MXPA00006535A - Process to reduce the aox level of wet-strength resins by treatment with base - Google Patents

Abstract

Process for reducing the AOX content of wet-strength resins, such as polyaminopolyamide-epi or polyalkylene polyamine-epi resins, by treatment with base, e.g. sodium hydroxide, while maintaining the wet-strength effectiveness of the resin.

Description

PROCEDURE TO REDUCE THE AOX LEVEL OF RESINS OF RESISTANCE IN THE WET STATE THROUGH BASE TREATMENT BACKGROUND OF THE INVENTION FIELD OF THE INVENTION The present invention relates to the process for reducing the level of adsorbable organic halogen (AOX) in wet strength resins maintaining or improving its wet strength effectiveness and more particularly the present invention relates to the treatment of said resins with base. DESCRIPTION OF THE PREVIOUS TECHNIQUE Commercial polyamino-polyamide-epichlorohydrin resins typically contain from 1 to 10% (on a dry basis) of the byproducts of epichlorohydrin (epi), 1,3-dichloropropanol (1,3-DCP), 2, 3- dichloropropanol (2,3-DCP) and 3-chloropropanediol (3-CDP). The production of wet strength resins with reduced levels of epi byproducts has been the subject of much research. Environmental pressures to produce wet strength resins with lower levels of adsorbable organic halogen (AOX) species have been increased. "AOX" refers to the adsorbable organic halogen content of the wet strength resin that can be determined by means of carbon adsorption. Accordingly, AOX includes epichlorohydrin (epi) as well as byproducts of epi (1,3-dichloropropanol, 2,3-dichloropropanol and 3-chloropropanediol) as well as organic halogen bound to the polymer structure. Polyamnolopia ida-epi resins, containing acetidinium have been treated with a basic ion exchange column to provide a resin with low AOX content and low total chloride content (WO / 92/22601, assigned to Akzo NV). After this treatment, the resin was acidified. A disadvantage of this procedure is that the ion exchange column has a limited capacity and requires to be regenerated once the basic character is consumed. A further disadvantage is that the resin has a reduced effectiveness when treated with the basic ion exchange column. Other technologies remove the epi byproducts but do not remove polymer bound AOX (ie, polymeric aminoclorohydrin). The polyaminopolyamide-epi resins have been treated with microorganisms to reduce the by-products of epi to less than 10 ppm (EP 510987, assigned to Hercules Incorporated). This treatment, however, does not remove the organic halogen bound to the polymer structure. Another method for removing the byproducts of epi employs a column of carbon adsorbent (WO 93/21384, assigned to E.l. duPont de Nemours). Such columns have a limited capacity and require to be regenerated once the adsorbent no longer efficiently removes the epi byproducts.

SUMMARY OF THE INVENTION According to the present invention there is provided a process for reducing the AOX content of an initial water soluble wet strength resin comprising acetydinium ions as well as tertiary aminohalohydrin, which comprises treating said resin in a solution aqueous with base to form a treated resin, wherein at least about 20% of the tertiary aminohalohydrin present in the initial resin is converted to epoxide and the level of acetidinium ion remains substantially unchanged, and the effectiveness of the resin treated to provide the Wet strength is at least approximately equal to the effectiveness of said strength resin in the initial wet state. A water soluble wet strength resin prepared by the process of the present invention is further provided. The process for preparing paper using the wet strength resin prepared by the present invention and the paper made in this way is further provided. DETAILED DESCRIPTION OF THE INVENTION It has been discovered in a surprising manner that the OX content of wet strength resin containing acetydinium and aminoclorohydrin can be greatly reduced while retaining or improving its wet strength characteristics. The initial water-soluble wet strength resins of the present invention may be polyamino-polyamide-epi resins or polyalkylene-polyamine-epi resins and mixtures thereof. The conversion of tertiary aminochlorohydrin (ACH) of the wet strength resins of the present invention into tertiary epoxide by treatment with base can be illustrated by the following formula: JB. " The polyaminopolyamide-epichlorohydrin resins comprise the water-soluble polymer reaction product of epichlorohydrin and polyamide derived from polyalkylene polyamine and saturated aliphatic dibasic carboxylic acid containing from about 3 to about 10 carbon atoms. It has been found that resins of this type provide a wet strength to the paper whether processed under acidic, alkaline or neutral conditions. In addition, such resins are substantive for cellulosic fibers so that they can be economically applied there while the fibers are in dilute aqueous suspensions of the consistency employed in paper mills. In the preparation of the cationic resins contemplated for use herein, the dibasic carboxylic acid reacts first with the polyalkylene polyamine, under conditions such that a water-soluble polyamide is produced which contains the recurring NH groups (CnH2nNH) x CORCO where n and x are each 2 or more and R is the divalent hydrocarbon radical of the dibasic carboxylic acid. This water-soluble polyamide then reacts with epi to form the water-soluble cationic thermosetting resins. The dicarboxylic acids contemplated for use in the preparation of the resins of the invention are saturated aliphatic dibasic carboxylic acids containing from 3 to 10 carbon atoms such as, for example, succinic, glutaric, adipic, azelaic acid and the like. Saturated dibasic acids having from 4 to 8 carbon atoms in the molecule, such as for example adipic and glutaric acids are preferred. Mixtures of two or more of the saturated dibasic carboxylic acids can also be used. Various polyalkylene polyamines including polyethylene polyamines, polypropylene polyamines, polybutylene polyamines, polypentylene polyamines, polyhexylene polyamines, etc., and mixtures thereof can be used, polyethylene polyamines represent an economically preferred class. More specifically, the polyalkylene polyamines contemplated for use can be represented as polyamines wherein the nitrogen atoms are joined together by groups of the formula -Cn H2n- where n is a small integer greater than unity and the number of such groups in The molecule is located within a range of two to approximately eight. Nitrogen atoms can be attached to adjacent carbon atoms in the -Cn H2n group-or to carbon atoms that are remote, but not to the same carbon atom. The invention contemplates not only the use of such polyamines as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and dipropylenetriamine, which can be obtained in reasonably pure form, but also mixtures and various raw polyamine materials. For example, the mixture of polyethylenepolyamine obtained by the reaction of ammonia and ethylene dichloride, refined only to the extent of the removal of chlorides, water, excess ammonia, and ethylenediamine, is a satisfactory initial material. The term "polyalkylene polyamine" used in the claims, therefore, refers to any of the polyalkylene polyamines mentioned above or to a mixture of such polyalkylene polyamines and derivatives thereof and includes any of said aforementioned polyalkylene polyamines or a mixture of such polyalkylene polyamines and Their derivatives. In some cases it is desirable to increase the spacing of the secondary amino groups in the polyamide molecule in order to change the reactivity of the polyamide-epichlorohydrin complex. This can be achieved by substituting a diamine such as for example ethylene diamine, propylene diamine, hexamethylene diamine and the like for a portion of the polyalkylene polyamine. For this purpose, up to about 80% of the polyalkylene polyamine can be replaced by a molecular equivalent amount of diamine. Usually, a replacement of approximately 50% or less will serve this purpose. When converting polyamide, formed as described above, a cationic thermosetting resin, reacts with epichlorohydrin at a temperature of about 25 ° C to about 100 ° C and preferably at a temperature between about 35 ° C and about 70 ° C until the The viscosity of a solution with 20% solids at a temperature of 25 ° C has reached approximately C or more on the Gardner Holdt scale. This reaction is preferably carried out in an aqueous solution to moderate the reaction. Even when it is not necessary, the pH adjustment can be carried out to increase or decrease the crosslinking rate. When the desired viscosity is reached, sufficient water is then added to adjust the solids content of the resin solution to the desired amount, i.e. about 15% more or less. The product cooled to a temperature of about 25 ° C and then stabilized by a sufficient amount of acid to reduce the pH to at least about 6 and preferably about 5. Any suitable acid such as for example hydrochloric, sulfuric, nitric, formic acid , phosphoric and acetic can be used to stabilize the product. However, hydrochloric acid and sulfuric acid are preferred. In the polyamide-epichlorohydrin reaction, it is preferred to employ a sufficient amount of epichlorohydrin to convert most of the secondary amine groups to tertiary amine groups. However, more or less can be added to moderate or increase reaction rates. In general, satisfactory results can be obtained by employing from about 0.5 mol to about 1.8 mol of epichlorohydrin for each secondary amine group of the polyamide. It is preferred to employ from about 0.6 mol to about 1.5 mol for each secondary amine group of the polyamide. Epichlorohydrin is the preferred epihalohydrin for use in the present invention. The present invention relates to epichlorohydrin specifically in certain cases, however, the person skilled in the art will recognize that these teachings apply to epihalohydrin in general. Water-soluble cationic resins, derived from the reaction of epihalohydrins, such as for example epichlorohydrin and polyalkylene polyamines, for example, ethylenediamine (EDA), bis-hexamethylenetriamine (BHMT) and hexamethylenediamine (HMDA) have been known for a long time. These polyalkylene polyamine-epihalohydrin resins have been described in Patents such as in U.S. Patent No. 3,655,506 to J. M. Baggett, et al., And in others such as, for example, in U.S. Patent No. 3,248,353 and in the U.S. Patent No. 2,595,935 to Daniel et al., From which its generic description is derived as "resins of Daniel". The polyalkylene polyamine used in the present invention is selected from the group consisting of polyalkylene polyamines of the formula: H 2 N- [CHZ- (CH 2) n-NR-] X H where: n = 1-7, x = 1-6 R = H or CH2Y, Z = H or CH3, and Y = CH2Z, H, NH2, or CH3, polyalkylenepolyamines of the formula: H2N- [CH2- (CHZ) m- (CH2) "-NR-] XH where: m = 1-6, n = 1-6, and m + n = 2-7, R = H or CH2Y, Z = H or CH3, YY = CH2Z, H, NH2, or CH3, and mixtures of the same. The polyalkylene polyamine-epihalohydrin resins comprise the product of the water-soluble polymer reaction of epihalohydrin and polyalkylenepolyamine. Making the Daniel resins, the polyalkylene polyamine is added to an aqueous mixture of the epihalohydrin in such a way that during the addition, the temperature of the mixture does not exceed 60 ° C. Lower temperatures cause additional improvements, even when too low a temperature can cause a dangerous latent reactivity in the system. Preferred temperatures are within the range of about 25 ° C to about 60 ° C. More preferably, it is within a range of about 30 ° C to about 45 ° C. The alkylation of the polyamine occurs rapidly proceeding to the formation of secondary and tertiary amines according to the relative amounts of epihalohydrin and polyamine. The levels of epihalohydrin and polyamine are such that between about 50 and 100% of the available amine nitrogen sites are alkylated in tertiary amines. Preferred levels are between about 50 and about 80% alkylation of the amine nitrogen sites. An excess of epihalohydrin beyond what is required to fully rent all the amine sites in the tertiary amine is less preferred since this results in an increased production of by-products of epihalohydrin. To minimize the byproducts of epi and AOX, preferably the time spent combining the polyamine and the epichlorohydrin should be minimized. This is required to minimize the period during which the combination of reagents, where there is a significant level of non-alkylated or partially alkylated polyamine in the presence of non-combined epichlorohydrin. This condition results in an alkaline system in which the conversion into byproducts of epihalodrine is accelerated. Through experience it has been found that the time for the addition of at least about 90% by weight of the polyamine, while retaining the reaction temperature within the specified range, should not exceed 150 minutes if the levels of 1,3- DCP should stay below the maximum levels desired. A more preferred addition time is 120 minutes or less for the addition of at least about 90% of the amine with especially preferred 100 minutes or less in addition time. Once approximately 90% of the polyamine is added, then the time of addition of the remainder becomes less important. This condition is specifically related to the termination of the alkylation reaction between the polyamine and the epihalohydrin, at that point practically all the epihalohydrin has been consumed in the alkylation of the polyamine. After a complete addition of the polyamine, the temperature rise of the mixture is allowed and / or the mixture is heated to effect crosslinking and acetidinium formation. The rate of crosslinking depends on the concentration, temperature, agitation and addition conditions of the polyamine all of which can be easily determined by a person skilled in the art. The rate of crosslinking can be accelerated by the addition of small amounts of the polyamine or other polyamines of the present invention or by the addition of various alkaline substances at or near the crosslinking temperature. The resin is stabilized against additional crosslinking to form gel by addition of acid, dilution in water, or through a combination of both. Acidification of a pH of 5.0 or less is generally adequate. Preferred polyamines are bis-hexamethylenetriamine, hexamethylenediamine, and mixtures thereof. A wide range of levels of aminoclorohydrin (ACH) and acetydinium (AZE) is possible with polyaminopolyamide-epi and polyamine-epi resins and is suitable for use in the invention. The relationship between ACH: AZE is at least about 2:98, preferably at least about 5:95 and especially about at least 10:90. The ACH.-AZE ratio can be up to about 98: 2, preferably up to about 95: 5 and more preferably up to about 90:10. The initial water-soluble wet strength resins of the present invention always contain tertiary ACH. Optionally, they can also contain secondary ACH and / or quaternary ammonium chlorohydrin as well. The following structures illustrate functionalities mentioned in the present application. The crosslinking functionalities of amine, glycol, epoxide and ACH are illustrated in terms of their tertiary species. acetidinio aminoclorohidrina epoxide tertiary tertiary tertiary glycol crosslinking of ammonium chloroamylamine tertiary hydroquinone quaternary hydrine (R = alkyl) Through the process of the present invention, generally at least about 20% of the aminoclorohydrin present in the initial resin has been converted to epoxide. Preferably, at least about 50% and more preferably at least about 90% of the aminoclorohydrin present in the initial resin has been converted to epoxide. Through the present invention, up to about 100% of the aminoclorohydrin present in the initial resin can be converted to epoxide. It will be understood that the term "aminohalohydrin" as used in the present application may refer to a secondary aminohalohydrin, tertiary aminohalohydrin and quaternary ammoniumhalohydrin unless otherwise specified. It will also be understood that the term "epoxide" and "aminoepoxide" are used interchangeably in the present application and refer to secondary aminoepoxides, tertiary aminoepoxide as well as quaternary aminoepoxide unless otherwise specified. Both organic bases and inorganic bases can be used herein in the present invention. A base is defined as any proton acceptor (see Advanced Organic Chemistry, third edition, Jerry March, John Wiley &Sons: New York, 1985, pages 218-236, which is incorporated herein by reference) . Typical bases include alkali metal hydroxides, alkali metal carbonates and alkali metal bicarbonates, ferrous alkali metal hydroxides, trialkylamines, tetraalkylammonium hydroxides, ammonia, organic amines, alkali metal sulphides, ferrous alkali sulphides, alkali metal alkoxides, and alkoxides of alkaline earths. Preferably, the base is alkali metal hydroxide (lithium hydroxide, sodium hydroxide and potassium hydroxide) or alkali metal carbonates (sodium carbonate and potassium carbonate). More preferably, the ase is sodium hydroxide or potassium hydroxide. The amount of base varies widely from resin to resin and depends on the type of resin, the amount and type of polymeric aminoclorohydrin, the amount of the byproducts epi (1,3-dichloropropanol, 2,3-dichloropropanol and 3-chloropropanediol), amount of stabilizing acid in the resin and the conditions used to activate the resin. The amount of base can be at least about 0.5 mmol, preferably at least about 1.5 mmol per gram of dry resin. The amount of base can be up to about 10 mmol, preferably up to about 8 mmol per gram of dry resin. The pH may be within a range of from 13.0 to 8.0, preferably from 12.5 to 9.0, more preferably from 12.0 to 10.0, and especially from 11.5 to 10.5. The treatment temperature may be at least about 0 ° C, preferably at least about 20 ° C, preferably at least about 40 ° C, more preferably at least about 45 ° C and especially at least about 50 ° C. The treatment temperature can be up to about 100 ° C, preferably up to about 80 ° C, and especially up to about 60 ° C. The treatment time may be at least about 1 minute, preferably at least about 3 minutes, and especially at least about 5 minutes. The treatment time can be up to about 24 hours, preferably up to about 4 hours and especially up to about 1 hour. The resin may employ about 1 minute to about 24 hours after the treatment with the base, preferably from 1 minute to about 6 hours after the base treatment, and especially from about 1 minute to about 1 hour after the treatment with the base. . The resin solids for base treatment can be at least about 1%, preferably at least about 2%, preferably at least about 6%, preferably greater than at least about 8% and especially at least about 10% based on the weight of the composition. In the context of the present invention the term "resin solids" refers to the active polyamino-polyamide-epi and / or the active polyalkylene polyamine-epi of the composition. Resin solids for base treatment can constitute up to about 40%, preferably up to about 25%, and especially preferably up to about 15%. After treatment with the base, the resin can be diluted, typically with water. In the case of most resins with high molecular weights, the preferred treatment conditions convert more than 90% of the amino-chlorohydrin functionality into epoxide functionality, with a reduction of less than 10% in the amount of acetydinium functionality. In the case of some resins, especially resins with low molecular weight, it may be preferred to allow a part of the epoxide functionality or all of the epoxide functionality to be consumed by crosslinking reactions. Less preferred treatment conditions are conditions wherein more than 5 mol% of the acetydinium and / or epoxide is converted into glycol functionality. This conversion reduces the total amount of relative functionality that generally reduces the effectiveness of the treated resin. To have a highly effective resin, the molar percentage of hydrolysis of the total reactive functionality (acetydinium, epoxide and / or aminoclorohydrin) relative to the glycol is from about 0% to about 20%, preferably up to about 10%, preferably even greater up to about 5% and especially up to about 2%. To obtain a highly effective resin, the level of acetydinium ion in the treated resin will be substantially unchanged as compared to the level to the treatment. In the context of the present invention, this means that the treated resin will have at least about 80 mole% of the acetydinium functionality in the untreated resin, preferably about 90 mole%, preferably even more about 95 mole% and especially about 100 mole%. % molar. The effectiveness of the wet strength of the treated resin of the present invention will not be substantially diminished by the base treatment. In the context of the present invention this means that the treated resin will have at least about 80% of the effectiveness of the untreated resin, preferably at least about 95% and especially preferably about 100%. With resins containing more than about 5 mol% aminohalohydrin, the present invention can offer a resin treated with greater effectiveness than the untreated resin. The improvement in effectiveness may be from about 2 to 50%, preferably the improvement is greater than about 5% and especially greater than about 10%. The treatment conditions for each resin can be optimized to a given set of conditions, however, one skilled in the art will recognize that other conditions also offer good results. For example, if a shorter reaction time is desired, then a higher temperature can be employed with good results. The treatment conditions can reduce the AOX content to less than 50%, preferably less than 25%, preferably less than 10%, preferably less than 5%, preferably less than 1%, and especially less than 0.5% of the AOX content in the untreated resin at a base of equal solids level. Although the approach of the present invention is the reduction of AOX, it can also be used to reduce the levels of epichlorohydrin by-products (epi), 1,3-dichloropropanol (1,3-DCP), 2,3-dichloropropanol (2,3-DCP) and 3-chloropropandiol (3-CPD), in polyaminopolyamide-epi resins or in polyalkylenepolyamine-epi resins. In addition, the present invention can be used to convert 1,3-DCP and 2,3-DCP into epi. This epi could be removed from the resin through further treatment, for example, by distillation or extraction. Gas chromatography (GC) was used to determine epi and epi byproducts in the treated and untreated resins using the following method. The resin sample was absorbed in an Extrelut column (available from EM Science, Extrelut QE, Part No. 901003-1) and extracted by passage of ethyl acetate through the column. A portion of the ethyl acetate solution was subjected to chromatography on a large orifice capillary column. If a flame ionization detector was used, the components were quantified using n-octanol as the internal standard. If an electrolytic conductivity detector (ELCD) was used or if the XSD detector was used, an external standard method using peak matching quantization was employed. The data system was either a HP Millennium ChemStation 2010. The FID detector was purchased from Hewlett-Packard (HP). The ELCD detector, model 5220, was purchased from Oí Analytical. The XSD detector was acquired in 01 Analytical, Model 5360 XSD. The GC instrument used was an HP 5890 Series II model. The column was DB wax 30 m x 53 mm with a film thickness of 1.5 microns. For FID and ELCD, the vehicle gas was helium with a flow rate of 10 mL / min. The oven program was 35 ° C for 7 minutes, followed by a progressive increase at 8 ° C / min up to 200 ° C and keeping at 200 ° C for 5 minutes. The FID used hydrogen at 30 mL / min and air at 400 mL / min at a temperature of 250 ° C. The ELCD employed n-propanol as the electrolyte with an electrolyte flow rate setting of 50% with a reactor temperature of 900 ° C. The XSD reactor was operated in an oxidizing mode at 1100 ° C with a high purity air flow rate of 25 mL / min. A wet strength resin Kymene® ULX is a polyamino-polyamide-epi resin available from Hercules Incorporated. The first sample used had resin solids of 12.7% and a charge density of 3.36 meq / g at a pH of 1.8, 1.73 meq / g at a pH of 8 1.51 meq / g at a pH of 10. The second sample of resistance resin in the wet state Kymene® ULX used resin solids of 12.7% and a charge density of 3.28 meq / g at a pH of 1.8, 1.72 meq / g at a pH of 8, and 1.56 meq / g at a pH of 10. The resin of Moisture resistance E7045 is a polyamino-polyamide-epi resin available from Hercules Incorporated. The sample used had a charge density of 3.34 meq / g at a pH of 1.8, 1.96 meq / g at a pH of 8 and 0.89 meq / g at a pH of 10 and total solids of 13.0%. Kymene® 557 LX wet strength resin is a polyamino-polyamide-epi resin available from Hercules Incorporated. It has a pH of 3.5, total solids of 12.5%, and a Brookfield viscosity of 47 cps. It has a charge density of 1.39 meq / g at a pH of 10. The wet strength resin Kymene® 736 is a polyalkylenepolyamine-epi resin available from Hercules Incorporated. It has a pH of 3.3, total solids of 37.8%, and a Brookfield viscosity of 250 cps. It has a charge density of 2.24 meq / g at a pH of 8. The Kymene® ULX2 wet strength resin is a polyamino-polyamide-epi resin available from Hercules Incorporated. The scope of the present invention in accordance with the claimed is not limited to the following examples that are offered for illustrative purposes only. All parts and percentages are by weight unless otherwise indicated. EXAMPLE 1, Ib and COMPARATIVE EXAMPLE 1 Treatment with wet strength basis Kymene® ULX A 48.15 g (wet basis) of Kymene® ULX resin, first sample, (12.7% resin solids) 6.25 g of deionized water were added . Magnetic stirring was initiated and the solution was heated to a temperature of 55 ° C with a water bath equipped with a Cole-Parmer Polystat® temperature controller. The pH was monitored with a Beckman 10 pH meter connected to an automatic temperature compensator and a Ross pH electrode, of safe flow. The pH meter was calibrated daily with buffer solutions of pH 7 and 10. To the Kymene® ULX solution, 6.72 g (6.11 mL) of 10% aqueous sodium hydroxide (w / w) was injected. (This provided a solution with 10% resin solids). The peak pH was 10.9 and the temperature dropped to 54 ° C for about one minute. The pH was 10.1 after 5 minutes at this time the resin was cooled rapidly to room temperature and analyzed by 13C NMR and to determine AOX (Table 1). A Mitsubishi Kasei Corporation instrument (model TOX-lOÓ) was used for the analysis of AOX, using the procedure described in the operation manual. The 13C NMR spectra are acquired using BRUKER AMX spectrometers equipped with a 10mm wideband probe. A 13C NMR operating at a frequency of 100 MHz (AMX400) or 125 MHz (AMX500) is sufficient for data collection. In any case, the spectra are acquired with continuous H disconnection. The electronic integration of the appropriate signals provides molar concentrations of the following alkylation components; ACH, EPX, GLY and AZE, where: ACH = polymeric aminoclorohydrins EPX = polymeric epoxides GLY = polymeric glycols AZE = acetidinium ions In order to calculate the concentrations of each of these species, the integral values must be placed in one (1) carbon base. For example, the spectral region between 20-42 ppm represents six (6) carbons of the diethylenetriamine-adipate structure, therefore the integral value is divided by six. This value is used as the common denominator of the polymer (PCD) for the calculation of the alkylation species. The chemical changes of these species are given below (using an acetonitrile field reference of 1.3 ppm). The corresponding integral value of each alkylation product is used in the numerator for calculations, see the following examples: the ACH signal at 68-69 ppm represents a carbon; integral of ACH + PCD = ACH of molar fraction - the GLY signal at 69-70 ppm represents a carbon; integral of GLY -r PCD = GLY of molar fraction - the signal of EPX at 51-52 ppm represents a carbon; integral EPX -r PCD = molar fraction EPX -the AZE signal at 73-74 ppm represents two carbons, therefore a division factor of two is required; integral of AZE / 2 -f PCD = AZE of molar fraction. The following spectral parameters are standard experimental conditions for 13C NMR analysis of resins Kymene treated based on the Bruker AMX400. Temperature: 25 ° C Resonance frequency: 100MHz No. of data points: 64K Residence time: 20 microseconds Acquisition time: 1.3 seconds Sweep width: 25000 Hz No. of scans: 1K Relaxation delay: 3 seconds Angle of pulse point: 70 degrees Pulse program: zgdc Processed spectral size: 64K Apodization function: exponential Line spreading: 3 Hz Paper sheets were prepared in a machine to form Noble and Wood leaves at a pH of 7.5 with a dry pulp 50:50 Kraft paper bleached with Rayonier: Kraft hardwood paper bleached with James River refined to 500 mL of freedom according to the Canadian standard. The sheets were generated which had a base weight of 40 pounds / 3000 square feet with a content of 0.5 to 1.0% treated resin (based on the solids of the untreated resin). The leaves were pressed in the wet state to a content of 33% solids and dried in a drum dryer at a temperature of 230 ° C for 55 seconds. Natural aging refers to conditioned paper in accordance with TAPPI's T-402 method. All the paper tested had more than two weeks of natural aging at a relative humidity of 50% +/- 2% and at a temperature of 23 ° C +/- 1 ° C. Dry tensile strength was determined using TAPPI's T-494 method. The tensile strength in the wet state was determined using the TAPPI T-456 method with a soak time of two hours. As can be seen in Table 1, on an equal solids basis, the AOX content of the Kymene® ULX resin was reduced from 2600 ppm (comparative example 1) to 35 ppm (example 1) through the base treatment process of this invention. Example Ib used the same conditions as Example 1 except that the reaction time was 30 minutes. Kymene® ULX resin treated with base presented 99-109% of the effectiveness of untreated Kymene® ULX resin for cured and natural aging leaves at addition levels of 0.5% and 1.0% (see tables 7 and 8). Using the conditions of Example 1, the polymeric chlorohydrin functionality was cleanly converted to epoxide functionality without a significant reduction in the amount of acetydinium functionality, as determined by 13C NMR. The increase in total reactive functionality (epoxide and acetydinium) resulted in the high effectiveness of this resin treated with base. In addition to the low level of AOX and high effectiveness, an additional advantage compared to the prior art is that no additional processing step is required, e.g. regeneration of a carbon column or ion exchange. EXAMPLES 2-9 Kymene® ULX was treated as in Example 1, except as shown in Table 1. The unreacted aminoclorohydrin (ACH) in examples 2 and 4 shows that the conditions did not provide an optimal reduction of AOX. One skilled in the art will understand that ACH is a contributing factor to AOX and that an AOX determination is not required when ACH is present. It is also understood that the epoxide functionality is more reactive than the ACH functionality and that the additional epoxide functionality in a resin will increase the resistance effectiveness in the wet state of the resin in many applications. Example 3 shows that the longer reaction time does not significantly reduce the level of ACH but the epoxide was consumed. In a base quantity like in Example 1, examples 5 and 6 show that a lower temperature causes an incomplete conversion of ACH even after a reaction time of four hours. Examples 8 and 9 show that sodium carbonate and sodium hydroxide can be used to reduce AOX, but are less effective, all other conditions being equal. EXAMPLES 10-12 AND COMPARATIVE EXAMPLE 2 A different lot (second sample) of Kymene® ULX wet strength resin (comparative example 2) was treated as in example 1, except as shown in table 2. Example 10 shows that Example 1 could be reproduced with a different batch of Kymene® ULX resin. With reference to Example 10, Example 12 shows that a similar result can be obtained by using a lower temperature (40 ° C) and a longer reaction time (30 minutes). Compared to example 11, example 12 shows that a reaction time of 30 minutes at 40 ° C provided a reduction of AOX closer to the optimum level. As can be seen in Figure 9, on a solid base equal, the level of epichlorohydrin byproducts in the. Kymene® ULX resin was also reduced by the treatment process based on this invention. For example, the level of 3-chloropropanediol (3-CPD) was reduced from 57 ppm (comparative example 2) to 6 ppm (example 10). EXAMPLE 13 AND COMPARATIVE EXAMPLE 3 Treatment with Resistance Base of Resistance in Wet State E7045 The procedure and equipment used to treat E70 resin 5 (which is a polyamino polyamide-epi resin available from Hercules Incorporated, Comparative Example 3) were the same than in example 1, except for the following changes. To 47.15 g (wet base) of resin E7045 7.28 g of deionized water were added. The magnetic stirring was started and the solution was heated to a temperature of 55 ° C. To the solution was injected 6.72 g (6.11 mL) of 10% aqueous sodium hydroxide (w / w). The peak pH was 10.8. The pH was 10.1 after 5 minutes at this time the resin was cooled rapidly to room temperature and analyzed by 13C NMR and for AOX (see table 3). Compared with comparative example 3, the treatment procedure based on example 13 reduced the level of AOX while maintaining the level of acetidinium. { AZE). As can be seen in table 9, on an equal solids basis, the level of epichlorohydrin by-products in resin E7045 was also reduced by the treatment method based on this invention. For example, the level of 3-chloropropanediol (3-CPD) was reduced from 188 ppm (Comparative Example 3) to 10 ppm (Example 13). EXAMPLES 14-20 AND COMPARATIVE EXAMPLE 4 Kymene® 557LX Moisture Resistance Resin-based Treatment (Example 17) The procedure and equipment used to treat the Kymene® 557LX polyamino-polyamide-epi resin (comparative example 4) were the same as in Example 1, except for the following changes. A 48. 92 g (wet basis) of Kymene® 557LX resin were added 6.36 g of deionized water. The magnetic stirring was started and the solution was heated to a temperature of 55 ° C. To this solution was injected 5.87 g (5.87 L) of 10% aqueous sodium hydroxide (w / w). The peak pH was 10. 9. The pH was 10.2 after 5 minutes at this time the resin was cooled rapidly to room temperature and analyzed by 13C NMR and for AOX (see table 4). The procedure of Examples 14, 15, 16, 18, 19 and 20 was similar to Example 17 except as indicated in Table 4. In Example 16, the Kymene® 557LX resin based treatment procedure resulted in a resin with slightly decreased effectiveness, 89-101% Kymene® 557LX resin, with 188 ppm (corrected at 12.5% solids). ) of AOX (see tables 7 and 8). The results of AOX and NMR suggest that this resin was over-treated, in such a way that using less hydroxide of sodium would have obtained an improved effectiveness. Example 17 showed that a lower amount of base (2.4 mole NaOH / g dry resin versus 2.8) could have been used with a comparable reduction of AOX and with a decrease of only 4% in terms of AZE (see table 4). Example 18 shows that a further reduction in the amount of base (to 2.0 mmol NaOH / g dry resin) causes an incomplete conversion of ACH to epoxide with the resulting increase in AOX (see table 4). From these results, under the same reaction conditions, the optimum amount of base is greater than about 2.0 and less than about 2.8 mmol NaOH / g dry resin. Examples 19 and 20 show that a lower temperature and a longer reaction time is a less effective procedure for reducing AOX compared to example 18. As can be seen in table 9, on a solid basis equal, the total level of epichlorohydrin and epichlorohydrin by-products in the wet strength resin Kymene® 557LX was also reduced by the treatment method based on this invention. For example, the level of 3-chloropropanediol (3-CPD) was reduced from 190 ppm (comparative example 4) to 163 ppm (example 18) and the level of 1,3-dichloropropanol (1,3-DCP) was reduced from 800 ppm to 14 ppm. EXAMPLES 21-22 AND COMPARATIVE EXAMPLE 5 Synthesis of poly (adipic-co-diethylenetriamine acid) A resin pot was equipped with a heavy duty mechanical stirrer, a Dean-Stark water condenser / trap, a temperature controller and a sprayer of nitrogen. 297.13 g (2.88 mol) of diethylenetriamine (Aldrich, 99%) were charged to the bottle and then 438.42 g (3.00 mol) of adipic acid (Aldrich, 99%) were slowly added in such a way that the exotherm was kept below 120. ° C. The yellow pasty mixture was slowly heated to a temperature of 170-173 ° C for 3 hours. The water started to collect at approximately 150 ° C. After an additional two hours at a temperature of 170173 ° C, the viscous polymer was allowed to cool to a temperature of about 145 ° C and 465 g of deionized water was carefully added. The solution was allowed to cool to room temperature and was bottled. [Total solids: 60.37%, intrinsic viscosity (IV) = 0.160 in 1 M ammonium chloride at a temperature of 25 ° C]. Synthesis of polyamino-polyamide-epi resin containing approximately 13 mol% of acetidinium (comparative example 5) _ A 500 ml flask was equipped with a condenser, a pH meter, a temperature controller, and a heating jacket, a funnel additional and a mechanical agitator. To the bottle were added 105.99 g (63.98 g of solids, 0.30 mol, IV = 0.160) of poly (adipic acid-co-diethylenetriamine) 60.37% aqueous synthesized above and 53. 97 g of deionized water (to provide 40% solids) ). The solution was heated to a temperature of 30 ° C under controlled Maria in terms of temperature and then 24.98 g (0.27 mol) of epichlorohydrin (Aldrich, 99%) was added in 3 minutes. The temperature was raised to 35 ° C. The pH dropped from 9.4 to 7.6 during the course of the reaction. After 5 hours at 35 ° C, 526. 8 g of deionized water was added and the pH was adjusted to 2.9 with 11.42 g of concentrated sulfuric acid. Analysis: total solids, 13.56%; AOX, 0. 96%. Polyamino-polyamide-epi resin based treatment of comparative example 5 (Example 21) The procedure and equipment used to activate comparative example 5 were identical as in example 1 except as shown in table 5 and below . To 45.10 g (wet basis) of Comparative Example 5 3.82 g of deionized water was added. The magnetic stirring was started and the solution was heated to a temperature of 55 ° C. To this solution, 12.22 g of 10% aqueous sodium hydroxide (w / w) were injected. The peak pH was 11. 6. The pH was 10.9 after 5 minutes at this time the resin was cooled rapidly to room temperature and analyzed by 13C NMR and for AOX (see table 5). Example 22 was prepared as in example 21 except as indicated in table 5. Example 21 shows that the ACH functionality was cleanly converted to epoxide functionality. The level of AOX was greatly reduced from 9600 ppm in Comparative Example 5 (ie, untreated resin) to 244 ppm in Example 21. This resin dramatically increased its effectiveness when treated on the basis of 121-134% of the resin not treated in a sheet evaluation (see tables 7 and 8). Example 22 shows conditions that result in an incomplete conversion of the ACH functionality and a less than optimal reduction of AOH. As can be seen in Table 9, on an equal solids base, the total level of epichlorohydrin and epichlorohydrin by-products in this resin was also reduced by the treatment method based on this invention. For example, the level of 3-chloropropanediol (3-CPD) was reduced from 528 ppm (Comparative Example 5) to 132 ppm (Example 22) and the level of 1,3-dichloropr-opanol (1,3-DCP) was reduced from 896 ppm to 23 ppm. EXAMPLES 23-28 and COMPARATIVE EXAMPLE 6 Kymene® 736 Wet Resistance Resin-Based Resin Treatment (Example 24) The process and equipment used to treat the Kymene® 736 polyamine-epi wet strength resin (Comparative Example 6) ) were identical to those employed in Example 1 except as indicated below. To 15.8 g (wet basis) of Kymene® resin were added 35.75 of deionized water. Magnetic stirring was started and the solution was heated to a temperature of 55 ° C. To this solution, 9.60 g (8.73 mL) of 10% (weight / weight) aqueous sodium hydroxide was injected. The peak pH was 10.3. The pH was 0.1 after 5 minutes at that time the resin was cooled rapidly to room temperature and analyzed by 13, NMR and for AOX (see table 6). Examples 23, 25, 26, 27 and 28 were the same as Example 24 except as indicated in Table 6. Example 24 shows that, with respect to Comparative Example 6, the level of AOX (the level of ACH is an indicator of the level of AOX) was reduced with only a slight reduction in the level of acetidinium. Example 23 shows that a lower amount of base (all other conditions being equal) resulted in an incomplete conversion of ACH, which, if measured, provides a higher level of AOX. Example 25 shows the level of AOX reduction that can be obtained with this procedure. Example 25 and example 26 show that the increase in the base level (all other conditions being equal) resulted in a reduction in the amount of acetidinium compared to Example 24. This reduction can be expected to reduce the effectiveness of the resin . Example 27 shows that the pH increase of the Kymene® 736 resin to 8.0 results only in a slight decrease in the level of ACH. The reaction at lower temperature (example 28) gives results according to 13C NMR comparable as in example 25, but the level of AOX is higher. As can be seen in table 9, on an equal solids basis, the total level of epichlorohydrin and epichlorohydrin by-products in the Kymene® 736 wet state resin was also reduced by the treatment method based on this invention. For example, the level of 3-chloropropanediol (3-CPD) was reduced from 175 ppm (comparative example 6) to 53 ppm (example 25) and the level of 1,3-dichloropropanol (1,3-DCP) was reduced from 1000 ppm to 8 ppm. EXAMPLE 29 and COMPARATIVE EXAMPLE 7 Kymene® ULX2 Wet Strength Resin-based Resin Treatment 62.50 g (wet basis) of Kymene® ULX2 resin (12.8% resin solids) were added 8.70 g of deionized water. Magnetic stirring was initiated and the solution was heated to 55 ° C with a water bath equipped with a Polystat® temperature controller from Cole-Parmer. The pH was monitored with a Beckman 10 pH meter connected to an automatic temperature compensator and Ross pH electrode, safe flow. The pH meter was calibrated daily with buffer solutions of pH 7 and 10. To the Kymene® ULX2 solution, 8.80 g (8.00 mL) of 10% aqueous sodium hydroxide (w / w) was injected. (This provided a solution with 10% resin solids). The peak pH was 10.4. The pH was 10.1 after 5 minutes at that time the resin was cooled rapidly to room temperature and analyzed by gas chromatography (GC) (see table 9). As can be seen in table 9, on an equal solids basis, the level of epichlorohydrin by-products in the Kymene® ULX2 resin was reduced by the treatment method based on this invention. For example, the level of 3-chloropropanediol (3-CPD) was reduced from 2.5 ppm (comparative example 7) to 0.5 ppm (example 29). Table 1 () Analysis of resistance resin in humid condition Kymena® ULX treated with base by 13C NMR and AOX Example Conditions mmol NaOH / AOX (ppm) of treatment g resin (based on (dry) equal level of solids) (1 ) Example of No treatment None 2600 comparison 1 example 1 55 ° C for 2.8, pH 35 5 peak minutes: 10.9 example 2 25 ° C for 2.3, pH 5 peak minutes: 9.9 example 3 25 ° C for 2.3, pH 4 hours 4 hours 9.6 example 4 55 ° C for 2.3, pH 743 5 peak minutes: 10.4 example 5 25 ° C for 2.8, pH 5 peak minutes: 11.7 example 6 25 ° C for 2.8, pH 4 hours 4 hours: 10.6 example 7 55 ° C during 3.3, pH 5 peak minutes: 11.1 example 8 55 ° C for 3.3 (Na2C03) 1226 5 minutes example 9 55 ° C for 0.79 (Ca (OH) 2) 2477 - minutes example% AZE (2)% ACH (3) %% of amine glycol tertiary epoxide example 37.2 7.0 2.8 0.0 17.0 comparison 1 example 1 36.2 0.0 4.8 8.4 20.9 example 2 39.0 5.5 3.9 4.2 17.7 example 3 36.2 5.2 4.8 0.0 21.4 example 4 36.4 3.8 3.9 4.4 21.3 example 5 36.9 0.9 4.5 7.7 23.4 example 6 34.5 0.7 3.5 7.1 23.7 example 7 35.8 0.0 6.3 6.5 24.1 example 8 example 9 (1) AOX = adsorbable organic allogen (2) AZE = acetydinium (3) ACH = aminoclorohid rina (4) All percentages of AEZ, ACH, glycol, epoxide, and tertiary amine are molar percentages based on the resin in this table and in all the other tables. Table 2 Resistance analysis in the wet state Kymene® ULX treated on the basis of 13C NMR and AOX Example: Conditions mmol NaOH / AOX (ppm) of treatment g resin (based on (dry) equal solids level) eg no treatment none 2500 comparison 2 example 10 55 ° C for 2.8, pH 11 5 peak minutes: 10.7 example 11 40 ° C for 2.8, pH 83 5 peak minutes: 10.7 example 12 0 ° C for 2.8, pH 12 30 peak minutes: 10.7 example% AZE% ACH% of% of amine glycol tertiary epoxide example of 43.1 6.3 2.5 0.0 13.9 comparison 2 example 10 41.9 0.0 2.8 5.8 16.7 example 11 example 12 40.4 0.0 3.2 5.5 15.9 Table 3 Analysis of resistance resin in state Moisture E7045 treated with base by 1J "33, C NMR and AOX Example Conditions mmol NaOH / AOX (ppm) of treatment g resin (based on dry) equal level of solids) comparison 3 example 13 55 ° C for 2.8, pH 78 5 minutes peak: 10.8 example% AZE% ACH% of% of amine glycol tertiary epoxide example of 35.4 0.8 1.3 0.0 8.8 comparison 3 example 13 35.7 0.0 2.5 0.0 10.1 Table 4 Analysis of resistance resin in wet condition Kymena® 557LX treated with base on 13C NMR and AOX Ex eg Conditions mmol NaOH / AOX (ppm) of treatment g resin (based on (dry) equal solids level) Example of No treatment None 3200 comparison 4 example 14 25 ° C for 1.6, pH 2500 10 minutes peak: 10.7 example 15 25 ° C for 1.6, pH 1750 4 hours peak: 8.8 example 16 55 ° C for 2.8, pH 188 5 minutes peak: 11.4 example 17 55 ° C for 2.4, pH 200 5 peak minutes: 10.9 example 18 55 ° C for 2.0, pH 663 5 peak minutes: 10.4 example 19 25 ° C for 2.0, pH 1663 5 peak minutes: 11.3 example 20 25 ° C for 2.0, pH 763 4 hours 4 hours: 9.4 example% AZE% ACH% of% of amine glycol tertiary epoxide example of 51.6 8.8 1.9 0.0 12.9 comparison 4 example 14 49.5 7.8 1.0 1.6 12.7 example 15 49.2 7.5 0.9 1.5 11.8 example 16 44.8 0.0 2.0 7.3 19.0 example 17 47.5 0.0 1.7 7.9 19.5 example 18 51.0 1.5 0.7 5.0 21.3 example 19 51.5 3.0 1.0 4.1 21.1 example 20 Table 5 Analysis of comparative example 5 treated based on 1A3C NMR and AOX Example Conditions mmol NaOH / AOX (ppm) of treatment g resin (based on (dry) equal solids level) Example of No treatment None 9600 comparison 5 example 21 55 ° C for 5.0, pH 244 5 peak minutes: 11.6 example 22 55 ° C for 4.3, pH 759 5 peak minutes: 11.2 example% AZE% ACH%%% amine tertiary epoxide glycol example of 13.1 54.8 ND 0.0 52.8 comparison 5 example 21 11.8 0.0 ND 53.4 59.2 example 22 12.8 5.1 0.7 39.1 53.7 Table 6 Analysis of wet strength resin Kymene® 736 treated with base 13C NMR and AOX Example Conditions mmol NaOH / AOX (ppm) of treatment g resin (with base (dry) in 10% solids) Example of No treatment None 4820 comparison 6 example 23 55 ° C for 2.8, pH 5 peak minutes: 9.8 example 24 55 ° C for 3.9, pH 5 peak minutes: 10.3 example 25 55 ° C for 4.3, pH 165 5 peak minutes: 10.8 example 26 55 ° C during 5.1, pH 5 peak minutes: 11.1 example 27 25 ° C during pH adjusted 5 minutes at 8.0 example 28 25 ° C for 4. .3, PH 770 5 peak minutes: 11.8 example% AZE% ACH Example% glycol epoxide glycol of 42 30 < 2 < 2 comparison 6 example 23 41 8-10 < 5 14 example 24 41 < 2 < 5 14 example 25 38 < 2 5-10 13 example 26 32 < 2 10-20 7 e emplo 27 42 28 < 2 1 example 28 37 < 2 5-10 13 Table 7 Evaluation of base treated resin sheet (naturally aged paper) Example of resin base weight thickness tension in Aggregate (lbs / 3000 (thousandths dry state111 Feet2) inch) (lbs / inch) White 0.0 40.7 4.88 17.49 Example 0.5 40.0 5.00 21.00 Comparison 1 Example 1.0 40.2 5.07 21.69 Comparison 1 Example 0.5 40.8 4.88 20.59 1 Example 1.0 38.9 4.95 21.29 1 Example 0.5 39.8 4.93 21.41 Ib Example 1.0 40.0 5.07 23.40 Ib Example 0.5 40.2 5.00 20.30 7 Example 1.0 39.9 4.97 21.55 7 Example 0.5 40.9 5.08 19.56 8 Example 1.0 41.0 5.15 22.34 8 Example 0.5 39.9 4.94 20.05 Compare-Tivo 4 Example 1.0 40.3 5.05 22.03 Comparison 4 Example 0.5 40.3 4.91 20.15 16 Example 1.0 40.3 4.89 22.43 16 Example 0.5 40.4 4.90 19.60 Comparison 5 Example 1.0 40.8 4.93 19.80 Comparison 5 Example 0.5 38.8 4.77 20.21 21 Example 1.0 40.2 4.92 23.08 21 Example Tension in resistance resistance in Wet state (1) in a humid state (lbs / inches) wet / dry%% (2) White 0.50 3 Example 3.95 19 comparative 1 Example 4.90 23 comparative 1 Example 1 3.89 19 99 Example 1 5.05 24 103 Example Ib 4.28 20 108 Example Ib 5.36 23 109 Example 7 3.81 19 96 Example 7 4.85 23 99 Example 8 3.79 19 96 Example 8 5.01 22 102 Example 4.32 22 Comparison 4 Example 5.16 23 Comparison 4 Example 16 4.31 21 100 Example 16 5.20 23 101 Example 3.18 16 Comparison-Tivo 5 Example 4.04 20 Comparison 5 Example 21 3.99 20 126 Example 21 5.40 23 134 Notes for table 7 and table 8: (1) The tensions in the wet state and in the dry state were linearly normalized by a weight of 40 pound / 3000 square foot base (2) The wet strength of the paper made with the treated resin expressed as% of the wet strength of the paper made with the untreated resin with the same percentage of resin added. Table 8 Evaluation of leaf with resin treated with base Example of resin weight of base thickness tension in Aggregate (lbs / 3000 (thousandths of dry state (1! Pies2) of inch) (lbs / inch) White 0.0 40.6 4.83 16.06 Example 0.5 40.2 4.96 20.80 Comparison 1 Example 1.0 39.4 5.02 21.12 Comparative 1 Example 0.5 40.1 5.03 20.55 1 Example 1.0 39.1 4.93 21.28 1 Example 0.5 40.2 5.06 21.89 Ib Example 1.0 40.2 5.04 23.88 Ib Example 0.5 40.6 4.97 20.89 Example 1.0 39.8 4.98 22.21 7 Example 0.5 40.4 4.93 21.19 8 Example 1.0 40.8 5.00 21.96 8 Example 0.5 39.6 4.93 21.92 Comparison 4 Example 1.0 40.2 4.93 21.59 Comparison 4 Example 0.5 40.7 4.92 21.13 16 Example 1.0 40.8 4.95 20.78 16 Example 0.5 41.0 4.87 20.00 Comparison 5 Example 1.0 40.8 4.99 20.59 Comparison 5 Example 0.5 39.4 4.82 20.51 21 Example 1.0 40.2 4.92 22.09 21 Example Tension in resistance resistance in Wet state (1 > Wet state) (lbs / inches) wet / dry%% (2) White 0.52 3 Example 4.17 20 Comparison 1 Example 5.43 25 Comparative 1 Example 4.50 22 108 1 Example 5.49 26 103 1 Example 4.52 21 108 Ib Example 5.66 24 106 Ib Example 4.23 20 101 7 Example 5.17 23 97 7 Example 4.36 21 104 8 Example 5.23 24 98 8 Example 5.05 23 Comparison 4 Example 5.68 26 Comparison 4 Example 4.51 21 89 16 Example 5.52 27 97 16 Example 3.47 17 Comparison 5 Example 4.41 21 Comparison 5 Example 4.19 20 121 21 Example 5.59 25 127 21 Table 9 GC analysis of wet strength resins treated with base for epichlorohydrin byproducts Example mmole conditions NaOH / g epi Resin treatment (dry basis) Example without treatment none < 1 Comparative 2 Example 10 55 ° C for 2.8 < 1 5 minutes Example 11 0 ° C for 2.8 < 1 5 minutes Example without treatment < 0.1 < 0.1 Comparative 7 Example 29 55 ° C for 2.8 < 0.1 5 minutes Example without treatment none < 1 Comparative 3 Example 13 55 ° C for 2. 8 108 5 minutes Example without treatment none < 10 Comparative 4 Example 19 25 ° C for 2.0 440 5 minutes Example 18 55 ° C for 2.0 439 5 minutes Example without treatment none <1 Comparative 5 Example 22 5555 °° < C for 4.3 479 5 5 mm: inutos Example ssiinn treatment none < 10 Comparative 6 Example 28 2 255 °° (C for 4.3 450 o5 ImGUinutes Example 25 5555 °° CC for 4.3 193 55 minutes Example 11..33 DCP 2.3 DCP 3-CPD eg emplo < 1 1 57 comparative 2 example 10 < 1 <1 6 example 11 <1 1 51 example <0.1 0.7 2.5 comparative 7 example 29 <0.1 0.5 0.5 example 178 8 188 comparative 3 example 13 <1 <1 10 example 800 <10 190 comparative 4 example 19 45 <1 324 example 18 14 <1 163 example 896 <1 528 comparative 5 example 22 23 1 132 example 1000 <10 175 comparative 6 example 28 53 4 144 example 25 8 4 53 (1) epi = epichlorohydrin, ppm = parts per million in the resin (dry base) The data for the base treated resins were corrected at a solids level equal to the corresponding untreated resin (2) 1,3-DCP = 1,3- dichloropropanol, ppm = parts per million in the resin (dry base) The data for the base-treated resins were corrected to a solid level equal to the corresponding untreated resin. (3) 2,3-DCP = 2,3-dichloropropanol, ppm = parts per million in the resin (dry base). The data for the base treated resins were corrected at a solids level equal to the corresponding untreated resin. (4) 3-CPD = 3-chloropropanediol, ppm = parts per million in the resin (dry base). The data for the base treated resins were corrected at a solids level equal to the corresponding untreated resin.

Claims (142)

1. Claims 1. A process for reducing the AOX content of an initial water soluble wet strength resin comprising acetydinium ions and tertiary aminohalohydrin, which comprises treating said resin in aqueous solution with a base to form a treated resin, wherein at least about 20% of the tertiary aminohalohydrin present in the initial resin is converted to epoxide, the level of acetydinium ion is substantially unchanged, and the effectiveness of the resin treated to impart a wet strength is at least approximately large as the effectiveness of said resistance resin in initial wet state.
2. 2. The process according to claim 1 wherein the initial water soluble wet strength resin is selected from the group consisting of polyaminopolyamide-epichlorohydrin resins and polyamine-epichlorohydrin resins and mixtures thereof.
3. 3. The process according to claim 1 wherein the base is selected from the group consisting of alkali metal hydroxides, carbonates and bicarbonates, iron alkali metal hydroxides, trialkylamines and tetraalkylammonium hydroxides.
4. 4. The process according to claim 1 wherein the initial, water-soluble wet strength resin further comprises aminohalohydrin selected from the group consisting of secondary aminohalohydrin and quaternary ammoniumhalohydrin.
5. 5. The process according to claim 1 wherein up to about 100% of the aminohalohydrin present in the initial resin is converted to epoxide.
6. 6. The process according to claim 1 wherein the initial, water-soluble wet strength resin concentration is at least about 1%.
7. The process according to claim 1 wherein the concentration of resistance resin in the wet, water soluble, initial state is up to about 40%.
8. 8. The process according to claim 1 wherein the amount of the base is at least about 0.5 millimole per gram of initial resin in a dry base.
9. 9. The process according to claim 1 wherein the amount of base is up to about 10 millimoles per gram of initial resin in a dry base.
10. 10. The method according to claim 1 wherein the temperature is up to about 100 ° C.
11. 11. The process according to claim 1 wherein the initial, water-soluble wet strength resin is treated with a base for at least about 1 minute.
12. 12. The process according to claim 1 wherein the initial, water-soluble wet strength resin is treated with a base for up to about 24 hour s.
13. The process according to claim 2 wherein the base is selected from the group consisting of alkali metal hydroxides, carbonates and bicarbonates, alkali metal hydroxides, trialkylamines and tetraalkylammonium hydroxides, up to about 100% of the tertiary aminohalohydrin present in the initial resin is converted to epoxide, the initial water-soluble resin concentration is from about 1% to about 40%, the amount of base is from about 0.5 to about 10 millimoles per gram of initial resin on dry basis, the temperature is up to about 100 ° C, and the initial, water-soluble wet strength resin is treated with a base for a period of about 1 minute to about 24 hours.
14. The process according to claim 13 wherein (a) the polyamino polyamide-epichlorohydrin resin comprises the product of the reaction of epichlorohydrin and polyamide derived from polyalkylene polyamine and dibasic carboxylic acid or dibasic carboxylic ester containing from about 3 to 10 carbon atoms. carbon, (b) the polyamine-epichlorohydrin resin comprises the product of the reaction of epichlorohydrin and polyalkylenepolyamine; and wherein the polyalkylene polyamine is selected from a group consisting of polyethylene polyamines, polypropylene polyamines, polybutylene polyamines, polypentylene polyamines, polyhexylene polyamines and mixtures thereof.
15. 15. The process according to claim 13 wherein the base is selected from the group consisting of sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide.
16. 16. The process according to claim 13 wherein the tertiary aminohalohydrin is tertiary aminoclorohydrin.
17. 17. The process according to claim 13 wherein at least about 50% of the aminohalohydrin present in the initial resin is converted to epoxide.
18. 18. The process according to claim 13 wherein the initial, water-soluble wet strength resin concentration is at least about 2%.
19. The process according to claim 13 wherein the concentration of resistance resin in the wet, water soluble, initial state is up to about 25%.
20. The process according to claim 13 wherein the amount of the base is at least about 1.5 millimoles per gram of initial resin in a dry base.
21. 21. The process according to claim 13 wherein the amount of base is up to about 8 millimoles per gram of initial resin in a dry base.
22. 22. The process according to claim 13 wherein the temperature is at least about 20 ° C.
23. 23. The method according to claim 13 wherein the temperature is up to about 80 ° C.
24. 24. The process according to claim 13 wherein the initial, water-soluble wet strength resin is treated with base for at least about 3 minutes.
25. 25. The procedure in accordance with the claim Wherein the resistance resin in the wet, water-soluble, initial state is treated with base for up to about 4 hours.
26. 26. The procedure in accordance with the claim Wherein the base is selected from the group consisting of sodium carbonate, potassium carbonate, sodium hydroxide, and potassium hydroxide, the tertiary aminohalohydrin is tertiary aminochlorohydrin from about 50 to about 100% of the tertiary aminohalohydrin present in the resin initial is converted to epoxide, the concentration of the resistance resin in wet state, soluble in water, initial is from about 2% to about 25%, the amount of base is from about 1.5 to about 8 millimoles per gram of initial resin in a dry base, the temperature is from about 20 ° C to about 80 ° C and the initial, water-soluble wet strength resin is treated with a base for a period of about 3 minutes to about 4 hours.
27. 27. The process according to claim 26 wherein (a) the polyaminopolyamide-epichlorohydrin resin comprises the product of the reaction of epichlorohydrin and polyamide derivative of polyalkylenepolyamine selected from the group consisting of diethylenetriamine, triethylene tetra, tetraethylenepentamine and mixtures thereof. same and dibasic carboxylic acid or dibasic carboxylic ester selected from the group consisting of glutaric acid, adipic acid, their esters and mixtures thereof and (b) the polyamine-epichlorohydrin resin comprises the reaction product of selected epichlorohydrin and polyalkylene polyamine. within the group consisting of hexamethylenediamine, bihexamethylenetriamine and mixtures thereof.
28. 28. The process according to claim 26 wherein the base is selected from the group consisting of sodium hydroxide and potassium hydroxide.
29. 29. The process according to claim 26 wherein at least about 90% of the tertiary aminoclorohydrin present in the initial resin is converted to epoxide.
30. 30. The process according to claim 26 wherein the initial, water-soluble wet strength resin concentration is at least about 5%.
31. 31. The process according to claim 26 wherein the initial, water-soluble wet strength resin concentration is up to about 15%.
32. 32. The process according to claim 26 wherein the temperature is at least about 40 ° C.
33. 33. The method according to claim 26 wherein the temperature is up to about 60 ° C.
34. 34. The process according to claim 26 wherein the initial, water-soluble wet strength resin is treated with base for at least about 5 minutes.
35. 35. The process according to claim 27 wherein the initial, water-soluble wet strength resin is treated with base for up to about 1 hour.
36. 36. The process according to claim 27 wherein the base is selected from the group consisting of sodium hydroxide and potassium hydroxide, from about 90 to about 100% "of the tertiary aminohalohydrin present in the initial resin is converted to epoxide. , the initial, water soluble, wet strength resin concentration is from about 5% to about 15%, the temperature is from about 40 ° C to about 60 ° C, and the wet strength resin, water soluble, initial is treated with a base for a period of about 5 minutes to about 1 hour.
37. 37. The water-soluble wet strength resin prepared by the process according to claim 1.
38. 38. The water-soluble wet strength resin prepared by the process according to claim 13.
39. 39. The water-soluble wet strength resin prepared by the process according to claim 26.
40. 40. The water-soluble wet strength resin prepared by the process according to claim 36.
41. 41. A process for the preparation of paper comprising: (a) supplying a pulp of aqueous pulp; (b) adding to the aqueous pulp slurry the water soluble, solid state strength resin of claim 37 (c) forming sheets and drying the pulp of aqueous pulp to produce a paper.
42. 42. A process for preparing paper comprising: (a) supplying an aqueous pulp paste; (b) adding to the aqueous pulp slurry the water-soluble wet strength resin of claim 38 (c) forming sheets and drying the pulp of aqueous pulp to produce a paper.
43. 43. A process for preparing paper comprising: (a) supplying an aqueous pulp paste; (b) adding to the aqueous pulp slurry the water-soluble wet strength resin of claim 39 (c) forming sheets and drying the pulp of aqueous pulp to produce a paper.
44. 44. A process for preparing paper comprising: (a) supplying an aqueous pulp paste; (b) adding to the aqueous pulp slurry the water-soluble wet strength resin of claim 40 (c) forming sheets and drying the pulp of aqueous pulp to produce a paper.
45. 45. Paper prepared according to the method of claim 41.
46. 46. Paper prepared according to the method of claim 42.
47. 47. Paper prepared according to the method of claim 43.
48. 48. Paper prepared in accordance with - process of claim 44.
49. 49. The process comprising the treatment of an initial, water-soluble wet strength resin comprising acetydinium ions and tertiary aminohalohydrin ions in aqueous solution with a base to form a treated resin, wherein the initial, water-soluble wet strength resin is selected from the group consisting of polyaminopolyamide-epichlorohydrin resins and polyamine-epichlorohydrin resins and mixtures thereof and the base is selected from the group consisting of hydroxides, carbonates and bicarbonates of alkali metals, hydroxides of ferrous alkali metals, trialkylamines, hydro tetraalkylammonium oxides, ammonia, organic amines, alkali metal sulphides, alkali earth sulphides, alkali metal alkoxides and alkaline earth alkoxides.
50. 50. The procedure in accordance with the claim Wherein up to about 100% of the tertiary aminohalohydrin in the initial resin is converted to epoxide, the initial water soluble resin concentration is from about 1% to about 40%, the amount of base is from about 0.5 to about 10 millimoles per gram of initial resin in a dry base, the temperature is up to about 100 ° C, and the initial wet, water-soluble strength resin is treated with a base for a period of about 1 minute to about 24 hours .
51. 51. A process for reducing the AOX content of a composition comprising a halohydrin and acetydinium ion functionality, which comprises treating the composition with base.
52. 52. A method for reducing the AOX content of a composition comprising tertiary amines with a halohydrin functionality, comprising treating the composition with base.
53. 53. A method for reducing the AOX content of a composition comprising a halohydrin functionality, comprising treating the composition based on a temperature of at least about 40 ° C.
54. 54. A method for reducing the AOX content of a composition comprising a halohydrin functionality, comprising treating the composition based on a temperature of up to about 100 ° C.
55. 55. A method for reducing the AOX content of a composition comprising a halohydrin functionality, which comprises treating the composition based on a solids content of at least about 6% based on the weight of the composition.
56. 56. A method for reducing the AOX content of a composition comprising a halohydrin functionality, which comprises treating the composition based on a solids content of up to about 40% based on the weight of the composition.
57. 57. The process according to claim 51 wherein the pH is at least about 8.
58. 58. The method according to claim 51 wherein the pH is up to about 13.
59. 59. A method for reducing the AOX content of a composition comprising a halohydrin functionality, comprising treating the base composition wherein the AOX content is reduced to less than about 50% of the AOX component in the untreated composition on an equal solids level basis.
60. 60. A method for reducing the AOX content of a composition comprising quaternary amines with a halohydrin functionality comprising the treatment of the composition based on a temperature of about 40 ° C to about 100 ° C.
61. 61. A method for reducing the AOX content of a composition comprising quaternary amines with a halohydrin functionality comprising the treatment of the composition based on a solids content of about 6% to about 40% based on the weight of the composition. composition.
62. 62. The procedure in accordance with the claim Wherein the composition comprises an aqueous solution containing a wet strength agent.
63. 63. The procedure in accordance with the claim Wherein the composition comprises an aqueous solution containing wet strength agent.
64. 64. The process according to claim 53 wherein the composition comprises an aqueous solution containing wet strength agent.
65. 65. The process according to claim 54 wherein the composition comprises an aqueous solution containing wet strength agent.
66. 66. The method according to claim 55 wherein the composition comprises an aqueous solution containing resistance agent * in the wet state.
67. 67. The procedure in accordance with the claim 56 wherein the composition comprises an aqueous solution containing wet strength agent.
68. 68. The procedure in accordance with the claim 57 where the pH is at least about 9.
69. 69. The procedure in accordance with the claim 58 where the pH is up to about 12.5.
70. 70. The procedure in accordance with the claim 59 wherein the composition comprises an aqueous solution containing wet strength agent.
71. 71. The procedure in accordance with the claim Wherein the composition comprises an aqueous solution containing wet strength agent.
72. 72. The procedure in accordance with the claim Wherein the composition comprises an aqueous solution containing wet strength agent.
73. 73. The process according to claim 62 wherein the solids of the aqueous solution of wet strength agent are treated with a base prior to the addition of the wet strength agent to the aqueous paper pulp.
74. 74. The process according to claim 63 wherein the solids of the aqueous solution of wet strength agent are treated with a base prior to the addition of the wet strength agent to an aqueous paper pulp.
75. 75. The procedure in accordance with the claim Wherein the solids of the aqueous solution of wet strength agent are treated with a base before the addition of the wet strength agent to the aqueous paper pulp.
76. 76. The procedure in accordance with the claim Wherein the solids of the aqueous solution of wet strength agent are treated with a base prior to the addition of the wet strength agent to the aqueous paper pulp ..
77. 77. The process according to the claim 66 where the solids of the aqueous solution of wet strength agent are treated with a base before the addition of the wet strength agent to the aqueous paper pulp ..
78. 78. The process according to the claim 67 where the solids of the aqueous solution of wet strength agent are treated with a base before the addition of the wet strength agent to the aqueous paper pulp ..
79. 79. The method according to claim 68 wherein the pH is at least about 10.
80. 80. The process according to the claim 69 wherein the pH is at least about 12.
81. 81. The process according to claim 70 wherein the solids in the aqueous solution of wet strength agent are treated with base before the addition of the wet strength agent. to the aqueous paper pulp.
82. 82. The process according to claim 71 wherein the solids of the aqueous solution of wet strength agent are treated with base before the addition of the wet strength agent to the aqueous paper pulp.
83. 83. The process according to claim 72 wherein the solids of the aqueous solution of wet strength agent are treated with base before the addition of the wet strength agent to the aqueous paper pulp.
84. 84. The process according to claim 73 comprising the addition of the treated wet strength agent to the aqueous pulp of paper within a period of about 1 minute to about 24 hours after the base treatment has reached the level desired reduction of AOX content.
85. 85. The process according to claim 74 comprising the addition of the treated wet strength agent to the aqueous pulp of paper within about 1 minute to about 24 hours after the base treatment has reached the desired level of reduction. of AOX content.
86. 86. The procedure in accordance with the claim 75 comprising the addition of the treated wet strength agent to an aqueous pulp of paper within about 1 minute to about 24 hours after the base treatment has reached the desired level of AOX content reduction.
87. 87. The procedure in accordance with the claim 76 comprising the addition of the treated wet strength agent to the aqueous pulp of paper within a period of about 1 minute to about 24 hours after the base treatment has reached the desired level of AOX content reduction.
88. 88. The procedure in accordance with the claim 77 comprising the addition of the treated wet strength agent to the aqueous pulp of paper within about 1 minute to about 24 hours after the base treatment has reached the desired level of AOX content reduction.
89. 89. The process according to claim 78 comprising the addition of the treated wet strength agent to the aqueous pulp of paper within about 1 minute to about 24 hours after the base treatment has reached the desired level of reduction. of AOX content.
90. 90. The process according to claim 79 wherein the pH is at least about 10.5.
91. 91. The method according to claim 80, wherein the pH is up to about 11.5.
92. 92. The process according to claim 81 comprising the addition of the treated wet strength agent to an aqueous pulp of paper within about 1 minute to about 24 hours after the base treatment has reached the desired level of reduction of AOX content.
93. 93. The procedure in accordance with the claim 82 comprising the addition of the treated wet strength agent to an aqueous pulp of paper within about 1 minute to about 24 hours after the base treatment has reached the desired level of AOX content reduction.
94. 94. The procedure in accordance with the claim 83 comprising the addition of the treated wet strength agent to an aqueous pulp of paper within about 1 minute to about 24 hours after the base treatment has reached the desired level of AOX content reduction.
95. 95. The procedure in accordance with the claim 51 where up to 100% of the halohydrin functionality is converted to epoxide.
96. 96. The procedure in accordance with the claim 52 where up to 100% of the halohydrin functionality is converted to epoxide.
97. 97. The procedure in accordance with the claim 53 where up to 100% of the halohydrin functionality is converted to epoxide.
98. 98. The procedure in accordance with the claim 54 where up to 100% of the halohydrin functionality is converted to epoxide.
99. 99. The process according to claim 55 wherein up to 100% of the halohydrin functionality is converted to epoxide.
100. 100. The process according to claim 56 wherein up to 100% of the halohydrin functionality is converted to epoxide.
101. 101. The method according to claim 53 wherein the temperature is at least about 45 ° C.
102. 102. The method according to claim 54 wherein the temperature is at least about 80 ° C.
103. 103. The method according to claim 59 wherein up to 100% of the halohydrin functionality is converted to epoxide.
104. 104. The process according to claim 60 wherein up to 100% of the halohydrin functionality is converted to epoxide.
105. 105. The method according to claim 61 wherein up to 100% of the halohydrin functionality is converted to epoxide.
106. 106. The method according to claim 51 wherein the level of acetydinium ion is substantially unchanged.
107. 107. The method according to claim 52 wherein the level of acetydinium ion is substantially unchanged.
108. 108. The method according to claim 53 wherein the level of acetydinium ion is substantially unchanged.
109. 109. The method according to claim 54 wherein the level of acetydinium ion is substantially unchanged.
110. 110. The method according to claim 55 wherein the level of acetydinium ion is substantially unchanged.
111. 111. The method according to claim 56 wherein the level of acetydinium ion is substantially unchanged.
112. 112. The process according to claim 55 wherein the solids content is at least about 8%.
113. 113. The process according to claim 56 wherein the solids content is up to about 25%.
114. 114. The method according to claim 59 wherein the level of acetydinium ion is substantially unchanged.
115. 115. The method according to claim 60 wherein the level of acetydinium ion is substantially unchanged.
116. 116. The method according to claim 61 wherein the level of acetydinium ion is substantially unchanged.
117. 117. The process according to claim 51 wherein the wet strength effectiveness of the composition is not substantially diminished.
118. 118. The process according to claim 52 wherein the effectiveness of wet strength of the composition is not substantially diminished.
119. 119. The process according to claim 53 wherein the wet strength effectiveness of the composition is not substantially diminished.
120. 120. The process according to claim 54 wherein the wet strength effectiveness of the composition is not substantially diminished.
121. 121. The process according to claim 55 wherein the wet strength effectiveness of the composition is not substantially diminished.
122. 122. The process according to claim 56 wherein the wet strength effectiveness of the composition is not substantially diminished.
123. 123. The method according to claim 59 wherein the AOX content is reduced to less than about 25% of the AOX content in the untreated composition on an equal solids level basis.
124. 124. The method according to claim 123 wherein the AOX content is reduced to less than about 10% of the AOX content in the untreated composition on an equal solids level basis.
125. 125. The process according to claim 59 wherein the wet strength effectiveness of the composition is not substantially diminished.
126. 126. The process according to claim 60 wherein the wet strength effectiveness of the composition is not substantially diminished.
127. 127. The process according to claim 61 wherein the wet strength effectiveness of the composition is not substantially diminished.
128. 128. A process for preparing a polymer comprising acetydinium ion and aminoepoxide having a reduced content of AOX, comprising the treatment with base of a polymer containing halohydrin functionality and acetydinium ions.
129. 129. The process according to claim 128 wherein the polymer having a reduced content of AOX comprises a crosslinkable polymer.
130. 130. The process according to claim 128 wherein the polymer having a reduced content of AOX comprises a water soluble polymer.
131. 131. The process according to claim 128 wherein the polymer having a reduced content of AOX comprises a cross-linked polymer.
132. 132. The process according to claim 51 wherein the halohydrin functionality comprises tertiary aminohalohydrin.
133. 133. The procedure in accordance with the claim 101 where the temperature is at least about 50 ° C.
134. 134. The procedure in accordance with the claim 102 where the temperature is at least about 60 ° C.
135. 135. The method according to claim 112 wherein the solids content is at least about 10%.
136. 136. The method according to claim 113 wherein the solids content is up to about 15%.
137. 137. The process according to claim 124 wherein the AOX content is reduced to less than about 5% of the AOX content in the untreated composition in a base of equal solids level.
138. 138. The procedure in accordance with the claim 137 where the AOX content is reduced to less than about 1% of the AOX content in the untreated composition based on an equal level of solids.
139. 139. The procedure in accordance with the claim 138 where the AOX content is reduced to less than about 0.5% of the AOX content in the untreated composition based on an equal level of solids.
140. 140. The process according to claim 51 wherein the base is selected from the group consisting of alkali metal hydroxides, carbonates and bicarbonates, alkali metal hydroxides, trialkylamines, tetraalkylammonium hydroxides, ammonia, organic amines, metal sulphides alkaline, alkaline earth sulfides, alkali metal alkoxides and alkaline earth alkoxides.
141. 141. The process according to claim 140 wherein the base is selected from the group consisting of alkali metal hydroxides and alkali metal carbonates.
142. 142. The procedure in accordance with the claim 141 where the base is selected from the group consisting of sodium hydroxide and potassium hydroxide.