamide monomer. The membrane according to item 1.

QS The matrix polymer consists of polyvinylidene fluoride or chlorinated vinyl chloride polymer, the first monomer of the copolymer consists of methyl methacrylate, and the second monomer of the copolymer consists of acrylate methyl methacrylate. The membrane according to claim 1, comprising propanesulfonic acid.

(Ieff) The lithics polymer consists of a polyvinylidene fluoride polymer or a chlorinated vinyl chloride polymer, the first monomer consists of methyl methacrylate, and the second monomer consists of dimethylaminoalkyl methacrylate or t-butyl A membrane according to claim 1, comprising an aminoalkyl methacrylate.

A patent claim in which the aη copolymer is a silicon-containing cationic copolymer, the first monomer is methyl methacrylate, and the second monomer is selected from the group consisting of dimethylaminoethyl methacrylate and vinyl imidazole. The membrane according to item 1.

ae copolymer is an anionic copolymer, the first monomer is selected from the group consisting of methyl methacrylate, cyclohexyl methacrylate and octafluoropentyl methacrylate, and the second monomer is 2-'acrylamide-2-methyl The membrane according to claim 1, which is propanesulfonic acid.

Vinylidene fluoride matrix polymer and -
) a copolymer compatible with and in intimate blend with the matrix polymer, said copolymer comprising a water-soluble sulfonated acrylate monomer and a water-insoluble Prepared by copolymerization with atarylate or methacrylate monomers, the weight percent of the copolymer to the layer polymer is in the range of about 10-55 weight percent, and the weight percent of the monomer in the copolymer is about 40 percent by weight. ~60% by weight, preferably from 40 to 60% by weight (1) vinylidene fluoride matrix polymer and -) this -r)
Compatible with and intimately blended with the 9x polymer, the copolymer is composed of a water-soluble secondary or tertiary acrylate monomer and a water-insoluble acrylate monomer. Prepared by copolymerization with acrylate or methacrylate monomers, the weight percent of the copolymer to the layer polymer ranges from about 40 to 60, and the weight percent of the monomer in the copolymer ranges from about 20 to 60. 80 tg, preferably about 40~
60 weight −〇lυ −) casting a solvent solution of the casting solution containing the polymer formulation; (B) evaporating at least a portion of the solvent of the casting solution; In a method for producing a compounded polymer membrane, which comprises immersing the evaporated nonapolymer thin film in a water bath and υ) recovering the compounded polymer membrane, a rounded non-aqueous polymer membrane that provides support and strength to the polymer membrane to be prepared is used. An organic solvent solution consisting of a matrix polymer and a water-insoluble and organic solvent-soluble copolymer that is compatible with and intimately blended with the matrix polymer after film formation is prepared. If the copolymer is homopolymerized, it will produce a water-insoluble homopolymer compatible with the membrane's ff) a second monomer which, when homopolymerized, produces a homopolymer that is incompatible with the polymer of the membrane or becomes water-soluble but soluble in the casting solution. A method for producing a blended polymer membrane, characterized in that it is prepared by copolymerization with.

(2) The first monomer and the second monomer are polymerized in an organic solvent solution to produce a copolymer, and then copolymerization is performed to form a matrix polymer and a solvent in an organic solvent solution. Claim 21, which includes creating a casting solution by adding
The method described in section.

22. The method of claim 21, wherein the total polymer content of the casting solution ranges from 8 to 35% by weight.

(Foundation) il [The solution is dimethyl acetate
22. The method according to claim 21, which comprises hydrogen or N-methyl bitetralidone.

(to) Casting the casting solution as a thin film in the range of about 1 to 30 mils onto a fiber support backing.
The method described in Section 1.

(2) The viscosity of the casting solution is about 1 to 11)0.0
22. The method of claim 21, wherein the range is 0.00 cpl'.

(Incorporated) a tank in which the film is formed at a speed of about i to 20 feet per minute;
22. The method of claim 21, wherein the curing time is in the range of about 1 to 3.0 seconds.

(2) The first monomer is an acrylate or methacrylate monomer, and the second monomer has a second attached tertiary amino group, and the amino group is quaternized to form a quaternary ammonium 22. The method of claim 21, comprising producing a group ".

@! 22. The method according to claim 21, comprising a matrix polymer, a salt-enriched vinyl chloride polymer or a copolymer.

■ The weight of the copolymer in the membrane chamber coalescence is approximately 1.~35
22. The method according to claim 21, which is in the range of heavy weight.

01) The weight of one monomer of the copolymer is about 2e to 80
22. A method according to claim 21, wherein the weight arc preferably ranges from about 40 to 60 weight arcs.

(to) Claims in which the first monomer is a water-insoluble methacrylate or acrylate monomer, and the second monomer is a water-soluble sulfonated methacrylate or acrylate monomer. [Article 11121.

- A claim in which the copolymer is a nitrogen-containing cationic copolymer, the first monomer is methyl methacrylate, and the second monomer is selected from the group consisting of dimethylaminoethyl methacrylate and vinylimidazole. range 21st
The method described in section.

The copolymer is an anionic copolymer, the first monomer is selected from the group consisting of methyl methacrylate, Schiff-tetrahexyl methacrylate, and octafluoro-tetrapentyl methacrylate, and the second monomer is 2- 22. The method according to claim 21, wherein the acrylic acid is 2-methylpypanesulfonic acid.

Claims (1)

[Scope of Claims] (1) (a) a water-insoluble matrix polymer for providing support and strength to the membrane, and (b) a non-water-insoluble matrix polymer that is compatible with and intimately blended with the matrix polymer a water-soluble copolymer; , θ Todoroki) is produced by copolymerization with a second monomer that, when homopolymerized, produces a homopolymer that is incompatible with the matrix polymer of the membrane, thereby incorporating it into the matrix polymer. A compounded polymer membrane characterized in that it provides a mutual compounding of incompatible monomer functions. (2) The membrane according to claim 91, wherein one of the monomers has a positive, negative, or non-conductive functional group. (3) The membrane according to claim 1, wherein one of the polymers has a positive ** atomic group. (4) The membrane according to claim 1, wherein one of the monomers has a negative sulfone group or a hydroxyl group. (5) The development according to claim 1, wherein the matrix polymer comprises a hep-genated organic polymer. (6) The membrane according to claim th1, wherein the matrix polymer is a vinylidene fluoride polymer or a copolymer. (7)! 2. The method according to claim 1, wherein the silicon polymer is a chlorinated vinyl chloride polymer or copolymer. (8) #The bracken according to claim 1, wherein the copolymer content % in the polymer is in the range of about 1° to 5.5% (9) One of the copolymers Monomer km% is about 20~
Membrane according to claim 1, having a weight of 80 weight l-1, preferably in the range of 40 to 60 weight l-1. (10) The membrane according to item 1, wherein the first monomer is a methacrylate-4-adsorbed acrylate monomer. (11) The first monomer is an alkyl methacrylate JIIO)) The compound according to (12) #h
2. The membrane according to claim 1, wherein the two monomers are monomers having a secondary or tertiary amino group. (13) The second monomer comprises alkyl secondary or #i tertiary electronoethyl methacrylate or atarylege, and (14) the jll monomer is water-insoluble. (15) The matrix polymer according to claim 1, which is an acrylate or an acrylate monomer, and the 82 monomer is a water-soluble sulfonated methacrylamide or acrylamide monomer. is made of polyvinylidene fluoride or a chlorinated vinyl chloride polymer, the first monomer of the copolymer is made of methyl methacrylate, and the second monomer of the copolymer is made of ataryl atom-domethylpropylene sulfonic acid. (16) The matrix polymer consists of a polyvinylidene fluoride polymer or a chlorinated vinyl chloride monomer, the first unit consists of methyl methacrylate, and the second The agricultural product according to item 1, wherein the monomer is dimethylaminoalkyl methacrylate or t-butylaminoalkyl methacrylate. (17) The copolymer is a nitrogen-containing cationic copolymer, the 1h1 monocap is methyl methacrylate, and the 2 monomer jlIi 141: is selected from the group consisting of dimethylaminoethyl methacrylate and vinylimidazole. A membrane according to claim 1. (18) The copolymer is an anionic copolymer, the S1 monomer is selected from the group consisting of methyl methacrylate, cyclohexyl methacrylate, and otatafluoropentyl methacrylate, and the second monomer is 2-7 2. The membrane according to claim 1, which is chlorinated 2-methylbenzene sulfone. (19) (a) Vinylidene fluoride! a copolymer which is mutually compatible with and intimately blended with the matrix polymer, said copolymer being a water-soluble sulfonated acetoarylate monomer. and a water-insoluble acrylate or methacrylate monomer.
% L of the comonomer relative to the expanded polymer is about 10~
It is within the range of 551i attack, and the amount of comonomer U is 4 &m
%tJ about 20 to about 2 rich to 80. (20) consisting of (a) a vinylidene fluoride matrix polymer; and (b) a copolymer compatible with and intimately blended with the matrix polymer, said copolymer having a water-soluble Prepared by copolymerization of a secondary or tertiary aminoethyl atelylide monomer and a water-insoluble acrylate or methacrylate monomer, the weight of the copolymer to the layer polymer is about 10 to 35%.
The weight of the monomers in the copolymer is approximately 2
0 to 8' o weight, preferably about 40 to 40311 weight -
Compounded polymer membranes that range from . (21) (a) casting a solvent solution of the casting solution containing the polymer formulation; (B) evaporating at least a portion of the solvent of the casting solution; and (C) casting and partially evaporating the solvent of the casting solution. In a compounded polymer membrane tack manufacturing method comprising immersing the combined thin membrane in a water bath and (d) recovering the compounded polymer membrane. Non-water portability to provide support and strength to the polymer membrane to be prepared! An organic solvent casting solution is prepared consisting of a tritutas polymer and a water-insoluble, organic-glue-soluble copolymer that is compatible with and intimately blended with this matrix polymer after membrane formation. , the copolymer is homopolymerized with a first monomer which, when homopolymerized, forms a water-insoluble homopolymer that is compatible with the matrix polymer and is soluble in the casting solution; When homopolymerized, it produces a single mold rod that is incompatible with the matrix polymer, or when it is water soluble, it is prepared by copolymerization with a second homopolymer that is soluble in the casting solution. A method for producing a blended polymer group, characterized by: (22) The first monomer and the second monomer are polymerized in an organic solvent solution to produce a copolymer, and then the matrix polymer and the solvent are added to the organic ffI medium solution in which the copolymerization is performed. The claims include creating a casting solution by adding [
1$ The method described in item 111. (25) The method according to claim 1121, wherein the total polymer content of the casting solution is in the range of 8 to 1% by weight. (24) The method according to claim 21, wherein the casting solution contains dimethyl acetate or tiN-methylvilleridone as an organic solvent. 25. The method of claim 21, comprising casting the casting solution as a thin film of about 1 to 30 mm on the fiber support backing. (26) The viscosity of the casting solution is about IQ, 000~10QO
The method of claim 21, wherein: The method described in Scope 21 (2B) The first monomer is an acrylate or methacrylate monomer, and the second monomer has a tri-amino group and an ano group. 22. The method of claim 21, comprising quaternizing to produce quaternary ammonium groups. (2?)Y) Claim 1121 wherein the 9x polymer comprises a chlorinated vinyl chloride polymer or copolymer.
The method described in section. (30) 1 M% of the copolymer in the layer polymer is about 10
~! 22. The method of claim 21, which is within the scope of No. 5311. (31) The weight it% of one monomer of the copolymer is about 20 to
(52) The first monomer is a water-insoluble methacrylate or arylate monomer. 22. The method of claim 21, wherein the second monomer is a water-soluble sulfonated methacrylamide or acrylamide monomer. (s3) The copolymer is a nitrogen-containing cationic copolymer, the first monomer is methyl methacrylate-F, and the second monomer is methyl methacrylate-F.
22. The method of claim 21, wherein the monomer is selected from the group consisting of dimethylabunoethyl methacrylate and vinylimidazole. (54) The copolymer is an anionic copolymer, the first monomer is selected from the group consisting of methyl methacrylate, cyclohexyl methacrylate, and octafluoropentyl methacrylate, and the second monomer is 2-acrylamide. -2-Methylbutanesulfonic acid, the method according to claim 21.