Office Action 1: Non-Final Rejection (2025-02-12)
Rejection types: 102 - Lack of Novelty

CLAIMS:
CLAIMS

What is claimed is:

1\. A method of processing a solution of vinylamine-containing polymers comprising;
\- providing the solution of vinylamine-containing polymer;
\- circulating the solution through a nanofiltration membrane and/or an ultrafiltration membrane thereby producing a vinylamine-containing retentate; and
\- collecting the vinylamine-containing polymer retentate.

2\. The method of claim 1, wherein the solution of vinylamine-containing polymer further comprises one or more of a salt or a by-product formed during vinylamine containing polymer synthesis and or modification of vinylamine containing polymer, and wherein circulating the solution through the nanofiltration membrane and/or an ultrafiltration membrane comprises separating the vinylamine-containing polymer retentate from at least a portion of the salts and/or a by-product.

3\. The method of claim 1, wherein collecting vinylamine containing polymer retentate comprises collecting the vinylamine-containing polymer retentate having a reduced amount of salts and/or a by-product as compared to the solution prior to circulating through the nanofiltration membrane and/or an ultrafiltration membrane.

4\. The method according to claim 2, wherein the salts and/or by-products are permeable molecules, unwanted reaction salts, small proteins, organic and/or inorganic solvents, residual monomers, monomeric impurities, monomer decomposition byproducts, monomer stabilizers, and byproducts from initiator decomposition, and/or impurities coming from cationizing and/or alkylating agent containing amine or amide functionality.

5\. The method according to claim 4, wherein the salts and/or by-products are monomeric impurities.

6\. The method according to claim 2, wherein the salts and by-products are impurities from reactions involving N-vinylformamide polymerization and copolymerization with other functional monomers, hydrolysis of polyvinylformamide by acid or caustic treatment, and post polymerization modification of vinylamine-containing polymers with functional monomers.

7\. The method of claim 1, wherein collecting the vinylamine-containing polymer retentate comprises colleting the vinylamine-containing polymer retentate having a higher concentration of vinylamine-containing polymer than the solution prior to circulating through the nanofiltration membrane and/or an ultrafiltration membrane.

8\. The method according to claim 1, wherein the nanofiltration membrane and/or an ultrafiltration membrane has a molecular weight cut-off of about 100 Dalton (Da) to about 10,000 Da, or about 200 Da to about 2,000 Da, or from about 500 Da to about 1,000 Da, and
can be 800 Da.

9\. A method of improving drainage in a papermaking process comprising adding the retentate according to claim 1, to a papermaking furnish.

10\. A method of preparing a solution of high molecular weight vinylamine-containing polymers comprising, - providing a solution of vinylamine-containing polymer comprising a low molecular weight vinylamine polymer component and a high molecular weight vinylamine polymer component; - circulating the solution through a nanofiltration and/or ultrafiltration membrane having a molecular weight cut-off of about 10,000 Da, thereby separating a fraction of low molecular weight vinylamine-containing polymer from a fraction of high molecular weight vinylamine-containing polymer; and - collecting the fraction of the higher molecular vinylamine-containing polymer.

11\. The method according to claim 10, wherein the weight average molecular weight of the collected fraction of the vinylamine-containing polymer retentate is from about 10,000 to about 1,000,000 Da.

12\. The method according to claim 11, wherein the weight average molecular weight of the collected fraction of vinylamine-containing polymer retentate is from about 20,000 to about 750,000 Da.

13\. The method according to claim 12, wherein the weight average molecular weight of the collected fraction of vinylamine-containing polymer retentate is from about 50,000 to about 400.000 Da.

14\. The method according to claim 13, wherein the weight average molecular weight of the collected fraction of vinylamine-containing polymer retentate is from about 100,000 to about 250.000 Da. 12 13 14

OFFICE ACTION:
Notice of Pre-AIA  or AIA  Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claim Rejections - 35 USC § 102
The following is a quotation of the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(1) the claimed invention was patented, described in a printed publication, or in public use, on sale, or otherwise available to the public before the effective filing date of the claimed invention.
Claims 1-14 are rejected under 35 U.S.C. 102(a) ((1) as being anticipated by US Patent 6,716,311 (US 311).	Bridging paragraph of col. 5-6 of the US 311 teaches that polymers containing vinylamine units are preferably used in salt-free form. Salt-free aqueous solutions of polymer containing vinylamine units can be prepared, for example, from the salt-containing polymer solutions with the aid of dialysis or ultrafiltration through suitable membranes with cut-offs of, for example, from 1,000 to 500,000, preferably from 10,000 to 300,000, Dalton. Other polymer containing amino and/or ammonium groups can also be obtained in salt-free form with the aid of dialysis or ultrafiltration. In the ultrafiltration through member having the abovementioned cut-offs, fractionation of the polymer resulting in polymer having a relatively narrow molar mass distribution M.sub.w /M.sub.n is achieved in addition to removal of salts which are formed. The fractions of polymers having a narrow distribution which are obtained as retentate in the ultrafiltration.
Regarding claims 2-4, as noted above the salts are removed through filtration.
Regarding claim 5, the polymers are made from monomeric salts for which the polymers are made from. See Col. 5, ll.5-61.
Regarding claim 6, the polymers are made from hydrolysis from polyvinyl formamide. See Col. 5, ll. 5-61.
Regarding claim 7, it would be inherent that the retentate would have a high concentration of polymers once it is screened through the membrane that filters out such polymer.
Regarding claim 8 and 11-14, see above noting the claimed Dalton.
Regarding claim 9, the abstract of US 311 teaches that the polymers can be used as fixing agents in papermaking stock.
Regarding claim 10, as noted in Col. 5, ll. 5-61 and example 3, high and low molecular weights polymers are used wherein the membrane collects the higher molecular polymer.
Conclusion

APPLICANT REBUTTAL: REMARKS/ARGUMENTSClaims 1-14 were pending in the application, claims 1-14 have been rejected. Claims 1, 6-8, and 10, have been amended and claims 2, 3, and 11 cancelled. Therefore, claims 1, 4-10, and 12-14, are pending and under consideration. No new matter has been added.CLAIM REJECTION UNDER 35 USC § 102 Claims 1-14 are rejected under 35 U.S.C. 102(a) ((1) as being anticipated by US Patent 6,716,311 (hereinafter referred to as "Decker").Applicants teach the use of activated media to filter these salts, by-products, and low molecular weight vinylamine-containing polymers while retaining the functional, higher molecular weight polymers that provide desired product performance, but it was not practical on a commercial scale due to pressure drop, yield loss and efficacy (pg. 1, para. [0003]). Decker teaches novel polymers which are effective asfixing agents in papermaking. Decker found that this object is achieved, according to the invention, by modified cationic polymers which are obtainable by reacting...(col. 1 lines 54 to col. 2, lines 14).Although Decker teaches some aspects of the present invention, their objective is clearly different. Decker fails to teach certain critical aspects of the present technology, i.e., circulating the vinylamine-containing polymer through membranes having cut-offs below 1,000 Da. Although Decker discloses membranes for example, 1,000 to 500,000 Da, Decker teaches cut-offs of preferably 10,000 to 300,000 Dalton, which is not claimed for the current technology (col. 6, lines 1-3, emphasis added). More relevant, Decker does not teach circulating the polymer through membranes having cut-offs offrom about 500 Da to 1,000 Da. In fact, Applicants teach in claim 8, that the cut-off is 800 Da.Applicants have amended claims 1 and 10, to clarify that the vinylamine- containing polymer comprises one or more of a salt or a by-product formed during vinylamine-containing polymer synthesis and/or modification of vinylamine containing polymer (pg. 4, para. [0014] and claim 2). In addition, the claims were amended to clarify that the nanofiltration membrane and/or an ultrafiltration membrane having a molecular cutoff of from about 500 Dalton to 1,000 Dalton (pg. 5, para. [0018]), thereby separating a retentate of the vinylamine-containing polymer from at least a portion of the salts and/or by-product (pg. 4, para. [0013] - [0014], claim 2).Finally, claims 1 and 10, were amended to clarify that the collected retentate has a reduced amount of salts and/or a by-product as compared to the solution prior to circulating through the nanofiltration membrane and/or an ultrafiltration membrane (pg.4, para. [0015]).It was only found through the careful selection of the membrane that removal of impurities could be accomplished with no loss of functional polymer or degradation of the polymer (pg. 5, para. [0021]).As the Examiner is likely aware, "[a] claim is anticipated only if each and every element as set forth in the claim is found, either expressly or inherently described, in a single prior art reference." Verdegaal Bros. v. Union Oil Co. of California, 814 F.2d 628, 631, 2 USPQ2d 1051, 1053 (Fed. Cir. 1987). As pointed out above, Decker does not teach cut-off lines of between 500 Da. and 1000 Da. and certainly not 800 Da as required from claim 8.Based on the teachings of Decker, one of ordinary skill in the art would use filtration cut-offs of at least 1,000 Da. or higher (col. 6, lines 1-3).CONCLUSIONIn view of Applicants' amendments and remarks, it is respectfully submitted that Examiner's rejections of claims 1-14, have been overcome. Accordingly, Applicants respectfully submit that the application, as amended, is now in condition for allowance, and such allowance is therefore earnestly requested. Should the Examiner have any questions or wish to further discuss this application and amended claims, Applicants request that the Examiner contact the Applicants' attorneys at 480-361-0466.No fees are believed to be due with this response. However, if there are any other fees required to have this amendment entered or to keep the application pending, the Commissioner is hereby authorized to charge Deposit Account No. 502091 for any fee which may be due.Respectfully submitted,

NEXT OFFICE ACTION: DETAILED ACTION
Notice of Pre-AIA  or AIA  Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Response to Arguments
Applicant’s amendments and arguments, filed 3/28/2025, have overcome the rejections based on 35 U.S.C. 102.  Said rejections have been withdrawn.  All rejections of Claims 2-3 and 11 have also been withdrawn due to cancellation of the claims.  The remaining rejections over the prior art have been modified to address the amendments to the claims and in view of newly cited prior art.
Applicant’s arguments have been carefully considered, but they are not convincing.
Regarding the argument that the prior art uses the filtered polymers for a different purpose, Applicant recognizes that Decker et al discloses using ultrafiltration with a membrane having a cut-off value as low as 1,000 Daltons, and that the instant claims recite a cut-off value of about 500 Daltons to 1,000 Daltons. One of ordinary skill in the art would have found no significant difference in the process between using a cut-off of 1,000 Daltons or slightly above 1,000 Daltons and a cut off of slightly lower than 1,000 Daltons.  Applicants have not provided convincing evidence of the criticality of the claimed range of about 500 daltons to 1000 Daltons.  Absent convincing evidence of such criticality and/or unexpected results commensurate in scope with the claims, it would have been obvious to one of ordinary skill in the art to select an ultrafiltration membrane having a cut-off of 1,000 Daltons or slightly above 1,000 Daltons for the ultrafiltration with a reasonable expectation of obtaining a retentate comprising a suitable polymer solution that has a reduced amount of salts compared to the solution prior to circulating through the ultrafiltration membrane.
Regarding the argument that Decker et al does not disclose circulating the polymer through membranes having the claimed cut-off values, the issue is addressed in the modified rejections detailed herein.
Regarding the assertion that It was only found through the careful selection of the membrane that removal of impurities could be accomplished with no loss of functional polymer or degradation of the polymer, Applicants have not provided convincing evidence commensurate in scope with the claims of the criticality of the claimed range of about 500 daltons to 1000 Daltons.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
The following is a quotation of pre-AIA  35 U.S.C. 112, fourth paragraph:
Subject to the following paragraph [i.e., the fifth paragraph of pre-AIA  35 U.S.C. 112], a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claims 12-14 are rejected under 35 U.S.C. 112(d) or pre-AIA  35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends.  Claims 12-14 depend from a cancelled claim, and therefore, fail to reference a claim previously set forth and then specify a further limitation of the subject matter claimed.  Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA  35 U.S.C. 102 and 103 (or as subject to pre-AIA  35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA  to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
. Claims 1, 4-10 and 12-14 are rejected under 35 U.S.C. 103 as being anticipated by Decker et al US 6,716,311 in view of Bennett et al (US 2006/0065599).
Bridging paragraph of col. 5-6 of the US 311 teaches that polymers containing vinylamine units are preferably used in salt-free form. Salt-free aqueous solutions of polymer containing vinylamine units can be prepared, for example, from the salt- containing polymer solutions with the aid of dialysis or ultrafiltration through suitable membranes with cut-offs of, for example, from 1,000 to 500,000 Daltons, which overlays or touches the upper end of the claimed range.  One of ordinary skill in the art would have found no significant difference in the ultrafiltration between using a cut-off of 1000 Daltons or slightly above 1000 Daltons and a cut off of slightly lower than 1000 Daltons.
Applicants have not provided convincing evidence of the criticality of the claimed range of about 500 daltons to 1000 Daltons.  Absent convincing evidence of such criticality and/or unexpected results commensurate in scope with the claims, it would have been obvious to one of ordinary skill in the art to select an ultrafiltration membrane having a cut-off of 1,000 Daltons for the ultrafiltration with a reasonable expectation of obtaining a retentate comprising a suitable polymer solution that is salt-free or, at least, has a reduced amount of salts compared to the solution prior to circulating through the ultrafiltration membrane.
Other polymers containing amino and/or ammonium groups can also be obtained in salt-free form with the aid of dialysis or ultrafiltration. In the ultrafiltration through a membrane having the abovementioned cut-off, fractionation of the polymer resulting in polymer having a relatively narrow molar mass distribution Mw /Mn is achieved in addition to removal of salts which are formed. The fractions of polymers having a narrow distribution are obtained as retentate in the ultrafiltration.
Decker et al discloses molar masses of polymers containing vinylamine units from 1,000 to 10 million Daltons (col 5, lines 55-57), which significantly overlays the claimed ranges or, at least, obtaining vinylamine-containing polymers having a claimed molecular weight would have been obvious absent convincing evidence of unexpected results commensurate in scope with the claims.
Decker et al does not disclose circulating the through circulating the solution through a nanofiltration membrane and/or an ultrafiltration membrane having a molecular cut-off from about 500 Dalton to 1,000 Dalton.
In the same field of endeavor, Bennett et al discloses a process for reducing the content of water-soluble salts of aqueous solutions of polymers containing vinylamine groups by ultrafiltration to achieve a desired reduced salt content.  Bennett et al discloses the theory of ultrafiltration, which is generally known to those of ordinary skill in the art, as follows ([0015]-[0019]);
“The theory of ultrafiltration states that during diafiltration, micro solutes (ions and low molecular weight polymers) freely permeate through the membranes and maintain the same concentration on both sides of the membrane. The concentration of membrane permeable species (sodium formate) remaining in the feed solution can be calculated by the following:
PNG
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35
148
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Greyscale
where:
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136
393
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Greyscale
Vd/Vo is the number of wash volumes (cycles or recirculation  that have been completed. One wash cycle (or wash volume) means the addition of an equivalent amount of fresh water to the starting solution volume and removal of the same amount of permeate solution. According to the equation, 95% of the initial sodium formate is removed after 3 wash volumes and 98% of the initial formate is removed after 4 wash volumes have been completed.”
Bennett et al shows that circulating the solution through the ultrafiltration membrane more than once may be necessary to achieve the desired reduction in salts and by-products.  To achieve the desired degree of purity for this process 4-5 wash cycles are normally required.  Therefore, the number of cycles, or the number of times the solution is circulated through the ultrafiltration membrane, is a result effective variable.
It would have been obvious to one of ordinary skill in the art to circulate the solution through the ultrafiltration membrane multiple times to obtain a desired reduction in salts and by-products.  Collecting the obtained vinylamine-containing polymer retentate would have been obvious as a purpose for performing the ultrafiltration.
Regarding claim 4, as noted above the salts are removed through filtration.
Regarding claim 5, the impurities include monomeric salts from which the polymers are made (col. 5, lines 5-61).
Regarding claim 6, the polymers are made from hydrolysis from polyvinyl formamide (col. 5, lines 5-61).
Regarding claim 7, it would be inherent that the retentate would have a high concentration of polymers once it is screened through the membrane that filters out such polymer.
Regarding claim 8, Bennett et al discloses that the cut-off value of the ultrafiltration or nanofiltration membrane can be as low as 400 Daltons and up to 10,000 Daltons, depending on the k-value (which is related to the molecular weight) of the polymer being filtered to achieve the [0039].  Therefore, the cut-off value for the membrane is also a result effective variable and it would have been obvious to one of ordinary skill in the art to determine the claimed cut-off value depending on the molecular weight of the polymer being filtered and the desired molecular weight to be obtained.
Regarding claim 9, the abstract of Decker et al teaches that the polymers can be used as fixing agents in papermaking stock, therefore adding the retentate to a papermaking furnish would have been obvious.
Regarding claim 10, as noted previously in Decker et al, the membrane collects the higher molecular weight polymer fraction in the retentate from the ultrafiltration, while polymers of low molecular weights are separated in the permeate from the ultrafiltration.
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.

CITED REFERENCE SUMMARIES: Ref US20240287742A1: Claims:
A method of processing a solution of vinylamine-containing polymers comprising: providing the solution of vinylamine-containing polymer: circulating the solution through a nanofiltration membrane and/or an ultrafiltration membrane thereby producing a vinylamine-containing retentate; and collecting the vinylamine-containing polymer retentate.
providing the solution of vinylamine-containing polymer:
circulating the solution through a nanofiltration membrane and/or an ultrafiltration membrane thereby producing a vinylamine-containing retentate; and
collecting the vinylamine-containing polymer retentate.
The method of claim 1 , wherein the solution of vinylamine-containing polymer further comprises one or more of a salt or a by-product formed during vinylamine containing polymer synthesis and or modification of vinylamine containing polymer, and wherein circulating the solution through the nanofiltration membrane and/or an ultrafiltration membrane comprises separating the vinylamine-containing polymer retentate from at least a portion of the salts and/or a by-product.
The method of claim 1 , wherein collecting vinylamine containing polymer retentate comprises collecting the vinylamine-containing polymer retentate having a reduced amount of salts and/or a by-product as compared to the solution prior to circulating through the nanofiltration membrane and/or an ultrafiltration membrane.
The method according to claim 2 , wherein the salts and/or by-products are permeable molecules, unwanted reaction salts, small proteins, organic and/or inorganic solvents, residual monomers, monomeric impurities, monomer decomposition byproducts, monomer stabilizers, and byproducts from initiator decomposition, and/or impurities coming from cationizing and/or alkylating agent containing amine or amide functionality.
The method according to claim 4 , wherein the salts and/or by-products are monomeric impurities.
The method according to claim 2 , wherein the salts and by-products are impurities from reactions involving N-vinylformamide polymerization and copolymerization with other functional monomers, hydrolysis of polyvinylformamide by acid or caustic treatment, and post polymerization modification of vinylamine-containing polymers with functional monomers.
The method of claim 1 , wherein collecting the vinylamine-containing polymer retentate comprises colleting the vinylamine-containing polymer retentate having a higher concentration of vinylamine-containing polymer than the solution prior to circulating through the nanofiltration membrane and/or an ultrafiltration membrane.
The method according to claim 1 , wherein the nanofiltration membrane and/or an ultrafiltration membrane has a molecular weight cut-off of about 100 Dalton (Da) to about 10,000 Da, or about 200 Da to about 2,000 Da, or from about 500 Da to about 1,000 Da, and can be 800 Da.
A method of improving drainage in a papermaking process comprising adding the retentate according to claim 1 , to a papermaking furnish.
A method of preparing a solution of high molecular weight vinylamine-containing polymers comprising, providing a solution of vinylamine-containing polymer comprising a low molecular weight vinylamine polymer component and a high molecular weight vinylamine polymer component; circulating the solution through a nanofiltration and/or ultrafiltration membrane having a molecular weight cut-off of about 10,000 Da, thereby separating a fraction of low molecular weight vinylamine-containing polymer from a fraction of high molecular weight vinylamine-containing polymer; and collecting the fraction of the higher molecular vinylamine-containing polymer.
providing a solution of vinylamine-containing polymer comprising a low molecular weight vinylamine polymer component and a high molecular weight vinylamine polymer component;
circulating the solution through a nanofiltration and/or ultrafiltration membrane having a molecular weight cut-off of about 10,000 Da, thereby separating a fraction of low molecular weight vinylamine-containing polymer from a fraction of high molecular weight vinylamine-containing polymer; and
collecting the fraction of the higher molecular vinylamine-containing polymer.
The method according to claim 10 , wherein the weight average molecular weight of the collected fraction of the vinylamine-containing polymer retentate is from about 10,000 to about 1,000,000 Da.
The method according to claim 11 , wherein the weight average molecular weight of the collected fraction of vinylamine-containing polymer retentate is from about 20,000 to about 750,000 Da.
The method according to claim 12 , wherein the weight average molecular weight of the collected fraction of vinylamine-containing polymer retentate is from about 50,000 to about 400,000 Da.
The method according to claim 13 , wherein the weight average molecular weight of the collected fraction of vinylamine-containing polymer retentate is from about 100,000 to about 250,000 Da.
Ref US20130118699A1: Claims:
A process for making vinylamine-vinylformamide-styrene terpolymer additives comprising: a) reacting vinylformamide with styrene or substituted styrene under free radical, emulsion polymerization reaction conditions; b) producing a first polymer product which comprises randomly distributed repeating units by the formula (I) and (II):
a) reacting vinylformamide with styrene or substituted styrene under free radical, emulsion polymerization reaction conditions;
b) producing a first polymer product which comprises randomly distributed repeating units by the formula (I) and (II):
wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R 1 is hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50; c) hydrolyzing the first polymer product with an acid or base treatment; d) producing a second polymer product comprising randomly distributed repeating monomer units having at least two of the formula (III), (IV), (V) and (VI):
wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R 1 is hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50;
c) hydrolyzing the first polymer product with an acid or base treatment;
d) producing a second polymer product comprising randomly distributed repeating monomer units having at least two of the formula (III), (IV), (V) and (VI):
wherein, R 2 and R 3 are H; R 4 is H or alkyl; m 1 and m 2 independently is a positive mole percent, and m 3 and m 4 independently may be 0 to 99 mole percent, and the sum of m 1 , m 2 , m 3 and m 4 is equal to or less than x mole percent of formula (I).
R 2 and R 3 are H;
R 4 is H or alkyl;
m 1 and m 2 independently is a positive mole percent, and m 3 and m 4 independently may be 0 to 99 mole percent, and the sum of m 1 , m 2 , m 3 and m 4 is equal to or less than x mole percent of formula (I).
The process of claim 1 , wherein Ar is phenyl and R 1 is H.
The process of claim 1 , wherein the first polymer product is vinylformamide-styrene copolymer.
The process of claim 1 , wherein the emulsion polymerization reaction is carried out at temperature in the range of from about 25° C. to about 125° C.
The process of claim 1 , wherein the emulsion polymerization reaction is carried out at temperature in the range of from about 30° C. to about 90° C.
The process of claim 1 , wherein the emulsion polymerization reaction is carried out at temperature in the range of from about 60° C. to about 85° C.
The process of claim 1 , wherein the ratio of x:y is in the range of from 80:20 to 51:49.
The process of claim 1 , wherein the ratio of x:y is in the range of from 80:20 to 70:30.
The process of claim 1 , wherein about 10% to 99% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d).
The process of claim 1 , wherein about 20% to 80% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d).
The process of claim 1 , wherein about 30% to 70% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d).
The process of claim 1 , wherein the second polymer product is a cationic, and water dispersible polymer.
An aqueous dispersion comprising the resulting polymer product from a process which comprises: a) reacting vinylformamide with styrene or substituted styrene under free radical, emulsion polymerization reaction conditions; b) producing a polymer product which comprises randomly distributed repeating units by the formula (I) and (II):
b) producing a polymer product which comprises randomly distributed repeating units by the formula (I) and (II):
wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R 1 is hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50; wherein, the polymer product in said aqueous dispersion is in a form of microparticles, and the particle size of the polymer product is in the range of from 30 nanometer to 2000 nanometer.
wherein, the polymer product in said aqueous dispersion is in a form of microparticles, and the particle size of the polymer product is in the range of from 30 nanometer to 2000 nanometer.
The aqueous dispersion of claim 13 , wherein the particle size of the polymer product is in the range of from 50 nm to 1000 nanometer.
The aqueous dispersion of claim 13 , wherein the particle size of the polymer product is in the range of from 70 nanometer to 200 nanometer.
A vinylamine-vinylformamide-styrene terpolymer additive comprising the resulting second polymer product from a process which comprises: a) reacting vinylformamide with styrene or substituted styrene under free radical, emulsion polymerization reaction conditions; b) producing a first polymer product which comprises randomly distributed repeating units by the formula (I) and (II):
wherein Ar is an aromatic selected from the group consisting of phenyl and phenyl substituted with alkyl, alkoxy, sulfonate, halo and pyridine or substituted pyridine; R 1 is hydrogen or alkyl; x and y are numbers greater than zero mole percent, and the sum of x and y is 100 mole percent, the ratio of x:y is in the range of from 99:1 to 50:50; c) hydrolyzing the first polymer product using and acid or base treatment; d) producing a second polymer product comprising randomly distributed repeating monomer units having at least two of the formulae (III), (IV), (V) and (VI):
c) hydrolyzing the first polymer product using and acid or base treatment;
d) producing a second polymer product comprising randomly distributed repeating monomer units having at least two of the formulae (III), (IV), (V) and (VI):
wherein, R 2 and R 3 are H; R 4 is H or alkyl; m 1 and m 2 independently is a positive mole percent, and m 3 and m 4 independently may be 0 to 99 mole percent, and the sum of m 1 , m 2 , m 3 and m 4 is equal to or less than x mole percent of formula (I), wherein, the first polymer product is in a form of microparticles, and the particle size of the first polymer product is in the range of from 30 nanometer to 2000 nanometer, and the second polymer product is vinylamine-vinylformamide-styrene terpolymer, and wherein, said vinyl amine-vinylformamide-styrene terpolymer additive is in a form of microparticles in aqueous dispersion, and the viscosity measured at ambient temperature (about 20° C. to about 25° C.) of active solids in the range of from 13.0% to 18.0% of vinylamine-vinylformamide-styrene terpolymer is in the range of from 100 to 500 cP.
m 1 and m 2 independently is a positive mole percent, and m 3 and m 4 independently may be 0 to 99 mole percent, and the sum of m 1 , m 2 , m 3 and m 4 is equal to or less than x mole percent of formula (I),
wherein, the first polymer product is in a form of microparticles, and the particle size of the first polymer product is in the range of from 30 nanometer to 2000 nanometer, and the second polymer product is vinylamine-vinylformamide-styrene terpolymer,
and wherein, said vinyl amine-vinylformamide-styrene terpolymer additive is in a form of microparticles in aqueous dispersion, and the viscosity measured at ambient temperature (about 20° C. to about 25° C.) of active solids in the range of from 13.0% to 18.0% of vinylamine-vinylformamide-styrene terpolymer is in the range of from 100 to 500 cP.
The vinylamine-vinylformamide-styrene terpolymer additive of claim 16 , wherein the particle size of the first polymer product is in the range of from 50 nm to 1000 nanometer.
The vinylamine-vinylformamide-styrene terpolymer additive of claim 16 , wherein the particle size of the first polymer product is in the range of from 70 nanometer to 200 nanometer.
The vinylamine-vinylformamide-styrene terpolymer additive of claim 16 , wherein about 10% to 99% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d).
The vinylamine-vinylformamide-styrene terpolymer additive of claim 16 , wherein about 20% to 80% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d).
The vinylamine-vinylformamide-styrene terpolymer additive of claim 16 , wherein about 30% to 70% of formamide groups of the first polymer product are subsequently hydrolyzed in step c) to introduce cationic functionality of the second polymer product of step d).
The vinylamine-vinylformamide-styrene terpolymer additive of claim 16 , wherein the vinylamine-vinylformamide-styrene terpolymer additive is added to the wet end of the paper making system to improve paper making process and paper wet and dry strength.
The vinylamine-vinylformamide-styrene terpolymer additive of claim 16 , wherein the vinylamine-vinylformamide-styrene terpolymer additive is applied on already formed paper to improve paper finish properties.
A paper product comprising the second polymer product of claim 1 .
A paper product comprising the vinylamine-vinylformamide-styrene terpolymer additive of claim 16 .
Ref US20240263397A1: Claims:
A cationic polyacrylamide (cPAM), comprising the radical polymerization reaction product of: an acrylamide (AM) monomer; a cationic monomer comprising a quaternary ammonium alkylation product of an aminoalkylacrylamide or aminoalkylacrylate precursor; and optionally, one or more additional ethylenically unsaturated monomer.
an acrylamide (AM) monomer;
a cationic monomer comprising a quaternary ammonium alkylation product of an aminoalkylacrylamide or aminoalkylacrylate precursor; and
optionally, one or more additional ethylenically unsaturated monomer.
The cationic polyacrylamide (cPAM) of claim 1 , wherein the aminoalkylacrylamide or aminoalkylacrylate precursor is an N,N-dialkylaminoalkylacrylamide or N,N-dialkylaminoalkylacrylate, and wherein the cationic monomer is further defined as a quaternary ammonium alkylation product of the N,N-dialkylaminoalkylacrylamide or N,N-dialkylaminoalkylacrylate and an alkylation agent.
The cationic polyacrylamide (cPAM) of claim 2 , wherein the alkylation agent is further defined as an electrophilic alkylation agent having the formula XâRâY, where X is a leaving group, R is a substituted or unsubstituted hydrocarbon linking group, and Y is a functional group selected from amines, esters, anhydrides, carboxylic acids, hydroxyl, sulfates, amides, sulfamides, imides, and aldehydes.
The cationic polyacrylamide (cPAM) of claim 3 , wherein X is a halogen, R is a divalent hydrocarbyl linking group having from 1 to 6 carbon atoms, and Y is selected from amides, amines, and hydroxyl.
The cationic polyacrylamide (cPAM) of claim 2 , wherein the cationic monomer has the structural formula (I):
wherein R is a substituted or unsubstituted hydrocarbon group, X is a counter anion, and Y is a functional group selected from amines, esters, anhydrides, carboxylic acids, hydroxyl, sulfates, amides, sulfamides, imides, and aldehydes.
The cationic polyacrylamide (cPAM) of claim 2 , wherein: (i) the alkylation agent is 2-chloroacetamide; (ii) the cationic monomer comprises N,N-dimethyl-N-2-acetamido-N-propylacryamide ammonium chloride (DMCA); or (iii) both (i) and (ii).
The cationic polyacrylamide (cPAM) of claim 1 , wherein: (i) the AM monomer comprises acrylamide; (ii) the one or more additional ethylenically unsaturated monomer, when present, comprises a monomer selected from styrenes, alkyl acrylates, and vinyl acetates; (iii) the AM monomer, the cationic monomer, and optionally the one or more additional ethylenically unsaturated monomer are polymerized in the presence of a chain transfer agent; or (iv) any combination of (i)-(iii).
(i) the AM monomer comprises acrylamide;
(ii) the one or more additional ethylenically unsaturated monomer, when present, comprises a monomer selected from styrenes, alkyl acrylates, and vinyl acetates;
(iii) the AM monomer, the cationic monomer, and optionally the one or more additional ethylenically unsaturated monomer are polymerized in the presence of a chain transfer agent;
or (iv) any combination of (i)-(iii).
The cationic polyacrylamide (cPAM) of claim 1 , wherein the one or more additional ethylenically unsaturated monomer is present in the radical polymerization reaction, and wherein the one or more additional ethylenically unsaturated monomer comprises at least one: (i) cationic comonomer; (ii) multi-functional crosslinking agent; or (iii) both (i) and (ii).
The glyoxalated polyacrylamide (gPAM) resin of claim 8 , wherein one or more additional ethylenically unsaturated monomer comprises the cationic comonomer, and wherein the cationic comonomer comprises dimethylaminopropylacrylamide (DIMAPA), diallyldimethylammonium chloride (DADMAC), (3-acrylamidopropyl)trimethylammonium chloride (APTAC), (3-methacrylamidopropyl)trimethyl ammonium chloride, (2-acrylamidoethyl)trimethylammonium chloride, (2-methacrylamidoethyl)trimethylammonium chloride, N-methyl-2-vinylpyridinium N-methyl-4-vinylpyridinium, p-vinylphenyltrimethylammonium chloride, p-vinylbenzyltrimethylammonium chloride, (2-acryloyloxyethyl)trimethylammonium chloride, (2-methacryloyloxyethyl)trimethylammonium chloride, (3-acryloyloxypropyl)trimethyl ammonium chloride, (3-methacryloyloxypropyl)trimethylammonium chloride, or a combination thereof.
The glyoxalated polyacrylamide (gPAM) resin of claim 8 , wherein the one or more additional ethylenically unsaturated monomer comprises the multi-functional crosslinking agent, and wherein the multi-functional crosslinking agent comprises N,N-dimethylacrylamide (DMA), methylene bis-acrylamide (MBA), a diallylamine, a triallylamine, a tetraallylamine, or a combination thereof.
The cationic polyacrylamide (cPAM) of claim 1 , wherein the cPAM is substantially free from: (i) non-nucleophilic cationic repeat units; (ii) repeat units derived from diallyldimethylammonium chloride (DADMAC) and/or (3-acrylamidopropyl)trimethylammonium chloride (APTAC); or (iii) both (i) and (ii).
The cationic polyacrylamide (cPAM) of claim 2 , wherein the cPAM further comprises a Michael adduct formed from a 1,4-conjugate addition reaction between the 
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