CA1188836A - Dicyandiamide-formaldehyde condensates modified with urea and process for preparing the same - Google Patents
Dicyandiamide-formaldehyde condensates modified with urea and process for preparing the sameInfo
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- CA1188836A CA1188836A CA000416581A CA416581A CA1188836A CA 1188836 A CA1188836 A CA 1188836A CA 000416581 A CA000416581 A CA 000416581A CA 416581 A CA416581 A CA 416581A CA 1188836 A CA1188836 A CA 1188836A
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-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
- D21H17/50—Acyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/043—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/043—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24
- C08G12/046—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with at least two compounds covered by more than one of the groups C08G12/06 - C08G12/24 one being urea or thiourea
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/46—Block or graft polymers prepared by polycondensation of aldehydes or ketones on to macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
- C08G73/0286—Preparatory process from polyamidoamines and epihalohydrins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/17—Ketenes, e.g. ketene dimers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
Abstract
Abstract of the Disclosure Disclosed are novel water-soluble, thermosettable resinous compositions derived by reacting a precondensate of dicyandiamide, formaldehyde, a salt of a water-soluble poly-aminopolyamide and an ammonium salt with urea and then con-densing the reaction product with additional formaldehyde.
The resinous compositions are cationic and have particular utility in the manufacture of paper sized with cellulose reactive sizing agents such as ketene dimer sizing agents.
The resinous compositions are cationic and have particular utility in the manufacture of paper sized with cellulose reactive sizing agents such as ketene dimer sizing agents.
Description
mhis invention relates to novel water-soluble, thermo-se-ttable resinous compositions containing dicyandiamide-formaldehyde condensates and more particularly relates -to the compositions produced b-y reacting a precondensate of dicyan-diamide, formaldehyde, an acid salt of a water-soluble poly-aminopolyamide and an ammonium salt with urea, and then con-densing the reaction produc-t with formaldehyde. The resinous compositions are cationic and water-soluble and have partic-ular utility in the manufacture of sized paper wherein the sizing agent employed is a cellulose reactive sizing agent such as a ketene dimer sizing agent.
In U.S. Patent 3,~40,4~6, Dumas describes water-soluble, ca-tionic; thermosettable resinous compositions derived from dicyandiamide, an ammonium salt, formaldehyde antd an acid salt of a water-soluble polyaminopolyamide and teaches their prep-aration by forming a precondensate by heat reacting in aqueous medium 1 mole of dicyandiamide, from 0.75 to 1.5 moles o-f formaldehyde, sufficient of an acid salt of a polyaminopoly--amide to provide about 0.125 to about 0.5 equivalent of basic nitrogen and an ammonium salt in an amount to provide a total of from 0.~ to about 1.2 equivalents of basic nitrogen until substantially all nitriles of the dicyandiamide have reacted, adding from about 1.25 to about 3.75 moles ort formaldehyde to the aqueous precondensate and refluxing the resulting mixture until the viscosity of a solution of the product is within a desired range. The resinous compositions of U.S. Patent 3,~40,426 are said to be useful as accelerators or hydro-phobic cellulose reactive sizing agents antl the combination is reported to provide higher off-the-machine sizing than is provided by an equivalent amount of the sizing agent alone.
i~
- -Dumas' resinous compositions, howeYer, do not impart si~ing to paper when used alone in amounts normally employed in the paper sizing art and -the use of Dumas' resinous co~positions in combinatio}l with cellulose reactive sizes 2S si~ing agents in the manufacture of paper does not provide an ultimate degree of sizing which is substantially different from that achieved with the sizing agent alone. Since nearly all grades of paper are sized to some extent, increased si~ing efficiency is an important objective of papermakers and any improvements which can be realized in the degree of si~ing can have pro-nounced economic significance.
Now, in accordance with this invention, it has been found that unique resins are produced by modifying the process of U.S. Patent 3~8~rO~4~6 ancl that the mo-lified resins so produced provide higher ultimate si~ing with cellulose reactive sizing agents such as ketene dimers, acid anhydrides and isocyanates on natural aging or oven curing as comparecl ~ith the unmodi-fied resins. Further, the resins produced in accordance with this invention accelera-te the rate of sizing development with cellulose reactive sizing agents and thus increase the overall efficiency of the sizing agents.
Accordingly, the present invention relates to a process for preparing improved water-soluble thermosettable resinous compositions containing dicyandianide-formalclehyde conden-2S sates, which process comprises (1) Eorming a precondensatesolution by refluxing Eor about 1 to abou-t 4 hours an aqueous mixture of (a) a base reaction product of 1 mole of dicyan-diamide, 0.75 mole to 1.5 moles oE formaldehyde and an acicl salt of a water-soluble polyaminopolyamide in an amount suffi-cient to provide from about 0.125 to about 0.5 equivalent ofbasic nitrogen and (b) an ammonium salt in an amount such that there will be from 0.7 equivalent to about 1.2 equivalents of basic nitrogen derived from the salt of the polyaminopolyamide and the ammonium salt in the aqueous medium, (2) adding to the precondensate solution from 0.30 to 0.45 mole of urea per equivalent of basic nitrogen derived from the salt of the polyaminopolyamide and the ammonium salt, and heating the 3B~3~
aqueous mixture at about 80 -to abou-t llO~C. for about 0.5 hour to abou-t 1.5 hours until a solution of modified precon~
densate is formed, (3) adding from about 1.25 -to about 3.75 moles of formalclehyde to the a~ueous solution of modified precondensate and (4) heating the resulting mixture at about 60 to about 100C. until the viscosity of an aqueous solution of the resulting reaction product a-t a solids content of 50%
is from about U to Z on the Gardner-Holdt scale, and to the resinous compositions so produced.
As above set forth, dicyandiami~e is one of the reactants employed in preparing the precondensate in the first step of the process of this invention. Dicyandiamide is also known as cyanoguanidine and has the following structure:
NH
H2~ -NH-C=~
Formaldehyde is another reactant employed to prepare the precondensate. As employed in this specification and in the claims, formaldehyde includes formaldehyde in the Eorm of 30-40% aqueous solutions and polymeric forms of formaldehyde such as, for example, paraformaldehyde, trioxane, and hexa-methylenetetramine. Chemical compounds such as acetals which will liberate formaldehyde on heating can be employed as a source of formaldehyde if desired.
The ammonium salt reactant is a water-soluble salt of an
In U.S. Patent 3,~40,4~6, Dumas describes water-soluble, ca-tionic; thermosettable resinous compositions derived from dicyandiamide, an ammonium salt, formaldehyde antd an acid salt of a water-soluble polyaminopolyamide and teaches their prep-aration by forming a precondensate by heat reacting in aqueous medium 1 mole of dicyandiamide, from 0.75 to 1.5 moles o-f formaldehyde, sufficient of an acid salt of a polyaminopoly--amide to provide about 0.125 to about 0.5 equivalent of basic nitrogen and an ammonium salt in an amount to provide a total of from 0.~ to about 1.2 equivalents of basic nitrogen until substantially all nitriles of the dicyandiamide have reacted, adding from about 1.25 to about 3.75 moles ort formaldehyde to the aqueous precondensate and refluxing the resulting mixture until the viscosity of a solution of the product is within a desired range. The resinous compositions of U.S. Patent 3,~40,426 are said to be useful as accelerators or hydro-phobic cellulose reactive sizing agents antl the combination is reported to provide higher off-the-machine sizing than is provided by an equivalent amount of the sizing agent alone.
i~
- -Dumas' resinous compositions, howeYer, do not impart si~ing to paper when used alone in amounts normally employed in the paper sizing art and -the use of Dumas' resinous co~positions in combinatio}l with cellulose reactive sizes 2S si~ing agents in the manufacture of paper does not provide an ultimate degree of sizing which is substantially different from that achieved with the sizing agent alone. Since nearly all grades of paper are sized to some extent, increased si~ing efficiency is an important objective of papermakers and any improvements which can be realized in the degree of si~ing can have pro-nounced economic significance.
Now, in accordance with this invention, it has been found that unique resins are produced by modifying the process of U.S. Patent 3~8~rO~4~6 ancl that the mo-lified resins so produced provide higher ultimate si~ing with cellulose reactive sizing agents such as ketene dimers, acid anhydrides and isocyanates on natural aging or oven curing as comparecl ~ith the unmodi-fied resins. Further, the resins produced in accordance with this invention accelera-te the rate of sizing development with cellulose reactive sizing agents and thus increase the overall efficiency of the sizing agents.
Accordingly, the present invention relates to a process for preparing improved water-soluble thermosettable resinous compositions containing dicyandianide-formalclehyde conden-2S sates, which process comprises (1) Eorming a precondensatesolution by refluxing Eor about 1 to abou-t 4 hours an aqueous mixture of (a) a base reaction product of 1 mole of dicyan-diamide, 0.75 mole to 1.5 moles oE formaldehyde and an acicl salt of a water-soluble polyaminopolyamide in an amount suffi-cient to provide from about 0.125 to about 0.5 equivalent ofbasic nitrogen and (b) an ammonium salt in an amount such that there will be from 0.7 equivalent to about 1.2 equivalents of basic nitrogen derived from the salt of the polyaminopolyamide and the ammonium salt in the aqueous medium, (2) adding to the precondensate solution from 0.30 to 0.45 mole of urea per equivalent of basic nitrogen derived from the salt of the polyaminopolyamide and the ammonium salt, and heating the 3B~3~
aqueous mixture at about 80 -to abou-t llO~C. for about 0.5 hour to abou-t 1.5 hours until a solution of modified precon~
densate is formed, (3) adding from about 1.25 -to about 3.75 moles of formalclehyde to the a~ueous solution of modified precondensate and (4) heating the resulting mixture at about 60 to about 100C. until the viscosity of an aqueous solution of the resulting reaction product a-t a solids content of 50%
is from about U to Z on the Gardner-Holdt scale, and to the resinous compositions so produced.
As above set forth, dicyandiami~e is one of the reactants employed in preparing the precondensate in the first step of the process of this invention. Dicyandiamide is also known as cyanoguanidine and has the following structure:
NH
H2~ -NH-C=~
Formaldehyde is another reactant employed to prepare the precondensate. As employed in this specification and in the claims, formaldehyde includes formaldehyde in the Eorm of 30-40% aqueous solutions and polymeric forms of formaldehyde such as, for example, paraformaldehyde, trioxane, and hexa-methylenetetramine. Chemical compounds such as acetals which will liberate formaldehyde on heating can be employed as a source of formaldehyde if desired.
The ammonium salt reactant is a water-soluble salt of an
2~ amine and an acid. Particularly suitable salts are those having the formula (NH4)mX; (RlNH3)mX; or (RlR2NH2) X
where ~1 and P~2 are alkvl radicals having from 1 through 4 carbon atoms such as me-thyl, ethyl, propyl, isopropyl and n-butyl; X is the acid anion such, for example, as Cl , Br , 30 I , SO4 , CE13COO , ~03 , and PO~ ; and m is an integer equal to the anion charge. Specific examples of suitable ammonium salts include ammonium sulfate, ammonium chloride, methyl ammonium chloride, dimethyl ammonium chloride, ethyl ammonium sulfate, and ammonium acetate.
0-ther suitable ammonium salts are the water-soluble salts of (1) a polyamine having the structure:
l3 H2~CnE~2n ( NCnH2n ) 1~M2 where R3 is hydrogen or methyl; n is an integer 2 through 6; ancl x is an integer 0 throug~l 3 and (2) an acid such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid ancl acetic acid. Specific examples of polyamines are ethylene diamine, propylene diamine, hexamethylene diamine, diethylenetriamine, tetra-ethylenepentamine, and bis(3-aminopropyl)amine.
Another reactant is an acid salt of a water-soluble poly-aminopolyamide. The polyaminopolyamide is derived by reaction of a dicarbo~ylic acid and a polyalkylenepolyamine in a mole ratio of polyalkylenepolyamine to dicarboxylic acid of from about 0.8:1 to about 1.~:1. Particularly suitable dicarbox~
ylic acids are diglycolic acid and saturated aliphatic dicar-boxylic acids containing from 3 through 10 carbon atoms such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
Other suitable dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid and alpha-unsaturated dicar-boxylic acids such as maleic acid, fumaric acid, itaconic acid, glutaconic acid, citraconic acid and mesaconic acid.
The available anhydrides of the above acids can be used for preparing the water-soluble polyaminopolyamide as ~ell as the esters of the acids. Mixtures of two or more of the above acid moieties can be employed if desired.
A number of polyalkylenepolyamines, including poly-ethylenepolyamines, polypropylenepolyamines, polybutylene-polyamines and the like can be employed to produce the poly-aminopolyamide. mhe polyal~ylenepolyamine employed will havetwo primary amine groups and can be represented as polyamines in which the nitrogen atoms are linked together by groups of the formula -CnH2n- where n is a small integer greater than unity and preferably 2 thro~lgh 6, and the number of such groups in the molecule ranges from -two up to about eight. ~he nitrogen atoms can be attached to adjacent carbon atoms in the group -CnM2n- or to carbon atoms farther apart, but not to the same carbon atoms. Polyamines such as diethylenetriamine, triethylenetetramine, tetraethvlenepentamine, and bis(3-amino-propyl)amine, which can be obtaine~ in reasonably pure form are suitable for preparing water-soluble polyaminopolyamides.
Other polyallcylenepolyamines that can be used include metl~yl bis(3-aminopropyl)amine; methyl bis(2-aminoethyl) amine; and 4,7-dimethyl-triethylenetetramine. Mi~tures of polyalkylene-polyamines can be used, if desired.
~he above polyalkylenepolyamines can be represented by the formula l3 H2NCnH2n ( NCnH2n ) yMH2 where P~3 is hydrogen or methyl; n is an integer 2 through 6, as above set forth, and y is an integer 1 through 3. Other polyalkylenepolyamines that can be employed and which are not included in the above formula include 1,4-bis(3-aminopropyl)-piperazine and 1-(2-aminoethyl)piperazine.
The spacing of an amino group on the polyaminopolyamide can be increased if desired. ~his can be accomplished by substituting a diamine such as ethylenediamine, propylene-diamine, he~amethylenediamine and the like for a portion of the polyalkylenepolyamine. For this purpose, up to about ~0%
of the polyalkylenepolyamine can be replaced by a molecularly equivalent amount of diamine. I1sually, a replacement of about 50~ or less will be adequate.
Temperatures employed for carrying out reaction between the dicarboxylic acid and the polyalkylenepolyamine to form the water-soluble polyaminopolyamide can vary from about 110C. to about 250C. or hi~her at atmospheric pressure. For most purposes, temperatures between about 1~0~. and 210C.
are preferred. The time of reaction will vary inversely with reaction temperatures employed and usually will be from about 1/2 to 2 hours. The reaction is desirably continued to sub-stantial completion, as determined by -the amount of water ~, evolved. In carrying out the reaction, it is preferred to use an amount of dicarbo~ylic acid sufficient to react sub-stantially completely with the primary amine groups of the polyalkylenepolyamine but insufficient to react with the secondary amine groups and/or tertiary amine groups to any substantial extent. This will usually require a mole ratio oE polyalkylenepolyamine to dicarboxylic acid of from about 0.9:1 to about 1.2:1. However, mole ratios of rrom about 0.8:1 to about 1.4:1 can be used.
The following example is illustrative of the preparation of a suitable water-soluble polyaminopolyamide for use as its salt in the preparation of the precondensate.
Example ~
A water-soluble polyaminopolyamide for use as its acid salt was formed by adding 146 parts (weight) of adipic acid slowly, with stirring, to 100 parts (weight) of diethylene-triamine in a reaction vesse] equipped with a s-tirrer, ther-mometer and a condenser for collecting water distillate. The reaction mixture was stirred and heated at a temperature of 20 from about 170C. to 175C. until amide formation was com-plete. After air cooling to approximately 140C., hot water was added with stirring to provide about a 50% solids solution of polyaminopolyamide resin having an intrinsic viscosity of 0.14 measured on a 2% solution in aqueous 1 M NH~Cl at 25C.
The preferred procedure for use in forming the precon-densate as set forth in the rirst step of the process of this invention is described below.
Into a reaction vessel are placed about one mole of dicyandiamide (cyanoguanidine), from about 3/~r mole to about 1-1/2 moles of formaldehyde, water-soluble polyaminopolyamide in an amount sufficient to provide from about 1/8 to about 1/2 of an equivalent of basic nitrogen (as distinguished from the amide nitrogens of the polyaminopolyamide), and an acid in an amount equivalent to the amount of the basic nitrogen of the polyaminopolyamide. Suitable acids include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, hydrobromic acid and hydroiodic acid. ~ater is conveniently employed as the reaction medium and sufficient water should be present in the mixture to provide an aqueous reaction mass that can be easily agitated (as by stirring) under reaction conditions. ~he amount of water employed is well within the skill of one versed in -t~le art having before him the teachings of this invention. ~he acid forms the polyaminopolyamide acid salt reactant.
The aqueous mixture is subsequently heated to reflux tem-perature (about 95C.-105C.) and refluxed for a period of time of about 15 minutes to about 30 minutes (or longer, if desired). Subsequently, the ammonium salt is added in an amount such that there will be from about 0.7 equivalent to about 1.2 equivalents (preferably about 1 equivalent) of basic nitrogen derived from the salt of the polyaminopolyamide and the ammonium salt present in the reaction mixture. ~hus, for example, when the polyaminopolyamide is employed in an amount equal to 1/2 (0.5) equivalent of basic nitrogen, the amount of ammonium salt employed will be such as to provide from about 0.2 equivalent to about 0.7 equivalent of basic nitrogen. 'rhe resulting mixture is heated to reflux and maintained at reflux temperature for about 1 to about 4 hours. Somew}lat shorter periods of time can be used if the heating is carried out under moderate pressure.
In the second step of the process of this invention, there is added to the precondensate solution from 0.30 to 0.45 mole and preferably from 0.35 to 0.~0 mole of urea per equiva-lent of basic nitrogen derived from the salt of the polyamino-polyamide and the ammonlum salt. The resulting mixture is then heated to about 80 to about 110C. and maintained at about 80 to about 110C. until a solution of modified precon-densate is formed. T}lis will usually require a period of time from about 0.5 hour to about 1.5 hours.
In steps (3) and (4) of the process of this invention, there are added to the modified precondensate from about 1.25 to about 3.75 moles of formaldehyde and the resulting mixture is then heated to between about 60 and about 100C. and main-tained thereat until the viscosity of an aqueous solution of L8~
the resinous reaction product, when measured at a solids con-tent of 50% at 25C. is Erom about U to ~ ancl preferably from about V to W, on the Gardner-Holdt scale. lhis will usually require a period of time of from about 20 minutes to about 3 hours. The aqueous solution is then diluted with water to a solids content of less than about 35% and pxeferably from about 15% to about 25% to terminate the reaction, and the pH
is adjusted to from about 6 to about 7.5 to provide storage stability.
If desired, the water-soluble thermosettable resinous compositions produced in accordance with the process of this invention can be further modified. Post modification is pre-ferably carried out by dilu-ting the solution of step ~4), if necessary, to a solids content less than 35~, adding to the solution from 0.03 to 0.75 mole and preferably ~rom 0.05 to 0.60 mole, per mole of formaldehyde added in step (3), o~ epi-halohydrin or a nitrogen-containing compound of the formula NFIRR', where R and R' are independently hydrogen, alkyl or hydroxyalkyl and, when R is hydrogen, R' is also aminoalkyl or an amido group, heating the mixture to about 45 to about 70C. and maintaining thereat for about 0.5 hour to about 2 hours. The nitrogen-containing compounds which can be used in this step include ammonia, mono- or dialkyl-amines and par-ticularly alkylamines wherein the alkyl group(s) contain(s) 1 to 4 carbon atoms, the mono- or di- alkanolamines, the alkylene diamines and urea. Particularly preferred compounds for the post-modification step are epichlorohydrin, ammonia, dimethylamine, diethanolamine, ethylenediamine and urea.
mhe best mode now contemplated for carrying out this invention is illustrated by the following e~amples of specific embodiments thereof and the invention is not limited to these specific embodiments. All percentages are by weight unless otherwise specified and the Gardner-Holdt viscosity measure-ments were made at 25C.
Example 1 Part 1 - Into a reaction vessel fitted with reflux con-denser, mechanical stirrer and -thermometer were placed the following to provide a mixture of ingredients:
Ingredient Grams Polyaminopolyamide solution of 522 (1.24 equivalents Example ~ (50.6% solids) of basic nitrogen) Formaldehyde (37~ aqueous solu-tion) 320 (3.97 moles) 5 Dicyandiamide 269 (3.2 moles) H2S4 (98~) 55.5 (.66 mole) Sulfuric acid was added last and was added dropwise. During addition of the sulfuric acid the temperature of the mixture increased to about 40-45C. The mixture was then heated to a temperature of about 100C. and refluxed for about 15 minutes.
Following cooling of the mixture to 85C., 137.5 grams (1.04 moles) of ammonium sulfate were added and the mixture was heated at 100C. for about 3 hours. The resulting solution of precondensate weighed 1300 grams and contained 62.5% solids.
Part 2 - Into a reaction vessel equipped with a mechan-ical stirrer, thermometer and reflux condenser were placed 272.4 grams of the precondensate solu-tion of Part 1 and 15.6 grams (0.26 mole) of urea. The mixture was heated at 100C.
for 1 hour, cooled to 70C. and then 136 grams (1.58 moles) of 37% aqueous formaldehyde were added over a 5 minute period.
The mixture was maintained at 70C. until the Gardner-Holdt viscosity of the aqueous solution of the resinous reaction product was V-W. ~ater, 600 ml, was added to the reaction vessel and the contents thereo cooled to room temperature.
m~he pH of the aqueous solution of the resinous reaction pro-duct was adjusted to 7.0 by adding thereto 34 ml of a 25~
aqueous solution of sodium hydroxide. Total solids was 21.2%
and the Gardner-Holdt viscosity of the aqueous solution was A-l .
Example 2 Part 1 - The procedure of Example 1, Part 1 was repeated and gave 1291 grams of a precondensate solution having a solids content of 62.1~.
Part 2 - Into a reaction vessel equipped with mechanical stirrer, thermometer and reflux condenser were placed 137.1 grams of the precondensate solution produced in Part 1, above,
where ~1 and P~2 are alkvl radicals having from 1 through 4 carbon atoms such as me-thyl, ethyl, propyl, isopropyl and n-butyl; X is the acid anion such, for example, as Cl , Br , 30 I , SO4 , CE13COO , ~03 , and PO~ ; and m is an integer equal to the anion charge. Specific examples of suitable ammonium salts include ammonium sulfate, ammonium chloride, methyl ammonium chloride, dimethyl ammonium chloride, ethyl ammonium sulfate, and ammonium acetate.
0-ther suitable ammonium salts are the water-soluble salts of (1) a polyamine having the structure:
l3 H2~CnE~2n ( NCnH2n ) 1~M2 where R3 is hydrogen or methyl; n is an integer 2 through 6; ancl x is an integer 0 throug~l 3 and (2) an acid such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, phosphoric acid ancl acetic acid. Specific examples of polyamines are ethylene diamine, propylene diamine, hexamethylene diamine, diethylenetriamine, tetra-ethylenepentamine, and bis(3-aminopropyl)amine.
Another reactant is an acid salt of a water-soluble poly-aminopolyamide. The polyaminopolyamide is derived by reaction of a dicarbo~ylic acid and a polyalkylenepolyamine in a mole ratio of polyalkylenepolyamine to dicarboxylic acid of from about 0.8:1 to about 1.~:1. Particularly suitable dicarbox~
ylic acids are diglycolic acid and saturated aliphatic dicar-boxylic acids containing from 3 through 10 carbon atoms such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
Other suitable dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid and alpha-unsaturated dicar-boxylic acids such as maleic acid, fumaric acid, itaconic acid, glutaconic acid, citraconic acid and mesaconic acid.
The available anhydrides of the above acids can be used for preparing the water-soluble polyaminopolyamide as ~ell as the esters of the acids. Mixtures of two or more of the above acid moieties can be employed if desired.
A number of polyalkylenepolyamines, including poly-ethylenepolyamines, polypropylenepolyamines, polybutylene-polyamines and the like can be employed to produce the poly-aminopolyamide. mhe polyal~ylenepolyamine employed will havetwo primary amine groups and can be represented as polyamines in which the nitrogen atoms are linked together by groups of the formula -CnH2n- where n is a small integer greater than unity and preferably 2 thro~lgh 6, and the number of such groups in the molecule ranges from -two up to about eight. ~he nitrogen atoms can be attached to adjacent carbon atoms in the group -CnM2n- or to carbon atoms farther apart, but not to the same carbon atoms. Polyamines such as diethylenetriamine, triethylenetetramine, tetraethvlenepentamine, and bis(3-amino-propyl)amine, which can be obtaine~ in reasonably pure form are suitable for preparing water-soluble polyaminopolyamides.
Other polyallcylenepolyamines that can be used include metl~yl bis(3-aminopropyl)amine; methyl bis(2-aminoethyl) amine; and 4,7-dimethyl-triethylenetetramine. Mi~tures of polyalkylene-polyamines can be used, if desired.
~he above polyalkylenepolyamines can be represented by the formula l3 H2NCnH2n ( NCnH2n ) yMH2 where P~3 is hydrogen or methyl; n is an integer 2 through 6, as above set forth, and y is an integer 1 through 3. Other polyalkylenepolyamines that can be employed and which are not included in the above formula include 1,4-bis(3-aminopropyl)-piperazine and 1-(2-aminoethyl)piperazine.
The spacing of an amino group on the polyaminopolyamide can be increased if desired. ~his can be accomplished by substituting a diamine such as ethylenediamine, propylene-diamine, he~amethylenediamine and the like for a portion of the polyalkylenepolyamine. For this purpose, up to about ~0%
of the polyalkylenepolyamine can be replaced by a molecularly equivalent amount of diamine. I1sually, a replacement of about 50~ or less will be adequate.
Temperatures employed for carrying out reaction between the dicarboxylic acid and the polyalkylenepolyamine to form the water-soluble polyaminopolyamide can vary from about 110C. to about 250C. or hi~her at atmospheric pressure. For most purposes, temperatures between about 1~0~. and 210C.
are preferred. The time of reaction will vary inversely with reaction temperatures employed and usually will be from about 1/2 to 2 hours. The reaction is desirably continued to sub-stantial completion, as determined by -the amount of water ~, evolved. In carrying out the reaction, it is preferred to use an amount of dicarbo~ylic acid sufficient to react sub-stantially completely with the primary amine groups of the polyalkylenepolyamine but insufficient to react with the secondary amine groups and/or tertiary amine groups to any substantial extent. This will usually require a mole ratio oE polyalkylenepolyamine to dicarboxylic acid of from about 0.9:1 to about 1.2:1. However, mole ratios of rrom about 0.8:1 to about 1.4:1 can be used.
The following example is illustrative of the preparation of a suitable water-soluble polyaminopolyamide for use as its salt in the preparation of the precondensate.
Example ~
A water-soluble polyaminopolyamide for use as its acid salt was formed by adding 146 parts (weight) of adipic acid slowly, with stirring, to 100 parts (weight) of diethylene-triamine in a reaction vesse] equipped with a s-tirrer, ther-mometer and a condenser for collecting water distillate. The reaction mixture was stirred and heated at a temperature of 20 from about 170C. to 175C. until amide formation was com-plete. After air cooling to approximately 140C., hot water was added with stirring to provide about a 50% solids solution of polyaminopolyamide resin having an intrinsic viscosity of 0.14 measured on a 2% solution in aqueous 1 M NH~Cl at 25C.
The preferred procedure for use in forming the precon-densate as set forth in the rirst step of the process of this invention is described below.
Into a reaction vessel are placed about one mole of dicyandiamide (cyanoguanidine), from about 3/~r mole to about 1-1/2 moles of formaldehyde, water-soluble polyaminopolyamide in an amount sufficient to provide from about 1/8 to about 1/2 of an equivalent of basic nitrogen (as distinguished from the amide nitrogens of the polyaminopolyamide), and an acid in an amount equivalent to the amount of the basic nitrogen of the polyaminopolyamide. Suitable acids include sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, hydrobromic acid and hydroiodic acid. ~ater is conveniently employed as the reaction medium and sufficient water should be present in the mixture to provide an aqueous reaction mass that can be easily agitated (as by stirring) under reaction conditions. ~he amount of water employed is well within the skill of one versed in -t~le art having before him the teachings of this invention. ~he acid forms the polyaminopolyamide acid salt reactant.
The aqueous mixture is subsequently heated to reflux tem-perature (about 95C.-105C.) and refluxed for a period of time of about 15 minutes to about 30 minutes (or longer, if desired). Subsequently, the ammonium salt is added in an amount such that there will be from about 0.7 equivalent to about 1.2 equivalents (preferably about 1 equivalent) of basic nitrogen derived from the salt of the polyaminopolyamide and the ammonium salt present in the reaction mixture. ~hus, for example, when the polyaminopolyamide is employed in an amount equal to 1/2 (0.5) equivalent of basic nitrogen, the amount of ammonium salt employed will be such as to provide from about 0.2 equivalent to about 0.7 equivalent of basic nitrogen. 'rhe resulting mixture is heated to reflux and maintained at reflux temperature for about 1 to about 4 hours. Somew}lat shorter periods of time can be used if the heating is carried out under moderate pressure.
In the second step of the process of this invention, there is added to the precondensate solution from 0.30 to 0.45 mole and preferably from 0.35 to 0.~0 mole of urea per equiva-lent of basic nitrogen derived from the salt of the polyamino-polyamide and the ammonlum salt. The resulting mixture is then heated to about 80 to about 110C. and maintained at about 80 to about 110C. until a solution of modified precon-densate is formed. T}lis will usually require a period of time from about 0.5 hour to about 1.5 hours.
In steps (3) and (4) of the process of this invention, there are added to the modified precondensate from about 1.25 to about 3.75 moles of formaldehyde and the resulting mixture is then heated to between about 60 and about 100C. and main-tained thereat until the viscosity of an aqueous solution of L8~
the resinous reaction product, when measured at a solids con-tent of 50% at 25C. is Erom about U to ~ ancl preferably from about V to W, on the Gardner-Holdt scale. lhis will usually require a period of time of from about 20 minutes to about 3 hours. The aqueous solution is then diluted with water to a solids content of less than about 35% and pxeferably from about 15% to about 25% to terminate the reaction, and the pH
is adjusted to from about 6 to about 7.5 to provide storage stability.
If desired, the water-soluble thermosettable resinous compositions produced in accordance with the process of this invention can be further modified. Post modification is pre-ferably carried out by dilu-ting the solution of step ~4), if necessary, to a solids content less than 35~, adding to the solution from 0.03 to 0.75 mole and preferably ~rom 0.05 to 0.60 mole, per mole of formaldehyde added in step (3), o~ epi-halohydrin or a nitrogen-containing compound of the formula NFIRR', where R and R' are independently hydrogen, alkyl or hydroxyalkyl and, when R is hydrogen, R' is also aminoalkyl or an amido group, heating the mixture to about 45 to about 70C. and maintaining thereat for about 0.5 hour to about 2 hours. The nitrogen-containing compounds which can be used in this step include ammonia, mono- or dialkyl-amines and par-ticularly alkylamines wherein the alkyl group(s) contain(s) 1 to 4 carbon atoms, the mono- or di- alkanolamines, the alkylene diamines and urea. Particularly preferred compounds for the post-modification step are epichlorohydrin, ammonia, dimethylamine, diethanolamine, ethylenediamine and urea.
mhe best mode now contemplated for carrying out this invention is illustrated by the following e~amples of specific embodiments thereof and the invention is not limited to these specific embodiments. All percentages are by weight unless otherwise specified and the Gardner-Holdt viscosity measure-ments were made at 25C.
Example 1 Part 1 - Into a reaction vessel fitted with reflux con-denser, mechanical stirrer and -thermometer were placed the following to provide a mixture of ingredients:
Ingredient Grams Polyaminopolyamide solution of 522 (1.24 equivalents Example ~ (50.6% solids) of basic nitrogen) Formaldehyde (37~ aqueous solu-tion) 320 (3.97 moles) 5 Dicyandiamide 269 (3.2 moles) H2S4 (98~) 55.5 (.66 mole) Sulfuric acid was added last and was added dropwise. During addition of the sulfuric acid the temperature of the mixture increased to about 40-45C. The mixture was then heated to a temperature of about 100C. and refluxed for about 15 minutes.
Following cooling of the mixture to 85C., 137.5 grams (1.04 moles) of ammonium sulfate were added and the mixture was heated at 100C. for about 3 hours. The resulting solution of precondensate weighed 1300 grams and contained 62.5% solids.
Part 2 - Into a reaction vessel equipped with a mechan-ical stirrer, thermometer and reflux condenser were placed 272.4 grams of the precondensate solu-tion of Part 1 and 15.6 grams (0.26 mole) of urea. The mixture was heated at 100C.
for 1 hour, cooled to 70C. and then 136 grams (1.58 moles) of 37% aqueous formaldehyde were added over a 5 minute period.
The mixture was maintained at 70C. until the Gardner-Holdt viscosity of the aqueous solution of the resinous reaction product was V-W. ~ater, 600 ml, was added to the reaction vessel and the contents thereo cooled to room temperature.
m~he pH of the aqueous solution of the resinous reaction pro-duct was adjusted to 7.0 by adding thereto 34 ml of a 25~
aqueous solution of sodium hydroxide. Total solids was 21.2%
and the Gardner-Holdt viscosity of the aqueous solution was A-l .
Example 2 Part 1 - The procedure of Example 1, Part 1 was repeated and gave 1291 grams of a precondensate solution having a solids content of 62.1~.
Part 2 - Into a reaction vessel equipped with mechanical stirrer, thermometer and reflux condenser were placed 137.1 grams of the precondensate solution produced in Part 1, above,
3~
and 7.8 grams (0.13 mole) of urea. ~le mixture was heated at 100C~ for 1 hour, cooled to 70C. and then 68 grams t0.8~
mole) of 37% aqueous formaldehyde solution were added over a 5 minute period. The mixture was maintained at 70C~ until the Gardner-Holdt viscosity of the aqueous solution of the resinous reaction product was W. Water, 150 ml, was added to the vessel and the contents were cooled to 50C. ~ext, 3 grams (0.05 mole) of ethylenediamine were added to the vessel and the contents were heated at 70C. for 30 minutes, after which time the resulting solution was cooled to room temper-ature, diluted with 150 ml of water and the pH was adjusted to 6.9 with 25% aqueous sodium hydroxide. Total solids was 22.2~ and the Cardner-Holdt viscosity of the diluted solutlon was B .
Exam~le 3 The procedure of Example 2, Part 2 was repeated except that 6.3 grams (0.105 mole) of urea dissolved in 25 ml of water were substituted for the 3 grams of ethylenediamine and added to the vessel with the contents at 60C. Total so]ids was 21.7% and the Gardner-Holdt viscositv as A .
Example 4 The procedure of Example 2, Part 2 was repeated except that following the addition of formaldehyde, the mixture was heated at 65C. until the Gardner-Holdt viscosity was W , 25 12.1 grams (0.21 mole) of 29.4% aqueous ammonium hydroxide were substituted for the 3 grams of ethylenediamine and the pH
of the diluted solution was adjusted to 7Ø Total solids was 21.9% and the Gardner-Holdt viscosity was A .
Exam~le 5 The procedure of Example 2, Part 2 was repeated except that 136.2 grams of the precondensate solution of Example 1, Part 1 were substituted for the precondensate solution of Example 2, Part 1, 9.7 grams (0.105 mole) of epichlorohydrin were substituted for the ethylenediamine and added to the vessel with the contents at 50C., and the pH of the diluted solution was adjusted to 7Ø Total solids was -1.7% and the Gardner-Holdt viscosity was A-2.
The resinous reaction products produced in accordance with this invention are thermosettable and water-soluble.
~hey have particular utility as sizing accelerators for hydro-phobic cellulose reactive si~ing agents such as acid anhy-drides, isocyanates, and ketene dimers.
Hydrophobic acid anhydrides useful as cel]ulose reactivesi~ing agents for paper include (A) rosin anhydride (see U.S.
Patent 3,582,4G4); (B) anhydrides having the structure:
(I) R -C
R4-C ~
where each R4 is alike or different and is a saturated or unsaturated hydrocarbon radical containing more than 7 and preferably 8 to 30 carbon atoms and is preferably selected Erom the group consisting of alkyl, alkenyl, aralkyl, aral-kenyl and alkaryl radicals, and (C) cyclic dicarboxylic acid anhydrides having the structure:
~o (II) R4-R~ o where R4 is as above defined and R5 represents a dimethyl-ene or trimethylene radical. Specific examples of anhydrides of formula (I) are myristoyl anhydride, palmitoyl anhydride, oleoyl anhydride, and stearoyl anhydride. Substituted cyclic dicarboxylic acid anhydrides falling within the above formula (II) are substituted succinic and glutaric anhydrides such as isooctadecenyl succinic acid anhydride; n-hexadecenyl succinic acid anhydride, dodecyl succinic acid anhydride, decenyl succinic acid anhydride, octenyl succinic acicl anhydride, and heptyl glutaric acid anhydride.
Isocyana-tes that can be used as cellulose reac-tive sizing agents include rosin isocyanate and isocyanates having the formula R~NC0 where R~ is as above defined. Speci~ic examples of such isocyanates are octadecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, eicosyl isocyanate, docosyl isocyanate and 6--phenyldecyliso-cyanate. Polyisocyanates such as 1,18-octadecyl diisocyanate and 1,12-dodecyl diisocyanate wherein one long chain alkyl group serves two isocyanate radicals and imparts hydrophobic properties to the molecule as a whole are also useful.
Ketena dimers used as cellulose reactive sizing agents are dimers having the formula:
[R6CH=C=0]2 where R6 is a hydrocarbon radical, such as an alkyl having at least 8 carbon atoms, cycloalkyl having at least 6 carbon atoms, aryl, aralkyl or alkaryl. In naming ketene dimers, the radical "R6" is named followed by "ketene dimer". mhus, phenyl ketene dimer is:
[ ~ -CH=C=0 benzyl ke~ene dimer is:
[ -C~2-CH=C=0 ]
and decyl ketene dimer is: [CloH21-CH=C=0]2- Examples of ketene dimers include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, beta-naphthyl and cyclohexyl ketene dimers, as well as the ketene dimers prepared from montanic acid, naphthenic acid,~ ' -decylenic acid, ~ 'l-dodecylenic acid, palmi-t-oleic acid, oleic acid, ricinoleic acia, linoleic acid, lino-lenic acid, and eleostearic acid, as well as ketene dimers prepared from naturally occurring mixtures o~ fatty acids, such as those mixtures found in coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanut oil, rape oil, beef tallow, lard (leaf) and whale blubber. ~lixtures of any oE the above-named fatty acids with each other may also be used.
The following examples illustrate the use of the novel resinous compositions produced in accordance with this inven-tion with a known ketene dimer paper sizing agent. The ketenedimer sizing agent was in emulsion form and contained, prior to dilution, 6.0% of the ketene dimer prepared from a mixture of palmitic and stearic acids and 1.5% o-f cationic starch as emulsion stabilizer.
Examples ~ to 10 -Separate emulsions, each containing 0.10% ofc ketene dimer and 0.15% of one of the resinous reaction products of Examples 1 to 5 were prepared and evaluated in a pulp blend of 40%
newsblank, 30% Rayonier bleached kraft and 30% Weyerhaeuser bleached hardwood kraft pulp beaten to a Canadian standard freeness of 350 cc. The pulp was diluted to 2.55%, the emul-sion was added to the dilute stock and the pH was adjusted to 8. The stock was formed into handsheets with a basis weight of 40 lb./3000 ft.2 and the sheets were dried to a moisture content of 3 to 5%. Part of the sheets was given an ex-tra cure of 5 minutes at 105C. In each case, the amount of emul-sion used provided a total of 0.25% ketene dimer plus resinous reaction product, based on dry pulp weight.
The Table below sets forth the size test results on the paper sized in accorclance with Examples 6 to 10 and with a control emulsion containing 0.10~ ketene dimer and 0.15% of a resin produced according to the general procedure of ~xample 5 of U.S. Patent 3,840,486, a separate control being used for each series of tests. The resin solution used for the con-trol had a solids content of 31.4% and was obtained by heatinga mixture of 136.2 grams of the solution of Example 1, Part 1 and 68 grams of 37~ aqueous formaldehyde at 99C. until the 1~
Gardner-Holdt viscosity was X, adding 100 ml. of 5% aqueous sodium hydro~ide and cooling to room temperature. ~11 size properties given herein were determined by use of the ~ercules Sizing Tester using Test Solution No. 2 to ~0% reflectance.
Table Size Test Results ln Seconds (Average Resinous of 5 Samples) Reaction Cured for Product of Natural aging 5 min.
10~xampleExample Off Machine 1 day 7 days @ 105C.
COI~mROL - 3 71 101 27 8 3 3 56 ~ 327 15CONTROL - 4 ~3 56 114 9 ~ 3 5~ 94 362 2 29 3~ 105 The resinous compositions produced in accordance with this invention, when employed in combination with hydrophobic cellulose reactive sizing agents in the internal or surface sizing of paper, accelerate the rate at which sizing develops and provide high ultimate sizing on natural aging or oven curing. The compositions can be added either separately to - the paper pulp (for internal sizing) or separately to the paper sheet (for external sizing), either be-fore or after addition of sizing agent. Alternatively, the resinous compo-sition and sizing agent can be added at the same time to the paper pulp or paper sheet as separate aqueous emulsions or as a single emulsion comprised of the two ingredients. mhe range of proportions of the sizing agent and the resinous composi-tion can vary from about 1:3 to about 3:1 and the amount of resinous composition incorporated into the paper sheet will usually be from about .05~ to aboui .5~ (preferably from about .05% to about .25%) by weight based on the dry weight of the paper.
and 7.8 grams (0.13 mole) of urea. ~le mixture was heated at 100C~ for 1 hour, cooled to 70C. and then 68 grams t0.8~
mole) of 37% aqueous formaldehyde solution were added over a 5 minute period. The mixture was maintained at 70C~ until the Gardner-Holdt viscosity of the aqueous solution of the resinous reaction product was W. Water, 150 ml, was added to the vessel and the contents were cooled to 50C. ~ext, 3 grams (0.05 mole) of ethylenediamine were added to the vessel and the contents were heated at 70C. for 30 minutes, after which time the resulting solution was cooled to room temper-ature, diluted with 150 ml of water and the pH was adjusted to 6.9 with 25% aqueous sodium hydroxide. Total solids was 22.2~ and the Cardner-Holdt viscosity of the diluted solutlon was B .
Exam~le 3 The procedure of Example 2, Part 2 was repeated except that 6.3 grams (0.105 mole) of urea dissolved in 25 ml of water were substituted for the 3 grams of ethylenediamine and added to the vessel with the contents at 60C. Total so]ids was 21.7% and the Gardner-Holdt viscositv as A .
Example 4 The procedure of Example 2, Part 2 was repeated except that following the addition of formaldehyde, the mixture was heated at 65C. until the Gardner-Holdt viscosity was W , 25 12.1 grams (0.21 mole) of 29.4% aqueous ammonium hydroxide were substituted for the 3 grams of ethylenediamine and the pH
of the diluted solution was adjusted to 7Ø Total solids was 21.9% and the Gardner-Holdt viscosity was A .
Exam~le 5 The procedure of Example 2, Part 2 was repeated except that 136.2 grams of the precondensate solution of Example 1, Part 1 were substituted for the precondensate solution of Example 2, Part 1, 9.7 grams (0.105 mole) of epichlorohydrin were substituted for the ethylenediamine and added to the vessel with the contents at 50C., and the pH of the diluted solution was adjusted to 7Ø Total solids was -1.7% and the Gardner-Holdt viscosity was A-2.
The resinous reaction products produced in accordance with this invention are thermosettable and water-soluble.
~hey have particular utility as sizing accelerators for hydro-phobic cellulose reactive si~ing agents such as acid anhy-drides, isocyanates, and ketene dimers.
Hydrophobic acid anhydrides useful as cel]ulose reactivesi~ing agents for paper include (A) rosin anhydride (see U.S.
Patent 3,582,4G4); (B) anhydrides having the structure:
(I) R -C
R4-C ~
where each R4 is alike or different and is a saturated or unsaturated hydrocarbon radical containing more than 7 and preferably 8 to 30 carbon atoms and is preferably selected Erom the group consisting of alkyl, alkenyl, aralkyl, aral-kenyl and alkaryl radicals, and (C) cyclic dicarboxylic acid anhydrides having the structure:
~o (II) R4-R~ o where R4 is as above defined and R5 represents a dimethyl-ene or trimethylene radical. Specific examples of anhydrides of formula (I) are myristoyl anhydride, palmitoyl anhydride, oleoyl anhydride, and stearoyl anhydride. Substituted cyclic dicarboxylic acid anhydrides falling within the above formula (II) are substituted succinic and glutaric anhydrides such as isooctadecenyl succinic acid anhydride; n-hexadecenyl succinic acid anhydride, dodecyl succinic acid anhydride, decenyl succinic acid anhydride, octenyl succinic acicl anhydride, and heptyl glutaric acid anhydride.
Isocyana-tes that can be used as cellulose reac-tive sizing agents include rosin isocyanate and isocyanates having the formula R~NC0 where R~ is as above defined. Speci~ic examples of such isocyanates are octadecyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, eicosyl isocyanate, docosyl isocyanate and 6--phenyldecyliso-cyanate. Polyisocyanates such as 1,18-octadecyl diisocyanate and 1,12-dodecyl diisocyanate wherein one long chain alkyl group serves two isocyanate radicals and imparts hydrophobic properties to the molecule as a whole are also useful.
Ketena dimers used as cellulose reactive sizing agents are dimers having the formula:
[R6CH=C=0]2 where R6 is a hydrocarbon radical, such as an alkyl having at least 8 carbon atoms, cycloalkyl having at least 6 carbon atoms, aryl, aralkyl or alkaryl. In naming ketene dimers, the radical "R6" is named followed by "ketene dimer". mhus, phenyl ketene dimer is:
[ ~ -CH=C=0 benzyl ke~ene dimer is:
[ -C~2-CH=C=0 ]
and decyl ketene dimer is: [CloH21-CH=C=0]2- Examples of ketene dimers include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, beta-naphthyl and cyclohexyl ketene dimers, as well as the ketene dimers prepared from montanic acid, naphthenic acid,~ ' -decylenic acid, ~ 'l-dodecylenic acid, palmi-t-oleic acid, oleic acid, ricinoleic acia, linoleic acid, lino-lenic acid, and eleostearic acid, as well as ketene dimers prepared from naturally occurring mixtures o~ fatty acids, such as those mixtures found in coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanut oil, rape oil, beef tallow, lard (leaf) and whale blubber. ~lixtures of any oE the above-named fatty acids with each other may also be used.
The following examples illustrate the use of the novel resinous compositions produced in accordance with this inven-tion with a known ketene dimer paper sizing agent. The ketenedimer sizing agent was in emulsion form and contained, prior to dilution, 6.0% of the ketene dimer prepared from a mixture of palmitic and stearic acids and 1.5% o-f cationic starch as emulsion stabilizer.
Examples ~ to 10 -Separate emulsions, each containing 0.10% ofc ketene dimer and 0.15% of one of the resinous reaction products of Examples 1 to 5 were prepared and evaluated in a pulp blend of 40%
newsblank, 30% Rayonier bleached kraft and 30% Weyerhaeuser bleached hardwood kraft pulp beaten to a Canadian standard freeness of 350 cc. The pulp was diluted to 2.55%, the emul-sion was added to the dilute stock and the pH was adjusted to 8. The stock was formed into handsheets with a basis weight of 40 lb./3000 ft.2 and the sheets were dried to a moisture content of 3 to 5%. Part of the sheets was given an ex-tra cure of 5 minutes at 105C. In each case, the amount of emul-sion used provided a total of 0.25% ketene dimer plus resinous reaction product, based on dry pulp weight.
The Table below sets forth the size test results on the paper sized in accorclance with Examples 6 to 10 and with a control emulsion containing 0.10~ ketene dimer and 0.15% of a resin produced according to the general procedure of ~xample 5 of U.S. Patent 3,840,486, a separate control being used for each series of tests. The resin solution used for the con-trol had a solids content of 31.4% and was obtained by heatinga mixture of 136.2 grams of the solution of Example 1, Part 1 and 68 grams of 37~ aqueous formaldehyde at 99C. until the 1~
Gardner-Holdt viscosity was X, adding 100 ml. of 5% aqueous sodium hydro~ide and cooling to room temperature. ~11 size properties given herein were determined by use of the ~ercules Sizing Tester using Test Solution No. 2 to ~0% reflectance.
Table Size Test Results ln Seconds (Average Resinous of 5 Samples) Reaction Cured for Product of Natural aging 5 min.
10~xampleExample Off Machine 1 day 7 days @ 105C.
COI~mROL - 3 71 101 27 8 3 3 56 ~ 327 15CONTROL - 4 ~3 56 114 9 ~ 3 5~ 94 362 2 29 3~ 105 The resinous compositions produced in accordance with this invention, when employed in combination with hydrophobic cellulose reactive sizing agents in the internal or surface sizing of paper, accelerate the rate at which sizing develops and provide high ultimate sizing on natural aging or oven curing. The compositions can be added either separately to - the paper pulp (for internal sizing) or separately to the paper sheet (for external sizing), either be-fore or after addition of sizing agent. Alternatively, the resinous compo-sition and sizing agent can be added at the same time to the paper pulp or paper sheet as separate aqueous emulsions or as a single emulsion comprised of the two ingredients. mhe range of proportions of the sizing agent and the resinous composi-tion can vary from about 1:3 to about 3:1 and the amount of resinous composition incorporated into the paper sheet will usually be from about .05~ to aboui .5~ (preferably from about .05% to about .25%) by weight based on the dry weight of the paper.
Claims (15)
1. A process for preparing improved water-soluble thermosettable resinous compositions containing dicyandiamide-formaldehyde condensates which process comprises (1) forming a precondensate solution by refluxing for about 1 to about 4 hours an aqueous mixture of (a) a base reaction product of 1 mole of dicyandiamide, 0.75 mole to 1.5 moles of formaldehyde and an acid salt of a water-soluble polyaminopolyamide in an amount sufficient to provide from about 0.125 to about 0.5 equivalent of basic nitrogen and (b) an ammonium salt in an amount such that there will be from 0.7 equivalent to about 1.2 equivalents of basic nitrogen derived from the salt of the polyaminopolyamide and the ammonium salt in the aqueous medium, (2) adding to the precondensate solution from 0.30 to 0.45 mole of urea per equivalent of basic nitrogen derived from the salt of the polyaminopolyamide and the ammonium salt, and heating the aqueous mixture at about 80° to about 110°C.
for about 0.5 to about 1.5 hours until a solution of modified precondensate is formed, (3) adding from about 1.25 to about 3.75 moles of formaldehyde to the aqueous solution of modified precondensate and (4) heating the resulting mixture at about 60° to about 100°C. until the viscosity of an aqueous solution of the resulting reaction product at a solids content of 50%
is from about U to Z on the Gardner-Holdt scale.
for about 0.5 to about 1.5 hours until a solution of modified precondensate is formed, (3) adding from about 1.25 to about 3.75 moles of formaldehyde to the aqueous solution of modified precondensate and (4) heating the resulting mixture at about 60° to about 100°C. until the viscosity of an aqueous solution of the resulting reaction product at a solids content of 50%
is from about U to Z on the Gardner-Holdt scale.
2. The process of claim 1 comprising the additional steps of diluting the solution of step (4), if necessary, to a solids content less than 35%, adding from 0.03 to 0.75 mole, per mole of formaldehyde added in step (3) of epihalo-hydrin or a nitrogen-containing compound of the formula NHRR' where R and R' are independently hydrogen, alkyl or hydroxy-alkyl and, when R is hydrogen, R' also is aminoalkyl or an amido group and heating the resulting mixture at about 45° to about 70°C. for about 0.5 hour to about 2 hours.
3. The process of claim 1 wherein the salt of the poly-aminopolyamide is the sulfuric acid salt of a water-soluble polyaminopolyamide derived from adipic acid and diethylenetri-amine.
4. The process of claim 3 wherein the ammonium salt is ammonium sulfate.
5. The process of claim 4 wherein step (4) is carried out until the reaction product has a viscosity of V to W on the Gardner-Holdt scale.
6. The process of claim 5 comprising the additional steps of diluting the solution of step (4), if necessary, to a solids content less than 35%, adding from 0.03 to 0.75 mole of epichlorohydrin per mole of formaldehyde added in step (3), and heating the resulting mixture at about 45° to about 70°C.
for about 0.5 hour to about 2 hours.
for about 0.5 hour to about 2 hours.
7. The process of claim 5 comprising the additional steps of diluting the solution of step (4), if necessary, to a solids content less than 35%, adding from 0.03 to 0.75 mole, per mole of formaldehyde added in step (3), of a nitrogen-containing compound of the formula NHRR' where R and R' are independently hydrogen, alkyl or hydroxyalkyl and, when R is hydrogen, R' also is aminoalkyl or an amido group and heating the resulting mixture at about 45° to about 70°C. for about 0.5 hour to about 2 hours.
8. The process of claim 7 wherein the nitrogen-contain-ing compound is ammonia.
9. The process of claim 7 wherein the nitrogen-contain-ing compound is urea.
10. The process of claim 7 wherein the nitrogen-contain-ing compound is ethylenediamine.
11. The water-soluble thermosettable resinous composi-tion produced by the process of claim 1.
12. An aqueous solution of the composition of claim 11 having a solids content of about 15% to about 25% and a pH of from about 6 to about 7.5.
13. The water-soluble thermosettable resinous composi-tion produced by the process of claim 2.
14. An aqueous solution of the composition of claim 13 having a solids content of about 15% to about 25% and a pH of from about 6 to about 7.5.
15. In the method of sizing paper wherein an emulsion of a hydrophobic cellulose reactive sizing agent is employed, the improvement wherein there is employed in combination therewith an aqueous solution of the resinous composition of claim 11 or claim 13, the amount of resinous composition being from about 0.05 to about 0.5% by weight based on the weight of paper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/328,753 US4383077A (en) | 1981-12-08 | 1981-12-08 | Dicyandiamide-formaldehyde condensates modified with urea and process for preparing the same |
| US328,753 | 1981-12-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1188836A true CA1188836A (en) | 1985-06-11 |
Family
ID=23282289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000416581A Expired CA1188836A (en) | 1981-12-08 | 1982-11-29 | Dicyandiamide-formaldehyde condensates modified with urea and process for preparing the same |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4383077A (en) |
| CA (1) | CA1188836A (en) |
| PH (1) | PH17854A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2092955C (en) * | 1992-04-06 | 1999-01-12 | Sunil P. Dasgupta | Stable blend of ketene dimer size and colloidal silica |
| US6395189B1 (en) | 1999-03-01 | 2002-05-28 | Polymer Ventures, Inc. | Method for the control of biofilms |
| US6149822A (en) * | 1999-03-01 | 2000-11-21 | Polymer Ventures, Inc. | Bio-film control |
| US9440890B2 (en) | 2010-04-30 | 2016-09-13 | Koch Agronomic Services, Llc | Reaction products and methods for making and using same |
| CN102939275B (en) * | 2010-04-30 | 2015-08-26 | 科奇农业服务有限公司 | Reactor product and preparation also use its method |
| US8157010B2 (en) | 2010-09-21 | 2012-04-17 | Polymer Ventures, Inc. | Treatment of subterranean formations |
| US9707520B2 (en) | 2012-01-18 | 2017-07-18 | Nch Corporation | Composition, system, and method for treating water systems |
| ES2795954T3 (en) | 2012-01-18 | 2020-11-25 | Nch Corp | Composition and procedure for treating hydraulic systems |
| US8631868B1 (en) | 2013-02-27 | 2014-01-21 | Polymer Ventures Inc. | Treatment of subterranean formations |
| US9506016B2 (en) | 2013-11-06 | 2016-11-29 | Nch Corporation | Composition and method for treating water systems |
| US9441190B2 (en) | 2013-11-06 | 2016-09-13 | Nch Corporation | Composition and method for treating water systems |
| EP3936209A1 (en) | 2020-07-07 | 2022-01-12 | Ahlstrom-Munksjö Oyj | Filtration media |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2440988A (en) | 1944-03-14 | 1948-05-04 | Geigy Ag J R | Dicyanodiamide condensation products and a process for making same |
| US2973239A (en) * | 1956-11-19 | 1961-02-28 | United Merchants & Mfg | Color fixing agents |
| US3594272A (en) * | 1969-05-05 | 1971-07-20 | Ciba Geigy Corp | Polymeric products of alkylene-polyamine-dihydrohalides,dicyandiamide,formaldehyde and epichlorohydrin and their use as retention aids in the manufacture of paper |
| US3840486A (en) * | 1972-07-03 | 1974-10-08 | Hercules Inc | Water-soluble,thermosettable resinous compositions prepared from dicyandiamide,hcho,ammonium salt and a salt of an aminopolyamide and method for preparing the same |
| US3914155A (en) * | 1972-09-07 | 1975-10-21 | Georgia Pacific Corp | Polyamide/formaldehyde/epichlorohydrin wet strength resins and use thereof in production of wet strength paper |
| US3951921A (en) * | 1973-02-21 | 1976-04-20 | Hercules Incorporated | Cationic water soluble resinous reaction product of polyaminopolyamide-epichlorohydrin and nitrogen compound |
-
1981
- 1981-12-08 US US06/328,753 patent/US4383077A/en not_active Expired - Lifetime
-
1982
- 1982-11-23 PH PH28180A patent/PH17854A/en unknown
- 1982-11-29 CA CA000416581A patent/CA1188836A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| PH17854A (en) | 1985-01-09 |
| US4383077A (en) | 1983-05-10 |
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