CA2148055A1 - Agents having high nitrogen content and high cationic charge based on dicyanimide, dicyandiamide or guanidine and inorganic ammonium salts - Google Patents
Agents having high nitrogen content and high cationic charge based on dicyanimide, dicyandiamide or guanidine and inorganic ammonium saltsInfo
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- CA2148055A1 CA2148055A1 CA002148055A CA2148055A CA2148055A1 CA 2148055 A1 CA2148055 A1 CA 2148055A1 CA 002148055 A CA002148055 A CA 002148055A CA 2148055 A CA2148055 A CA 2148055A CA 2148055 A1 CA2148055 A1 CA 2148055A1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
- D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/06—After-treatment with organic compounds containing nitrogen
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
-
- 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
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/02—Agents for preventing deposition on the paper mill equipment, e.g. pitch or slime control
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
Abstract
The present invention describes polymers having high nitrogen content and high cationic charges derived from dicyanimide, dicyandiamide or guanidine and inorganic ammonium salts. The new compositions are useful in the pulp and paper industries as pitch control agents, as well as adjuvants such as in felt cleaner applications. The new materials are also useful in paper sizing, as retention aids, as antistatic agents, and as coagulants and flocculating agents.
Description
AGENTS HAVING HIGH NITROGEN CONTENT AND HIGH CATIONIC CHARGE BASED
ON DICYANIMIDE, DICYANDIAMIDE OR GUANIDINE AND INORGANIC AMMONIUM
SALTS
BACKGROUND OF THE INVENTION
The present invention relates to compositions of matter which are useful in chemical, pulp and paper, mining, clay, textile and leather industries. The polymers and (co)polymers of the present invention can be used in pulp and paper industries as pitch control agents, as chemical additives and adjuvants such as felt cleaner, as tack reducing agents on paper machines, as paper sizings, as retention aids, additives for colorants, and as antistatic agents. The inventive materials are also useful as flame retardants in flame retardant formulations, as dispersing agents, as antimicrobials, as coagulants and as flocculating agents. Further still, the novel polymers and copolymers described herein are useful in compositions with sequestering agents.
The present invention further relates to linear and/or cyclic guanidine or polyguanidine or (co)polyguanidine, dicyanamide, polyguanidine ammonium chloride(PGAC) or polyguanidine urea ammonium chloride (PGUAC) which are further reactedwith cationic charged or multiply cationic charged reactive agents of the non-formaldehyde type.
21 4~055 Such products having cationic or multiple cationic charge are disclosed, for example, in U.S. Patent Nos. 4,891,422 and 4,902,779 (now Re 34,486), and in 5,135,613, these disclosures being fully incorporated herein by reference. U.S.
Patent Re 34,486 describes cationic polyguanidine and its alloy-type formation by 5 condensation according to the following reaction:
Dicyandiamide + Formaldehyde + Ammonium chloride (C2H4N4) (CH20) (NH4CI) H+/60 to 105C
NH C NH C NH C NH
ll ll ll N N N
_ n (PGAC) Alkylamine (C1-C12) or optionally hydroxyalkylamine, and urea are reacted to form a regular polyguanidine chain of the uncharged type as represented by the general -structure:
NH C NH C NH C NH HCI
Il l 11 1 11 N CN N CN N
CH20H Rl CH20H
_ n (I) where n is less than 100,000. The (co)polyguanidines are defined by the formulaeB(1), B(3), B(4), B(5), B(6), B(7) as disclosed in Re 34,486, and are further reacted with cationic or multiply cationic charged agents defined by formula B(2) and agents (a, b, c, d, e, f, g, h, i) also disclosed therein. The R1 and R2 moieties are well defined in U.S. Patent Re 34,486 and its contents are fully incorporated herein by reference.
The guanidines or polyguanidines of structural formula (I) according to Re 34,486 differ from those of the present invention. The reaction of dicyandiamidewith alkyl amine proceeds via a condensation process to form an inert (i.e., uncharged or non-cationic) guanidine or polyguanidine with high insoluble matter and is well known. For example, these products are described in:
German Patent No. 851,001, Ger. Offen. DE 3,400,051, U.S. Patent Nos.
2,649,354; 3,873,266; 3,488,742; 4,410,652; 4,439,303; 4,439,208; and in Fr.
Demande FR 2 567 897.
French patent 2,567,897 and the references cited therein describe condensation products for fixing, dyeing, and printing, and which are prepared by catalytic condensation of alkyl amine with dicyandiamide in the presence of a zinc chloride catalyst (optionally containing less than 50 mol% dicarboxylic acid or its ester and also aminoplasts, epihalohydrins and/or formaldehyde or its donors).
However, the use of zinc in the condensation process poses environmental concerns 5 such as restrictions regarding the disposal of waste zinc which is a known water pollutant.
U.S. Patent No. 3,873,266 and 2,649,354 disclose that these condensation products from diethylenetriamine and dicyandiamide are not homogeneous, are very difficult to be handle, and are not completely water soluble. The '266 patent 10 describes the process of making a solution from condensation products of (A) polyamines and (B) cyanamides, or their water soluble salts. These processes, however, require long reaction time and are very unpractical on an industrial scale.
U.S. Patent No. 4,410,652, incorporated herein reference, describes the use of the reaction product from an amine with cyanamide, dicyandiamide, guanidine or 15 biguanidine as a wet fastness agent for direct dyes on cellulose substrates. The '652 patent describes an in situ condensation in situ process which is very difficult when carried out on an industrial scale. A drawback to this kind of process is that the reaction mixture cannot properly be mixed. Hence the reagents do not properly migrate within the reaction chamber, leading to non-uniformity of reaction product.
20 This type of process also suffers from an inability to control the rate of decomposition of -CN groups. Accordingly, the dicyandiamides, dicyanamides, diguanidines or biguanidines thus formed can undergo cracking through loss of -CN radicals.
SUMMARY OF THE INVENTION
The present invention relates to non-formaldehyde cationic or multiply cationic 5 charged guanidine or polyguanidine products. These compounds are prepared from an inorganic ammonium salt, such as ammonium halide, ammonium sulfate, ammonium nitrate, an amine and occasional urea and from a monomer selected from the following:
1. Dicyandimide and its salts (preferably, ammonium, calcium or sodium):
1 0 HN(CN)2 2. Guanidine: H2N - C(NH) - NH2 3. Guanidine salts: H2N - C(NH) - NH2 . X
where X = HCI or HBr, acetate, carbonate, phosphate, or sulfate;
ON DICYANIMIDE, DICYANDIAMIDE OR GUANIDINE AND INORGANIC AMMONIUM
SALTS
BACKGROUND OF THE INVENTION
The present invention relates to compositions of matter which are useful in chemical, pulp and paper, mining, clay, textile and leather industries. The polymers and (co)polymers of the present invention can be used in pulp and paper industries as pitch control agents, as chemical additives and adjuvants such as felt cleaner, as tack reducing agents on paper machines, as paper sizings, as retention aids, additives for colorants, and as antistatic agents. The inventive materials are also useful as flame retardants in flame retardant formulations, as dispersing agents, as antimicrobials, as coagulants and as flocculating agents. Further still, the novel polymers and copolymers described herein are useful in compositions with sequestering agents.
The present invention further relates to linear and/or cyclic guanidine or polyguanidine or (co)polyguanidine, dicyanamide, polyguanidine ammonium chloride(PGAC) or polyguanidine urea ammonium chloride (PGUAC) which are further reactedwith cationic charged or multiply cationic charged reactive agents of the non-formaldehyde type.
21 4~055 Such products having cationic or multiple cationic charge are disclosed, for example, in U.S. Patent Nos. 4,891,422 and 4,902,779 (now Re 34,486), and in 5,135,613, these disclosures being fully incorporated herein by reference. U.S.
Patent Re 34,486 describes cationic polyguanidine and its alloy-type formation by 5 condensation according to the following reaction:
Dicyandiamide + Formaldehyde + Ammonium chloride (C2H4N4) (CH20) (NH4CI) H+/60 to 105C
NH C NH C NH C NH
ll ll ll N N N
_ n (PGAC) Alkylamine (C1-C12) or optionally hydroxyalkylamine, and urea are reacted to form a regular polyguanidine chain of the uncharged type as represented by the general -structure:
NH C NH C NH C NH HCI
Il l 11 1 11 N CN N CN N
CH20H Rl CH20H
_ n (I) where n is less than 100,000. The (co)polyguanidines are defined by the formulaeB(1), B(3), B(4), B(5), B(6), B(7) as disclosed in Re 34,486, and are further reacted with cationic or multiply cationic charged agents defined by formula B(2) and agents (a, b, c, d, e, f, g, h, i) also disclosed therein. The R1 and R2 moieties are well defined in U.S. Patent Re 34,486 and its contents are fully incorporated herein by reference.
The guanidines or polyguanidines of structural formula (I) according to Re 34,486 differ from those of the present invention. The reaction of dicyandiamidewith alkyl amine proceeds via a condensation process to form an inert (i.e., uncharged or non-cationic) guanidine or polyguanidine with high insoluble matter and is well known. For example, these products are described in:
German Patent No. 851,001, Ger. Offen. DE 3,400,051, U.S. Patent Nos.
2,649,354; 3,873,266; 3,488,742; 4,410,652; 4,439,303; 4,439,208; and in Fr.
Demande FR 2 567 897.
French patent 2,567,897 and the references cited therein describe condensation products for fixing, dyeing, and printing, and which are prepared by catalytic condensation of alkyl amine with dicyandiamide in the presence of a zinc chloride catalyst (optionally containing less than 50 mol% dicarboxylic acid or its ester and also aminoplasts, epihalohydrins and/or formaldehyde or its donors).
However, the use of zinc in the condensation process poses environmental concerns 5 such as restrictions regarding the disposal of waste zinc which is a known water pollutant.
U.S. Patent No. 3,873,266 and 2,649,354 disclose that these condensation products from diethylenetriamine and dicyandiamide are not homogeneous, are very difficult to be handle, and are not completely water soluble. The '266 patent 10 describes the process of making a solution from condensation products of (A) polyamines and (B) cyanamides, or their water soluble salts. These processes, however, require long reaction time and are very unpractical on an industrial scale.
U.S. Patent No. 4,410,652, incorporated herein reference, describes the use of the reaction product from an amine with cyanamide, dicyandiamide, guanidine or 15 biguanidine as a wet fastness agent for direct dyes on cellulose substrates. The '652 patent describes an in situ condensation in situ process which is very difficult when carried out on an industrial scale. A drawback to this kind of process is that the reaction mixture cannot properly be mixed. Hence the reagents do not properly migrate within the reaction chamber, leading to non-uniformity of reaction product.
20 This type of process also suffers from an inability to control the rate of decomposition of -CN groups. Accordingly, the dicyandiamides, dicyanamides, diguanidines or biguanidines thus formed can undergo cracking through loss of -CN radicals.
SUMMARY OF THE INVENTION
The present invention relates to non-formaldehyde cationic or multiply cationic 5 charged guanidine or polyguanidine products. These compounds are prepared from an inorganic ammonium salt, such as ammonium halide, ammonium sulfate, ammonium nitrate, an amine and occasional urea and from a monomer selected from the following:
1. Dicyandimide and its salts (preferably, ammonium, calcium or sodium):
1 0 HN(CN)2 2. Guanidine: H2N - C(NH) - NH2 3. Guanidine salts: H2N - C(NH) - NH2 . X
where X = HCI or HBr, acetate, carbonate, phosphate, or sulfate;
4. Biguanidine: H2N - C(NH) - NH - C(NH) - NH2 15 5. (C1-C20) Alkyl guanidine or biguanidine, or aryl or alkylaryl guanidine or biguanidine;
6. Dicyandiamide: H2N - C(NH) - NH - CN
and sulfate or acetate salts;
7. Guanylurea: H2N - C(NH) - C(0) - NH2 (or guanyl thiourea) 8. Cyanamide: H2N - CN;
6. Dicyandiamide: H2N - C(NH) - NH - CN
and sulfate or acetate salts;
7. Guanylurea: H2N - C(NH) - C(0) - NH2 (or guanyl thiourea) 8. Cyanamide: H2N - CN;
5 9. Guanidine, biguanidine and dicyandiamide and urea (co)polymer;
10. Polycyclic guanidine (see, e.g., Re.34,486 Col.5, Line 65).
The above starting materials are reacted in a high boiling point solvent, in thepresence of an amine, for example, cycloamine, aromatic amine, and hydroxyalkyl amine. The preferred amines are alkyl amines defined by the general formula:
H2N(CH2cH(Y)NH)x H
wherein Y is hydrogen or lower alkyl (C1-C4) and where x is from 1 to 5.
More specifically the (co)polymer of the cyanoguanidine, dicyanimide, guanidine or biguanidine are formed with comonomers of ammonium salt, urea, and alkylamine.
-The most preferred comonomer is alkyl amine as exemplified by ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, methyl or ethyl or butyl alkanolamine, e.g., aminotrihydroxyethylenediamine, monopropanolamine, diethanolamine, crude diaminopropanol and glycolamine. The solvent is selected from high boiling point organic solvents, such as a glycol, optionally in admixture with water.
Hence, the present invention describes the condensation process for preparing non-formaldehyde cationic or multiply cationic charged agents from dicyandiamide or dicyanimide, guanidine or biguanidine, or polymers or (co)polymers thereof, withamine and occasional urea present, in the presence of ammonium chloride, ammonium bromide or ammonium iodide, ammonium sulfate, or ammonium nitrate.
The presence of either the ammonium salt or urea will facilitate the reaction of the -CN group of, for example, the dicyandiamide monomer without cracking, thereby giving better yield and a more uniform product.
Another aspect of the present invention is that the products prepared in accordance with this process, and even the products according to the methods of the patents described above, may be further reacted with the herein described cationic or multiply cationic charged agents, to produce desired cationic polymer or (co)polymeric material.
For Example, the amine and the polyguanidines of the prior art, (for example, U.S. Patent No. 2,649,354; 3,873,266; 4,410,652; 4,439,203; 4,439,208), are 2 ~ 48055 suitable for reaction with chain transfer agents B(a) to B(j) shown below. U.S. Patent Nos. 2,304,369 and 2,945,774 teach the reaction of urea with cationic or anioniccoupling agents from fatty acids, diethylenetriamine, in reaction with quaternization agents. These disclosures are fully incorporated by reference. Another example is U.S. Patent No. 4,410,652, which describes the reaction of guanidine with alkyl amine in situ at 160C. This process is very difficult to carry out on an industrial scale, leads to the cracking and decomposition of the nitrile groups and produces an extremely viscous material, which is a nonionic product. However, such a productcan be used further in the reaction of the present invention with cationic or multiply cationic charged agents. However, the products described above in the prior art patents are very sensitive to bleaching compositions and are susceptible to "bleeding"
and dye discoloration.
In contrast, the cationic polyguanidine or its (co)polymer described by this invention has excellent dye fastness, improved color yield and bleaching composition with little or no dye discoloration. More particularly, the guanidine and/or polyguanidine or a co-polymer thereof is reacted from 25C to 195C, preferably 35C to 165C, in organic solvent or an aqueous medium or an aqueous/organic solvent system with reactive cationic or multiple cationic agents. The reactions may be carried out in the presence of a chain transfer agent, such as 2,2-sulfonyl-bis hyd roxyethyl .
The mole ratio ranges of (I) amine derivative, (Il) ammonium salt and (Ill) guanidine monomer and (IV) occasional urea are as follows:
0.1-2.0 M: 0.5-2.0M: 0.05-2.25 M: 0.25-1.5 M
11 : 111 : lV
5 where ll is an ammonium salt.
When the reaction is carried out in the presence of urea, the mole ratio ranges are:
0.1-1.5 M: 0.25-1.5 M: 0.15-2.5 M: 0.5-2.0 M
ll : lll : IV
10 where ll is ammonium salt.
The general reaction can be written as follows:
Cyanoguanidine/orguanidine derivative + ammonium salt + alkyl amine + solvent ------> polymer/or (co)polymer + DEG + water ----> aqueous (co)polymer, where DEG is diethylene glycol.
15 More preferably, the reactant side of the reaction scheme is as follows:
Cyanoguanidine + Ammonium chloride + diethylenetriamine + diethyleneglycol (DCDA) (NH4CI) (DETA) (DEG) The guanidine, polyguanidine or (co)polyguanidine are formed at pH 4.0 to 1 1 .0 in either free or salts form. These are further reacted with cationic or multiply 20 cationic chain transfer agents. Representative chain transfer agents useful in the practice of the invention have present a substituent which is a halo atom (chlorine, 214~055 bromine, iodine), a sulfate group substituted with methyl or ethyl, methoxy, or ethoxy, or a nitrate anion present.
Compounds B(a)-B(I) are suitable chain transfer agents in the practice of this Inventlon:
B(a): [ Cl - CH2 - CH(OH) - CH2 - N+ (CH3)3] Cl- or (C6H15N0CI);
B(b) [ CH2 - CH - CH2 - N+(CH3)3 ]Cl- or (C6H14NOCI);
o B(c): [Cl-CH2-CH(OH)-CH2-N + (CH3)2-CH2-CH(OH)-CH2-N + (CH3)2-CH2-CH(OH)CH2CI]Cl-2, or (C12H28N203CI4);
B(d): [Cl-CH2-CH(OH)-CH2-N + (CH3)2-[CH2-CH(OH)-CH2-N + (CH3)2-]n -CH2CH(OH)-cH2cl]cl ~1 + nl B(e): [CH2/CH-CH2- N + (CH3)2-CH2-CH2- N + (CH3)2-CH2-CH-CH2]C1-2 O O
or (c12H26N2o2cl2);
( )() LCICH2CH(OH)-CH2-N (CH3)2-(CH2)6-N+(CH3)2-cH2- CH(OH)-CI]SO4~2 or (c15H34N2o6cl2s) ( )( ) [Cl CH2-CH(OH)-CH2-N (cH3)2-(cH2)6-N+(cH3)2-cH2-cH(oH)-cl]cl-2 or (C15H34N202Cl4) B(g): [Cl-CH2-CH(OH)-CH2- N + (CH3)2-NH-C(0)-NH-N + (CH3)2-CH2-CH(oH)-cH2-cl]cl 2 or (C11H26N403CI4);
B~h) LCH2fH-CH2-N+(CH3)2-NH-C(0)-NH-N (CH3)2-CH2-CH-CH21C( 2 (C1 1 H24N4O3cl2);
B(i): N,N,N,N N N - hexaalkyl-B-hydroxy-trimethylene diammonium halide [(R)3- N+ - CH2-CH(OH)-CH2 - N+(R )3]X-2 10where: R is C1-C4 alkyl R is alkyl or alklylene-alkyl having C1-C3 atoms and X is selected from the group the consisting of chloride, bromide or iodide;
B(j): tetrakis-hydroxymethyl)-phosphoniumhalide,hydroxide,oxalate,acetate, sulfate, or phosphate;
B(k): 2,2-sulfonyl-hydroxyethyl;
_ B(l): a mixture of any of (a) through (k), as illustrated, for example, in Re.34,486 Example Nos. 15A, 16A, No.29-44 (steps 1 to 7).
Thus, first ammonium halide, sulfate or nitrate, is reacted with one of dicyanimide or dicyandimide or biguanidine, at 65-195C to form a polyguanidine 5 cation ammonium salt which will further react with alkylamine to generate the desired polymer or (co)polymer. This reaction can be written as follows:
H2N-C(NH)-NH-CN + NH4CI + H2N(CH2CH2N)n H + H20/DEG
(DCDA) (AMC) (DETA) --->[H2N-C(NH)-NH-C(NH)-NH2+]CI-+(H2N-CH2CH2)2NH
--HN C NH C NH (CH2CH2 NH)2-- Cl-(2m~
Il 11 NH2 + NH2 +
_ m The reaction is carried out at of from 110 to 200C, and preferably from 110 to 165C forming the polyguanidineor (co)polyguanidineof the formula [ - HN - C(NH) - NH - C(NH) - NH - R- ]m, where R represents H or (C1-C4) alkyl, optionally interrupted by oxygen, sulfur or nitrogen; R may also incorporate a saturated or unsaturated cyclic hydrocarbon nuclei in which the total number of carbon atoms directly interposed between the pair of nitrogen atoms linked between 0 guanidine radicals and amine radicals used and R is more than 1 and less than 500;
m is less than 100,000 When urea is used in addition to the ammonium salt reactant and an amine reactant, the (co)polyguanidine has the following structure:
[-NH-C(NH)-N-C(NH)-NH-R-]n I
C = O
I
[-NH-C(NH)-NH-C(NH)-NH-R-]n, where Ris as previously defined and n isfrom 1 to 5.
Secondly, the polyguanidines and (co)polyguanidines are reacted with cationic 10 or multiply cationic charged agents to form improved non-formaldehyde cationic polymeric materials.
The new non-formaldehyde improved cationic charged guanidine or polyguanidine according to the invention or its (co)polymer may have the following structures:
NH O
C NH C NH C NH C NH - C NH X Cl~(2n N NH NH2+
CHOH
N+
_ n n is less than 100,000 2t 48055 Y_ or:
NlI ~ Nl-l li; NlI --~ NlI
~'112 ~ 2 Cl- N (ctl3)2 1l2 Cl- N (Clt3)2 ~tl7 CllOll~Ctl2 L---~ Nl l ~ Nl l--~--Nl l--~--Nl l ---where n is less than 100,000 and X is either-H, -CN, -NH(CN), NH2 - C(NH)-, -C(0)-NH2.
The products according to the invention have utility as flame retardants, 5 dispersing agents, antistatic agents, paper sizing, as pitch control agents, in felt cleaner compositions, antimicrobial, precipitant and flocculating agents. The cationic or multiply cationic charged polyguanideines may also be used in combination with 2~ 48055 a sequestering agent such as a phosphonic acid or an aminotricarboxylic acid. The following non-limiting examples demonstrate various aspects of the invention, namely, polymeric and copolymeric products, their preparation and their utility. All parts and percentages are by weight and temperature is expressed in degrees 5 Centigrade.
Example No.1 A 500 ml resin kettle flask was equipped with a condenser, a mechanical stirrer, and a thermometer. To the flask was added diethylene triamine (71.719, 0.695 mole).
The triamine was heated to 55-60 with stirring, followed by the addition of ammonium chloride (44.889, 0.824 mole), added gradually over 20 minutes. The mixture was heated up to 95-100 and then mixed for 15 minutes. Diethylene glycol (12.99 9) was then added and the reaction temperature brought to a range of 95-105 until the reaction mixture was clear. Dicyandiamide (DCDA) (76.29 9, 0.908 mole) was added gradually as 10 portions over 50 minutes and the reaction was maintained at the prevailing temperature for 15 minutes. Gradually the reactor temperature was increased at a rate of 4-5/min. until reaching 195 according to the following protocol: upon reaching 165-170, the reaction was maintained within this temperature range for 2 hours; upon reaching 180-195, the reaction was maintained for an additional 2 hours. The reactor was cooled to 95-100 followed by the addition of hot water (50-95C) (100.00 9) in two equal portions.
21 4~055 The reaction medium was stirred until a uniform solution was obtained. The product obtained had the following physical and chemical properties:
Appearance: yellow to light yellow Sp.Gravity: 1.15 - 1.24 g/ml 10% pH (as is): 8.50 - 9.0 Viscosity (c.p.s.)(at 16): 275-500 cps (LVF, spindle #2, 60 rpm).
Example No. 2 Example No. 1 was repeated using the quantities of reactants previously specified according to the following general procedure. Diethylene triamine was charged to the reaction vessel. With stirring, ammonium chloride was added gradually in 14 portions at room temperature. Over approximately 0.5 hr., the mixture was heated to 90-95. Diethylene glycol was added slowly to the stirring mixture and the reactiontemperatures was maintained until a clear solution developed. DCDA was added in 10 portions over 50 minutes, and the reaction mixture was stirred for 15 min. at 95-105. The temperature was raised to 170-180 over 50 min. and maintained for 2 hrs. The reaction temperature was again raised to 185-190 over 1 hr. The reactor was then cooled to 100, followed by the addition of hot water as previously indicated in Example No. 1, with stirring until a clear solution was obtained. No filtration was required.
The product obtained has the following physical and chemical properties:
Appearance: deep yellow viscous solution 10 % pH: 8.50- 8.90 Sp. Gravity: 1.16- 1.22 g/ml Viscosity: 167.5 - 200 cps (LVF, spindle #2, 60 rpm;) Example No. 3 The embodiment of the invention employing urea in addition to an inorganic ammonium salt is now demonstrated. The resin kettle flask was equipped with a magnetic stirrer and a condenser as in the previous examples.
Diethylene triamine (71.739, 0.695 mole) was heated to 60-65 with stirring. Urea (12.36 9, 0.206 mole) and ammonium chloride (44.889, 0.824 mole) were added in 4 portions, and, if necessary, the temperature of the vessel was increased to 90-95 over approximately 25 min. Diethylene glycol (20.00 9) was added while the temperature was maintained at 90-95 for 15 min. DCDA (76.29 9, 0.908 mole) was added gradually (approx. 20 9. at a time) while the temperature was increased and then held in the range of 95-105. The reaction temperature was then raisedin increments of 3/min until reaching 180-190, where the reaction was held for 2 hrs. The flask contents, now a viscous liquid, were cooled to 100, followed by the addition of hot water (in two 50 9. portions) and mixing until a homogeneous solution was obtained.
The product obtained had the following physical and chemical properties:
Appearance: deep yellow semi-viscous liquid pH (as is) : 1 1 .0 - 1 1 . 5 pH (10% aqua sol.) :10.82 - 1 1 .06 Sp.Gravity: 1.15 - 1.20 g/ml Viscosity: 20 - 150 cps (LVF, spindle #2, 60 rpm;) Example No. 4 Reaction of Polyguanidine with Chain Transfer Agent 15 Using the reactor of the type in Example No. 1, 0.1 mole of the product of Example No. 1 was charged to the reactor with stirring. The reactor was heated to 65-70.
Chain transfer agent B(a) (0.1 mole) was added and the reaction was stirred for 1 hr, followed by cooling to room temperature. The copolymeric product obtained had the following physical and chemical characteristics:
Appearance: Light to deep yellow color Sp.Gravity: 1 .1 5 - 1 .20 g/ml Viscosity:
(LVF,spd.#2,60rpm): 50 to 250 cps.
10% aq.sol. pH : 6.5 - 8.0 To further exemplify and demonstrate the improved characteristics of the new 10 polymeric materials of this invention, numerous tests were conducted. The test procedures and their results are set forth in the following description and in the accompanying Tables below.
TEST-I
The following results demonstrate the characteristic of the inventive cationic 15 polyguanidine copolymers. Effluent waste water from a paper mill plant having a turgidity over 900 NTU was treated with 200 milligrams of each of the below-specified agents per liter, pH = 7.5. The results were as follows:
Product Turbidity before Turbidity after treatment treatment (NTU) (NTU) No pH Adjustment Original water control 925 Example No. 1 4.65 Example No. 4 3.75 Fr. PAT. 2567897 Example 1 10.75 PAT 'Re 34,486 Example No . 15 5.35 A staple fiber fabric, dyed with 3% Brilliant-Benzo-Fast-Violet BL, was impregnated with the aqueous solution described in Example 4. The fabric was then squeezed until its increase in weight was 100% by weight, followed by drying at 80-100C and heating to 150C for 5 minutes. The dried fabric was 2t48355 -soaped at 90C for 30 minutes, then rinsed and dried. The fabric had excellent fastness to washing.
Comparative Test - ll TEST-II was repeating by substituting the product of Example 4 with product No.1 5 (Example No.1 ) of Fr.Pat '897. The fabric had good fastness to washing.
TEST-III
Good dye fastness and bleaching resistance were observed when cotton cloth dyed with 2% C. I. Direct Violet was first soaked in a 0.5% aqueous solution of the product of Example No. 4 at 45 for 20 minutes. The cloth was then treated at 70C for 10 minutes with a 0.3% aqueous solution of a bleaching composition containing bleaching agent (Sodium Perporate) (50 parts), Sodium Carbonate (10 parts), sodium sulfate (35 parts), and the product of Example No. 4 (5 parts).
Comparative Test-lll The procedure of TEST-III was repeated except that the product of inventive Example No. 4 was replaced with product No. 1 (Example No. 1 ) of Fr. PAT '897.
The resultant dye was not bleach resistant, i.e., the color bled out of the fabric.
TEST-IV
The cationic polyguanidine (co)polymers of the present invention may be modified, having up to 25 percent in a form of other form of salts like chloride or sulfate, 20 acetate and formate. For example, viscose rayon fibers were treated with an 2%
aqueous solution of the product of No. 1 Example No. 1 as a in sulfate salt at pH
9.0-9.5 and was then washed. The fiber was treated with an aqueous solution containing 37.5% copper sulfate and 33.5% sodium thiosulfate for 30 minutes at 80C, washed and dried to give a fiber with surface resistivity 18 ohmi.
TEST-V
5 A) A filter paper was impregnated with solution of the product of Example No.
1, dried and cured in an oven. The paper was flame retardant with very low smoking properties.
B) TEST-V was repeated using a fabric "COTTON PRINT CLOTH STYLE 400"
and 44".
The fabric was padded to about 75% wet pick-up, dried on a center frame and cured in an oven. The fabric exhibited flame retardant properties.
C) TEST-V (B) was repeated using a conventional formulation for the finish as follows:
% in Component Padding Liquor Polymer of Example No . 1 30 Trimethylolmelamine 8 Urea 5 NaOH 2.5 Softener 1.0 Wetting Agent 0.1 The fabric was padded to about 75% wet pick-up, dried on a center frame and cured in a oven for 2 minutes at 1 60C. Very good fire retardance was obtained with low smoking properties.
Although the invention has been described with respect to the preferred embodiments, it is not intended that the innovation to be so limited as there are 15 numerous modifications and expansions that may be made and that are readily appreciated by those skilled in the art in view of the embodiments shown and, in keeping with the spirit and scope of the present invention.
10. Polycyclic guanidine (see, e.g., Re.34,486 Col.5, Line 65).
The above starting materials are reacted in a high boiling point solvent, in thepresence of an amine, for example, cycloamine, aromatic amine, and hydroxyalkyl amine. The preferred amines are alkyl amines defined by the general formula:
H2N(CH2cH(Y)NH)x H
wherein Y is hydrogen or lower alkyl (C1-C4) and where x is from 1 to 5.
More specifically the (co)polymer of the cyanoguanidine, dicyanimide, guanidine or biguanidine are formed with comonomers of ammonium salt, urea, and alkylamine.
-The most preferred comonomer is alkyl amine as exemplified by ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, methyl or ethyl or butyl alkanolamine, e.g., aminotrihydroxyethylenediamine, monopropanolamine, diethanolamine, crude diaminopropanol and glycolamine. The solvent is selected from high boiling point organic solvents, such as a glycol, optionally in admixture with water.
Hence, the present invention describes the condensation process for preparing non-formaldehyde cationic or multiply cationic charged agents from dicyandiamide or dicyanimide, guanidine or biguanidine, or polymers or (co)polymers thereof, withamine and occasional urea present, in the presence of ammonium chloride, ammonium bromide or ammonium iodide, ammonium sulfate, or ammonium nitrate.
The presence of either the ammonium salt or urea will facilitate the reaction of the -CN group of, for example, the dicyandiamide monomer without cracking, thereby giving better yield and a more uniform product.
Another aspect of the present invention is that the products prepared in accordance with this process, and even the products according to the methods of the patents described above, may be further reacted with the herein described cationic or multiply cationic charged agents, to produce desired cationic polymer or (co)polymeric material.
For Example, the amine and the polyguanidines of the prior art, (for example, U.S. Patent No. 2,649,354; 3,873,266; 4,410,652; 4,439,203; 4,439,208), are 2 ~ 48055 suitable for reaction with chain transfer agents B(a) to B(j) shown below. U.S. Patent Nos. 2,304,369 and 2,945,774 teach the reaction of urea with cationic or anioniccoupling agents from fatty acids, diethylenetriamine, in reaction with quaternization agents. These disclosures are fully incorporated by reference. Another example is U.S. Patent No. 4,410,652, which describes the reaction of guanidine with alkyl amine in situ at 160C. This process is very difficult to carry out on an industrial scale, leads to the cracking and decomposition of the nitrile groups and produces an extremely viscous material, which is a nonionic product. However, such a productcan be used further in the reaction of the present invention with cationic or multiply cationic charged agents. However, the products described above in the prior art patents are very sensitive to bleaching compositions and are susceptible to "bleeding"
and dye discoloration.
In contrast, the cationic polyguanidine or its (co)polymer described by this invention has excellent dye fastness, improved color yield and bleaching composition with little or no dye discoloration. More particularly, the guanidine and/or polyguanidine or a co-polymer thereof is reacted from 25C to 195C, preferably 35C to 165C, in organic solvent or an aqueous medium or an aqueous/organic solvent system with reactive cationic or multiple cationic agents. The reactions may be carried out in the presence of a chain transfer agent, such as 2,2-sulfonyl-bis hyd roxyethyl .
The mole ratio ranges of (I) amine derivative, (Il) ammonium salt and (Ill) guanidine monomer and (IV) occasional urea are as follows:
0.1-2.0 M: 0.5-2.0M: 0.05-2.25 M: 0.25-1.5 M
11 : 111 : lV
5 where ll is an ammonium salt.
When the reaction is carried out in the presence of urea, the mole ratio ranges are:
0.1-1.5 M: 0.25-1.5 M: 0.15-2.5 M: 0.5-2.0 M
ll : lll : IV
10 where ll is ammonium salt.
The general reaction can be written as follows:
Cyanoguanidine/orguanidine derivative + ammonium salt + alkyl amine + solvent ------> polymer/or (co)polymer + DEG + water ----> aqueous (co)polymer, where DEG is diethylene glycol.
15 More preferably, the reactant side of the reaction scheme is as follows:
Cyanoguanidine + Ammonium chloride + diethylenetriamine + diethyleneglycol (DCDA) (NH4CI) (DETA) (DEG) The guanidine, polyguanidine or (co)polyguanidine are formed at pH 4.0 to 1 1 .0 in either free or salts form. These are further reacted with cationic or multiply 20 cationic chain transfer agents. Representative chain transfer agents useful in the practice of the invention have present a substituent which is a halo atom (chlorine, 214~055 bromine, iodine), a sulfate group substituted with methyl or ethyl, methoxy, or ethoxy, or a nitrate anion present.
Compounds B(a)-B(I) are suitable chain transfer agents in the practice of this Inventlon:
B(a): [ Cl - CH2 - CH(OH) - CH2 - N+ (CH3)3] Cl- or (C6H15N0CI);
B(b) [ CH2 - CH - CH2 - N+(CH3)3 ]Cl- or (C6H14NOCI);
o B(c): [Cl-CH2-CH(OH)-CH2-N + (CH3)2-CH2-CH(OH)-CH2-N + (CH3)2-CH2-CH(OH)CH2CI]Cl-2, or (C12H28N203CI4);
B(d): [Cl-CH2-CH(OH)-CH2-N + (CH3)2-[CH2-CH(OH)-CH2-N + (CH3)2-]n -CH2CH(OH)-cH2cl]cl ~1 + nl B(e): [CH2/CH-CH2- N + (CH3)2-CH2-CH2- N + (CH3)2-CH2-CH-CH2]C1-2 O O
or (c12H26N2o2cl2);
( )() LCICH2CH(OH)-CH2-N (CH3)2-(CH2)6-N+(CH3)2-cH2- CH(OH)-CI]SO4~2 or (c15H34N2o6cl2s) ( )( ) [Cl CH2-CH(OH)-CH2-N (cH3)2-(cH2)6-N+(cH3)2-cH2-cH(oH)-cl]cl-2 or (C15H34N202Cl4) B(g): [Cl-CH2-CH(OH)-CH2- N + (CH3)2-NH-C(0)-NH-N + (CH3)2-CH2-CH(oH)-cH2-cl]cl 2 or (C11H26N403CI4);
B~h) LCH2fH-CH2-N+(CH3)2-NH-C(0)-NH-N (CH3)2-CH2-CH-CH21C( 2 (C1 1 H24N4O3cl2);
B(i): N,N,N,N N N - hexaalkyl-B-hydroxy-trimethylene diammonium halide [(R)3- N+ - CH2-CH(OH)-CH2 - N+(R )3]X-2 10where: R is C1-C4 alkyl R is alkyl or alklylene-alkyl having C1-C3 atoms and X is selected from the group the consisting of chloride, bromide or iodide;
B(j): tetrakis-hydroxymethyl)-phosphoniumhalide,hydroxide,oxalate,acetate, sulfate, or phosphate;
B(k): 2,2-sulfonyl-hydroxyethyl;
_ B(l): a mixture of any of (a) through (k), as illustrated, for example, in Re.34,486 Example Nos. 15A, 16A, No.29-44 (steps 1 to 7).
Thus, first ammonium halide, sulfate or nitrate, is reacted with one of dicyanimide or dicyandimide or biguanidine, at 65-195C to form a polyguanidine 5 cation ammonium salt which will further react with alkylamine to generate the desired polymer or (co)polymer. This reaction can be written as follows:
H2N-C(NH)-NH-CN + NH4CI + H2N(CH2CH2N)n H + H20/DEG
(DCDA) (AMC) (DETA) --->[H2N-C(NH)-NH-C(NH)-NH2+]CI-+(H2N-CH2CH2)2NH
--HN C NH C NH (CH2CH2 NH)2-- Cl-(2m~
Il 11 NH2 + NH2 +
_ m The reaction is carried out at of from 110 to 200C, and preferably from 110 to 165C forming the polyguanidineor (co)polyguanidineof the formula [ - HN - C(NH) - NH - C(NH) - NH - R- ]m, where R represents H or (C1-C4) alkyl, optionally interrupted by oxygen, sulfur or nitrogen; R may also incorporate a saturated or unsaturated cyclic hydrocarbon nuclei in which the total number of carbon atoms directly interposed between the pair of nitrogen atoms linked between 0 guanidine radicals and amine radicals used and R is more than 1 and less than 500;
m is less than 100,000 When urea is used in addition to the ammonium salt reactant and an amine reactant, the (co)polyguanidine has the following structure:
[-NH-C(NH)-N-C(NH)-NH-R-]n I
C = O
I
[-NH-C(NH)-NH-C(NH)-NH-R-]n, where Ris as previously defined and n isfrom 1 to 5.
Secondly, the polyguanidines and (co)polyguanidines are reacted with cationic 10 or multiply cationic charged agents to form improved non-formaldehyde cationic polymeric materials.
The new non-formaldehyde improved cationic charged guanidine or polyguanidine according to the invention or its (co)polymer may have the following structures:
NH O
C NH C NH C NH C NH - C NH X Cl~(2n N NH NH2+
CHOH
N+
_ n n is less than 100,000 2t 48055 Y_ or:
NlI ~ Nl-l li; NlI --~ NlI
~'112 ~ 2 Cl- N (ctl3)2 1l2 Cl- N (Clt3)2 ~tl7 CllOll~Ctl2 L---~ Nl l ~ Nl l--~--Nl l--~--Nl l ---where n is less than 100,000 and X is either-H, -CN, -NH(CN), NH2 - C(NH)-, -C(0)-NH2.
The products according to the invention have utility as flame retardants, 5 dispersing agents, antistatic agents, paper sizing, as pitch control agents, in felt cleaner compositions, antimicrobial, precipitant and flocculating agents. The cationic or multiply cationic charged polyguanideines may also be used in combination with 2~ 48055 a sequestering agent such as a phosphonic acid or an aminotricarboxylic acid. The following non-limiting examples demonstrate various aspects of the invention, namely, polymeric and copolymeric products, their preparation and their utility. All parts and percentages are by weight and temperature is expressed in degrees 5 Centigrade.
Example No.1 A 500 ml resin kettle flask was equipped with a condenser, a mechanical stirrer, and a thermometer. To the flask was added diethylene triamine (71.719, 0.695 mole).
The triamine was heated to 55-60 with stirring, followed by the addition of ammonium chloride (44.889, 0.824 mole), added gradually over 20 minutes. The mixture was heated up to 95-100 and then mixed for 15 minutes. Diethylene glycol (12.99 9) was then added and the reaction temperature brought to a range of 95-105 until the reaction mixture was clear. Dicyandiamide (DCDA) (76.29 9, 0.908 mole) was added gradually as 10 portions over 50 minutes and the reaction was maintained at the prevailing temperature for 15 minutes. Gradually the reactor temperature was increased at a rate of 4-5/min. until reaching 195 according to the following protocol: upon reaching 165-170, the reaction was maintained within this temperature range for 2 hours; upon reaching 180-195, the reaction was maintained for an additional 2 hours. The reactor was cooled to 95-100 followed by the addition of hot water (50-95C) (100.00 9) in two equal portions.
21 4~055 The reaction medium was stirred until a uniform solution was obtained. The product obtained had the following physical and chemical properties:
Appearance: yellow to light yellow Sp.Gravity: 1.15 - 1.24 g/ml 10% pH (as is): 8.50 - 9.0 Viscosity (c.p.s.)(at 16): 275-500 cps (LVF, spindle #2, 60 rpm).
Example No. 2 Example No. 1 was repeated using the quantities of reactants previously specified according to the following general procedure. Diethylene triamine was charged to the reaction vessel. With stirring, ammonium chloride was added gradually in 14 portions at room temperature. Over approximately 0.5 hr., the mixture was heated to 90-95. Diethylene glycol was added slowly to the stirring mixture and the reactiontemperatures was maintained until a clear solution developed. DCDA was added in 10 portions over 50 minutes, and the reaction mixture was stirred for 15 min. at 95-105. The temperature was raised to 170-180 over 50 min. and maintained for 2 hrs. The reaction temperature was again raised to 185-190 over 1 hr. The reactor was then cooled to 100, followed by the addition of hot water as previously indicated in Example No. 1, with stirring until a clear solution was obtained. No filtration was required.
The product obtained has the following physical and chemical properties:
Appearance: deep yellow viscous solution 10 % pH: 8.50- 8.90 Sp. Gravity: 1.16- 1.22 g/ml Viscosity: 167.5 - 200 cps (LVF, spindle #2, 60 rpm;) Example No. 3 The embodiment of the invention employing urea in addition to an inorganic ammonium salt is now demonstrated. The resin kettle flask was equipped with a magnetic stirrer and a condenser as in the previous examples.
Diethylene triamine (71.739, 0.695 mole) was heated to 60-65 with stirring. Urea (12.36 9, 0.206 mole) and ammonium chloride (44.889, 0.824 mole) were added in 4 portions, and, if necessary, the temperature of the vessel was increased to 90-95 over approximately 25 min. Diethylene glycol (20.00 9) was added while the temperature was maintained at 90-95 for 15 min. DCDA (76.29 9, 0.908 mole) was added gradually (approx. 20 9. at a time) while the temperature was increased and then held in the range of 95-105. The reaction temperature was then raisedin increments of 3/min until reaching 180-190, where the reaction was held for 2 hrs. The flask contents, now a viscous liquid, were cooled to 100, followed by the addition of hot water (in two 50 9. portions) and mixing until a homogeneous solution was obtained.
The product obtained had the following physical and chemical properties:
Appearance: deep yellow semi-viscous liquid pH (as is) : 1 1 .0 - 1 1 . 5 pH (10% aqua sol.) :10.82 - 1 1 .06 Sp.Gravity: 1.15 - 1.20 g/ml Viscosity: 20 - 150 cps (LVF, spindle #2, 60 rpm;) Example No. 4 Reaction of Polyguanidine with Chain Transfer Agent 15 Using the reactor of the type in Example No. 1, 0.1 mole of the product of Example No. 1 was charged to the reactor with stirring. The reactor was heated to 65-70.
Chain transfer agent B(a) (0.1 mole) was added and the reaction was stirred for 1 hr, followed by cooling to room temperature. The copolymeric product obtained had the following physical and chemical characteristics:
Appearance: Light to deep yellow color Sp.Gravity: 1 .1 5 - 1 .20 g/ml Viscosity:
(LVF,spd.#2,60rpm): 50 to 250 cps.
10% aq.sol. pH : 6.5 - 8.0 To further exemplify and demonstrate the improved characteristics of the new 10 polymeric materials of this invention, numerous tests were conducted. The test procedures and their results are set forth in the following description and in the accompanying Tables below.
TEST-I
The following results demonstrate the characteristic of the inventive cationic 15 polyguanidine copolymers. Effluent waste water from a paper mill plant having a turgidity over 900 NTU was treated with 200 milligrams of each of the below-specified agents per liter, pH = 7.5. The results were as follows:
Product Turbidity before Turbidity after treatment treatment (NTU) (NTU) No pH Adjustment Original water control 925 Example No. 1 4.65 Example No. 4 3.75 Fr. PAT. 2567897 Example 1 10.75 PAT 'Re 34,486 Example No . 15 5.35 A staple fiber fabric, dyed with 3% Brilliant-Benzo-Fast-Violet BL, was impregnated with the aqueous solution described in Example 4. The fabric was then squeezed until its increase in weight was 100% by weight, followed by drying at 80-100C and heating to 150C for 5 minutes. The dried fabric was 2t48355 -soaped at 90C for 30 minutes, then rinsed and dried. The fabric had excellent fastness to washing.
Comparative Test - ll TEST-II was repeating by substituting the product of Example 4 with product No.1 5 (Example No.1 ) of Fr.Pat '897. The fabric had good fastness to washing.
TEST-III
Good dye fastness and bleaching resistance were observed when cotton cloth dyed with 2% C. I. Direct Violet was first soaked in a 0.5% aqueous solution of the product of Example No. 4 at 45 for 20 minutes. The cloth was then treated at 70C for 10 minutes with a 0.3% aqueous solution of a bleaching composition containing bleaching agent (Sodium Perporate) (50 parts), Sodium Carbonate (10 parts), sodium sulfate (35 parts), and the product of Example No. 4 (5 parts).
Comparative Test-lll The procedure of TEST-III was repeated except that the product of inventive Example No. 4 was replaced with product No. 1 (Example No. 1 ) of Fr. PAT '897.
The resultant dye was not bleach resistant, i.e., the color bled out of the fabric.
TEST-IV
The cationic polyguanidine (co)polymers of the present invention may be modified, having up to 25 percent in a form of other form of salts like chloride or sulfate, 20 acetate and formate. For example, viscose rayon fibers were treated with an 2%
aqueous solution of the product of No. 1 Example No. 1 as a in sulfate salt at pH
9.0-9.5 and was then washed. The fiber was treated with an aqueous solution containing 37.5% copper sulfate and 33.5% sodium thiosulfate for 30 minutes at 80C, washed and dried to give a fiber with surface resistivity 18 ohmi.
TEST-V
5 A) A filter paper was impregnated with solution of the product of Example No.
1, dried and cured in an oven. The paper was flame retardant with very low smoking properties.
B) TEST-V was repeated using a fabric "COTTON PRINT CLOTH STYLE 400"
and 44".
The fabric was padded to about 75% wet pick-up, dried on a center frame and cured in an oven. The fabric exhibited flame retardant properties.
C) TEST-V (B) was repeated using a conventional formulation for the finish as follows:
% in Component Padding Liquor Polymer of Example No . 1 30 Trimethylolmelamine 8 Urea 5 NaOH 2.5 Softener 1.0 Wetting Agent 0.1 The fabric was padded to about 75% wet pick-up, dried on a center frame and cured in a oven for 2 minutes at 1 60C. Very good fire retardance was obtained with low smoking properties.
Although the invention has been described with respect to the preferred embodiments, it is not intended that the innovation to be so limited as there are 15 numerous modifications and expansions that may be made and that are readily appreciated by those skilled in the art in view of the embodiments shown and, in keeping with the spirit and scope of the present invention.
Claims (22)
1. A water soluble organic polymer having a high nitrogen content, obtained by reacting (a) 0.05-2.25 mole of guanidine monomers selected from the group consisting of dicyandiamide (DCDA), dicyanimide (DCDI), guanidine and biguanidine optionally substituted with alkyl, guanylurea, guanylthiourea, cyanamide, salts thereof, and mixtures thereof with, (b) 0.5-2.0 mole of inorganic ammonium salt selected from ammonium chloride, ammonium bromide, ammonium sulfate and ammonium nitrate, further reacted with, (c) 0.1-2.0 mole alkylamine and occasional urea ranging from 0.25-1.5 mole selected from the group consisting of primary and secondary (C1-C10) alkyl amine, (C2-C6) alkylene diamines and polyalkylene polyamines of the structure wherein y represents an integer of about 1 to 5, each R3 is individually selected from the group consisting of alkylene of 1 to 6 carbon atoms and R4 is selected from the group consisting of hydrogen, (C1-C3) alkyl and hydroxy (C1-C3) alkyl and optionally in the presence of urea at a temperature ranging from 25°C to 195°C in the presence of a high boiling point organic solvent comprising diethylene glycol and propylene glycol which is optionally admixed with water.
2. The product according to Claim 1, wherein reactant (a) is the product of dicyandimide (DCDI) and its ammonium, calcium or sodium salts, dicyandiamide (DCDA), guanidine, biguanidine, guanylurea, cyanamide, (C1-C20) alkylguanidine or (C1-C20) alkylbiguanidine, or mixtures thereof.
3. The product according to Claim 1, wherein reactant (c) is a (C2-C12) alkyl amine.
4. The product according to Claim 1, wherein reactant (b) is an inorganic ammonium salt selected from the group consisting of ammonium chloride, ammonium bromide, ammonium iodide, ammonium sulfate, ammonium nitrate, or mixtures thereof.
5. The product according to Claim 3, wherein reactant (c) is a product of a straight chain alkylene amine of the general formulae:
H2N-(C2H3(Y)NH)xC2H3(Y)NH2, H2N [CH2CH(Y)NH]nH
or H2N [C3H5(Y)NH]z C3H5(Y)NH2 wherein x is from 1 to 4, n is 1 to 10, and Y is selected from hydrogen and C1-C4 alkyl, and z is 1 or 2, and with an alkylene polyamine derived from methylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, aminotrihydroxyethylenediamine, polyethylenepolyamine, diethanolamine, diaminopropanol, glycolamine, admixtures of methyl, ethyl and butyl alkanolamine, C1-C4 alkyl or hydroxy (C1-C6) alkyl substituted 1,2-ethylene, 1,3-propylene or 1,3-(2-hydroxypropylene), urea, and mixtures thereof.
H2N-(C2H3(Y)NH)xC2H3(Y)NH2, H2N [CH2CH(Y)NH]nH
or H2N [C3H5(Y)NH]z C3H5(Y)NH2 wherein x is from 1 to 4, n is 1 to 10, and Y is selected from hydrogen and C1-C4 alkyl, and z is 1 or 2, and with an alkylene polyamine derived from methylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, aminotrihydroxyethylenediamine, polyethylenepolyamine, diethanolamine, diaminopropanol, glycolamine, admixtures of methyl, ethyl and butyl alkanolamine, C1-C4 alkyl or hydroxy (C1-C6) alkyl substituted 1,2-ethylene, 1,3-propylene or 1,3-(2-hydroxypropylene), urea, and mixtures thereof.
6. A polymeric product according to Claim 5, wherein said ammonium salt is ammonium chloride or bromide, or an admixture thereof.
7. The product according to Claim 1, wherein the product produced is a polycondensation product that has charge characteristic that is cationic or cationic-nonionic.
8. The product according to Claim 1, wherein dicyandiamide (DCDA), (reactant (a)) reacts with ammonium chloride (reactant (b)) to convert cyano groups (-CN) to imino groups.
9. The product according to Claim 8, which is further reacted with (C1-C12) alkylamine or hydroxy (C1-C6) alkyl amine and occasional urea to form a polymeric material.
10. The product according to Claim 8, wherein formation of imino groups proceeds at a temperature of from 20° to 110°C for 0.25 to 2.0 hours.
11. The product according to Claim 10, wherein the formation of imino groups proceeds between 80° to 110°C.
12. The product according to Claim 9, wherein the polymeric material is formed at a reaction temperature between 95° to 195°C.
13. The product according to claim 12, wherein the reaction temperature is between 95° to 165°C.
14. A polymeric product obtained by reacting a water soluble, organic, guanidine-based polymer in accordance with Claim 1 with an organic cationic or multiply cationic agent which is a chain transfer agent.
15. A polymer according to Claim 14, wherein said chain transfer agent is selected from compounds of the following formulae:
B(a): [ Cl - CH2 - CH(OH) - CH2 - N+ (CH3)3] Cl- or (C6H15NOCl);
B(b):
B(c): [Cl-CH2-CH(OH)-CH2-N + (CH3)2-CH2-CH(OH)-CH2-N+(CH3)2-CH2-CH(OH)CH2Cl]Cl-2, or (C12H28N2O3Cl4);
B(d): [Cl-CH2-CH(OH)-CH2-N+(CH3)2-[CH2-CH(OH)-CH2-N+(CH3)2-]n -CH2CH(OH)-CH2Cl]Cl-(1 + n) B(e):
or (C12H26N2O2Cl2);
B(f)(i): [Cl-CH2-CH(OH)-CH2-N+(CH3)2-(CH2)6-N+(CH3)2-CH2- CH(OH)-CI]SO4-2 or (C15H34N2O6Cl2) B(f)(ii): [Cl-CH2-CH(OH)-CH2-N+(CH3)2-(CH2)6-N+(CH3)2-CH2- CH(OH)-Cl]Cl-2 or (C15H34N2O2Cl4) B(g): [Cl-CH2-CH(OH)-CH2- N + (CH3)2-NH-C(O)-NH-N + (CH3)2-CH2-CH(OH)-CH2-Cl]Cl-2 or (C11H26N4O3Cl4);
B(h): or (C11H24N4O3Cl2);
B(i): N,N,N,N'N'N'- hexaalkyl-B-hydroxy-trimethylene diammonium halide [(R)3- N+ - CH2-CH(OH)-CH2 - N+ (R )3]X-2 where: R is C1-C4 alkyl R' is alkyl or alklylene-alkyl having C1-C3 atoms and X is selected from the group the consisting of chloride, bromide or iodide;
B(j): tetrakis-hydroxymethyl)-phosphonium halide, hydroxide, oxalate, acetate, sulfate, or phosphate;
B(k): 2,2'-sulfonyl-hydroxyethyl;
B(l): a mixture of any of (a) through (k).
B(a): [ Cl - CH2 - CH(OH) - CH2 - N+ (CH3)3] Cl- or (C6H15NOCl);
B(b):
B(c): [Cl-CH2-CH(OH)-CH2-N + (CH3)2-CH2-CH(OH)-CH2-N+(CH3)2-CH2-CH(OH)CH2Cl]Cl-2, or (C12H28N2O3Cl4);
B(d): [Cl-CH2-CH(OH)-CH2-N+(CH3)2-[CH2-CH(OH)-CH2-N+(CH3)2-]n -CH2CH(OH)-CH2Cl]Cl-(1 + n) B(e):
or (C12H26N2O2Cl2);
B(f)(i): [Cl-CH2-CH(OH)-CH2-N+(CH3)2-(CH2)6-N+(CH3)2-CH2- CH(OH)-CI]SO4-2 or (C15H34N2O6Cl2) B(f)(ii): [Cl-CH2-CH(OH)-CH2-N+(CH3)2-(CH2)6-N+(CH3)2-CH2- CH(OH)-Cl]Cl-2 or (C15H34N2O2Cl4) B(g): [Cl-CH2-CH(OH)-CH2- N + (CH3)2-NH-C(O)-NH-N + (CH3)2-CH2-CH(OH)-CH2-Cl]Cl-2 or (C11H26N4O3Cl4);
B(h): or (C11H24N4O3Cl2);
B(i): N,N,N,N'N'N'- hexaalkyl-B-hydroxy-trimethylene diammonium halide [(R)3- N+ - CH2-CH(OH)-CH2 - N+ (R )3]X-2 where: R is C1-C4 alkyl R' is alkyl or alklylene-alkyl having C1-C3 atoms and X is selected from the group the consisting of chloride, bromide or iodide;
B(j): tetrakis-hydroxymethyl)-phosphonium halide, hydroxide, oxalate, acetate, sulfate, or phosphate;
B(k): 2,2'-sulfonyl-hydroxyethyl;
B(l): a mixture of any of (a) through (k).
16. The product according to Claim 14, which is formed at a reaction temperature between 50 to 80°C over 0.5 to 2.0 hours.
17. The product according to Claim 15, wherein the product is a polycondensate having a charge character that is cationic or cationic-nonionic.
18. The product according to Claim 1 in combination with a sequestering agent.
19. A product according to Claim 1 which is useful in chemical, pulp, paper, leather, textile, mining and clay industries as chemical additives, antistatics, flame retardants, dispersing agents, sequestering agent additives, antimicrobials, precipitants and flocculating agents.
20. A product according to Claim 1 which is useful as an additive for pulp and paper, leather, textile, mining and clay industries as chemical additives and flocculating agents.
21. A product according to Claim 15 which is useful as an additive for water treatment streams and industrial waste waters, and as a metal remover, emulsion beaker and felt cleaner.
22. A composition useful for chemical, pulp and paper, leather, textile, mining and clay industries as chemical additives, antistatics, flame retardants, dispersing agents, sequestering agent additives, antimicrobials, precipitants and flocculating agents, which composition comprises a water soluble organic polymer product according to Claim 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/310,066 US5659011A (en) | 1994-09-23 | 1994-09-23 | Agents having high nitrogen content and high cationic charge based on dicyanimide dicyandiamide or guanidine and inorganic ammonium salts |
| US310,066 | 1994-09-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2148055A1 true CA2148055A1 (en) | 1996-03-24 |
Family
ID=23200867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002148055A Abandoned CA2148055A1 (en) | 1994-09-23 | 1995-04-27 | Agents having high nitrogen content and high cationic charge based on dicyanimide, dicyandiamide or guanidine and inorganic ammonium salts |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5659011A (en) |
| CA (1) | CA2148055A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6686054B2 (en) * | 1998-04-22 | 2004-02-03 | Sri International | Method and composition for the sizing of paper using azetidinium and/or guanidine polymers |
| EP1073558B1 (en) * | 1998-04-22 | 2004-06-23 | Sri International | Treatment of substrates to enhance the quality of printed images thereon using azetidinium and/or guanidine polymers |
| US6291023B1 (en) | 1998-04-22 | 2001-09-18 | Sri International | Method and composition for textile printing |
| US6197880B1 (en) | 1998-04-22 | 2001-03-06 | Sri International | Method and composition for coating pre-sized paper using azetidinium and/or guanidine polymers |
| AU4372099A (en) * | 1998-06-11 | 1999-12-30 | Ciba Specialty Chemicals Holding Inc. | Use of basic polycondensates as antimicrobial active substance |
| DE10202767A1 (en) * | 2002-01-25 | 2003-08-07 | Cht R Beitlich Gmbh | Process for the production of textile auxiliaries and their use |
| CN1282698C (en) * | 2002-03-15 | 2006-11-01 | 上海塑杰科技有限公司 | Functional agglomerates of polyolefin as well as its preparing method and application |
| US7041338B2 (en) | 2002-05-01 | 2006-05-09 | Pixterra, Inc. | Process for providing a coated paper, a resin coated paper, a polymeric film, and a flexible or inflexible woven fabric substrate by utilizing a coating composition containing a nitrogenous dye-fixing compound |
| US20040202832A1 (en) * | 2002-07-03 | 2004-10-14 | Asutosh Nigam | Ink-jet recording medium with at least two layers coated upon a substrate, method for recording a water-resistant image on the medium using an ink-jet printer and the recorded medium thereof |
| JP2006527763A (en) * | 2003-06-18 | 2006-12-07 | イッスム・リサーチ・ディベロップメント・カンパニー・オブ・ザ・ヘブルー・ユニバーシティ・オブ・エルサレム | Polyalkylamine conjugates of sphingolipids |
| US7906122B2 (en) * | 2003-06-18 | 2011-03-15 | Yissum Research Development Company Of The Hebrew University Of Jersusalem | Sphingoid polyalkylamine conjugates for Hepatitis B virus vaccination |
| KR101885503B1 (en) * | 2009-12-24 | 2018-08-07 | 사우디 아람코 테크놀로지스 컴퍼니 | Methods for the synthesis of polycyclic guanidine compounds |
| US8148490B2 (en) * | 2010-03-10 | 2012-04-03 | Ppg Industries Ohio, Inc. | Method of making a cyclic guanidine from a guanidinium salt and a weak acid and coating compositions containing the same |
| US8157010B2 (en) | 2010-09-21 | 2012-04-17 | Polymer Ventures, Inc. | Treatment of subterranean formations |
| US8563560B2 (en) | 2011-02-25 | 2013-10-22 | Ppg Industries Ohio, Inc. | Preparation of bicyclic guanidine salts in an aqueous media |
| US8631868B1 (en) | 2013-02-27 | 2014-01-21 | Polymer Ventures Inc. | Treatment of subterranean formations |
| US9068089B2 (en) | 2013-03-15 | 2015-06-30 | Ppg Industries Ohio, Inc. | Phenolic admix for electrodepositable coating composition containing a cyclic guanidine |
| US9688874B2 (en) | 2013-10-25 | 2017-06-27 | Ppg Industries Ohio, Inc. | Method of making a bicyclic guanidine-cured acrylic coating |
| CN113026396B (en) * | 2021-04-08 | 2023-02-24 | 绍兴盛鑫印染有限公司 | Color fixing agent and cotton cloth pad dyeing process applying same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57106782A (en) * | 1980-12-22 | 1982-07-02 | Sanyo Chemical Ind Ltd | Agent and method for increasing wet fastness |
| CH667360GA3 (en) * | 1984-07-21 | 1988-10-14 | ||
| JPS6233893A (en) * | 1985-07-31 | 1987-02-13 | 三洋化成工業株式会社 | Dye fixing liquid and its production |
| US5135613A (en) * | 1991-02-04 | 1992-08-04 | Maxichem, Inc. | Method for controlling pitch in paper industry using PGAC or PGUAC |
-
1994
- 1994-09-23 US US08/310,066 patent/US5659011A/en not_active Expired - Fee Related
-
1995
- 1995-04-27 CA CA002148055A patent/CA2148055A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| US5659011A (en) | 1997-08-19 |
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