WO2000035881A1 - Quaternized water soluble vinylpyridine carboxylate polymers - Google Patents
Quaternized water soluble vinylpyridine carboxylate polymers Download PDFInfo
- Publication number
- WO2000035881A1 WO2000035881A1 PCT/US1999/025797 US9925797W WO0035881A1 WO 2000035881 A1 WO2000035881 A1 WO 2000035881A1 US 9925797 W US9925797 W US 9925797W WO 0035881 A1 WO0035881 A1 WO 0035881A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- quatemized
- vinyl
- vinyl pyridine
- monomer
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3796—Amphoteric polymers or zwitterionic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F26/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F26/06—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
Definitions
- This invention relates to novel quatemized, dye- complexable N-vinylpyridine carboxylate polymers , and to the process for their preparation involving water based polymerization of N-vinyl pyridine monomer and subsequent quaternization of the resulting vinyl pyridine polymer emulsion .
- Dye complexing polymers have been used in laundry detergent and fabric softener compositions to stabilize and minimize leaching of dyes in colored fabrics .
- some of the dyes can bleed out of a colored fabric and a portion of the leached dye may deposit on white or lighter colored fabrics .
- the degree of bleeding is influenced by the character of the dye, the type of cloth and the pH, temperature and mechanical efficiency of the agitation process .
- the bled dye in the wash liquor can be washed off without altering the color of lighter colored fabrics , the dyed fabric looses a degree of brilliance resulting in a somewhat faded appearance .
- DTI dye transfer inhibitor
- Polyvinylpyrrolidone (PVP) , by virtue of its dye complexation ability, has been used to inhibit dye deposition during washing of colored fabrics under laundry conditions .
- the performance of PVP as a DTI is adversely affected by the presence of anionic surfactants usually present in the washing process .
- Vinylpyridine polymers such as those disclosed in U.S. Patent 4,824,910 and in our previous U.S.patent application, Serial No. 932,448, now U.S. Patent 5,776,879, were formerly synthesized in alcoholic media; however, the product of this process contains significantly high unreacted monomer for a given period of reaction time and requires separation of organic solvent to recover pure polymer product. Costly and time consuming treatments are employed to remove impurities with the organic solvent in order to recover a purified product having no objectionable color.
- Another object is to provide an economical and commercially feasible process for the preparation of a water soluble dye transfer inhibitor and agrochemically or pharmaceutically complexable polymers , which are obtained in high purity suitable for immediate use in formulations .
- a further feature of the invention is the provision of a water soluble poly (vinylpyridine polymer) containing a quaternary nitrogen and a carboxylate salt in high yield and purity.
- Another object of the invention is to provide a laundry detergent composition which effectively resists fabric dye transfer during the washing and rinsing cycles , even in the presence of anionic surfactants .
- This invention is directed to an a quatemized water soluble vinyl pyridine carboxylate polymer and to the economic and commercially desirable process for synthesizing the water soluble quatemized vinylpyridine carboxylate polymer product in high yield and purity which product is stable in aqueous and water media.
- the quatemized polymeric product of this invention which is obtained in water solution or in powder form, contains (a) from 30 to 99.9 wt.% of a quatemized monomer having 20 to 5,000 quatemized units, preferably 100 to 2,500 units , of the structure
- n in the above formula can be otherwise expressed as Ci to C ⁇ 2 alkylene optimally substituted with aryl.
- the above quatemized polymer contains both a quaternary nitrogen and a carboxylate salt.
- This polymer possesses superior complexing properties with dyes, drugs ,pesticides and plant growth regulants and with other active components for use in a wide variety of applications .
- its dye complexing property provides excellent dye transfer inhibition in laundry and rinse formulations for cleansing of fabrics .
- the comonomers of the above polymers are free radical polymerizable comonomers including styrene, alkyl styrene, N-vinylpyrrolidone , N-vinyl caprolactam, vinyl imidazole , N-vinyl amide , a lower alkyl acrylate , a lower alkyl methacrylate , acrylamide, methacrylamide and the like and mixtures thereof.
- the preferred products of the present process are polymers in which X is a halide; particularly chloride or bromide; Ri and R 2 are both hydrogen; n has a value of 1-3; M is an alkali metal, particularly sodium or potassium or calcium; and the polymer is at least 75% quatemized.
- the polymer products of the present process have a weight average molecular weight of from about 5,000 to about 1,000,000; preferably from 20,000 to 500,000.
- quatemized vinylpyridine carboxylate salt polymer QPVPYR
- the polymers of the process are preferably those containing from 100 to 2,000 monomer units ; which polymers or copolymers are particularly useful at a concentration of from about 2 to about 1,000 ppm in a laundry detergent or rinse, a drug or agrichemical formulation, ink and paint compositions, etc. to inhibit the migration of dye or to complex with an active chemical for contolled release .
- the vinyl pyridine polymer reactant of the present invention can be obtained by any.prior process for vinylpyridine polymerization, including solution, emulsion and precipitation polymerization processes in which a suitable solvent such as a Ci to C 4 alkanol, water or a mixture thereof is employed (see U.S. Patents 5, 627, 151. and 5,458,809; EP 0664332A and J.of Polymer Science 26/No.ll3/ pp25-254/1957) .
- the products of the polymerization reaction are obtained as an emulsion, suspension, dispersion or as fine dry particles or powder.
- the vinylpyridine polymer is employed as a water mixture containing from about 20 to about 50 wt.% solids .
- the quatemization is carried out under constant agitation at a temperature of between 40° and about 140°C, preferably between 70° and 120°C, optionally under a blanket of inert gas and in the presence of an aqueous solution of the selected quatemizing agent until the desired degree of quatemization occurs .
- the quatemized polymer products of the present invention are derived from a water based polymerization of monomers to non-quaternized vinyl pyridine polymers described in my copending U.S. patent application Serial No.
- the polymer product of this invention is conducted in the presence of a water soluble suspension agent and a free radical polymerization initiator, such as a peroxide, perester, percarbonate, redox initiator or a diazo compound.
- a water soluble suspension agent such as a peroxide, perester, percarbonate, redox initiator or a diazo compound.
- a free radical polymerization initiator such as a peroxide, perester, percarbonate, redox initiator or a diazo compound.
- the polymer product of this invention can be obtained in a wide range of molecular weights which include a number average molecular weight of from about 10,000 to about 1,000,000, preferably from about 20,000 to about 500,000.
- the molecular weight of the non-quaternized polymer can be varied according to preference by several methods .
- lower molecular weights are obtained at the higher temperatures within the above range, a higher concentration of initiator generally results in lower molecular weight product and the incorporation of a small amount, e.g. 0.5 to 20 wt.%, preferably 0.5 to 10 wt.%, of chain transfer agent, such as an alkyl thiol, isopropyl alcohol and the like, also provides lower molecular weight polymer.
- the water soluble suspension agent of this invention is employed at a concentration of from about 0.75 to about 20 wt.%, preferably from about 1 to about 10 wt.%.
- Suitable suspension agents for the product polymer include a poly vinyl lactarn, particularly polyvinyl- pyrrolidone having a K value of 12 to 120, hydroxyethyl cellulose, a polyvinyl alcohol, carboxymethyl cellulose and other inert water soluble types and mixtures thereof . Of these, polyvinylpyrrolidone is preferred.
- the suspension agent can also be added with an appropriate emulsifier, hereinafter described.
- the vinyl pyridine monomer in the presence or absence of comonomer, is mixed with the suspension agent and water at ambient temperature under constant agitation and a blanket of inert gas .
- the resulting mixture is then heated to reaction temperature while the free radical initiator is added continuously or in increments during a 1 to 8 hour reaction period or until the monomer concentration in the reactor is below 1 wt.%
- the resulting non-quaternized intermediate polymer product, suspended in water, is recovered as small particles as a stable emulsion. or used directly in the quatemization zone.
- the water emulsion containing from about 20 to about 50% solids of non-quaternized vinyl pyridine polymer intermediate is then contacted with a water soluble alkali metal halide or an alkali metal salt of a halogenated Ci to C 4 carboxy acid at a temperature of between about 70° and about 100°C. accompanied with vigorous agitation until the quatemization is completed to the desired amount.
- concentration of quatemizing agent employed depends on the number of quaternizable nitrogen sites in the polymer and the degree of quatemization desired. Generally, between about 0.5 and about 1.5 moles of quatemizing agent per nitrogen in the polymer is utilized.
- the resulting vinyl betaine polymer containing monomer units having quatemized nitrogen and carboxylate metal salt moieties is suitable for incorporation into a detergent or dye formulation without further purification.
- Specific agents suitable to effect the quatemization of the vinyl pyridine polymer include an alkali metal salt of a halogenated carboxylic acid such as for example a sodium or potassium salt of chloro- or bromo- acetic acid; 3-chloro- or 3-bromo- propionic acid; 4-chloro- or 4-bromo- butyric acid; 4-chloro- or 4-bromo- 2-phenyl butyric acid; 2 ,2-dimethyl-3-chloro propionic acid and the like and mixtures thereof.
- a halogenated carboxylic acid such as for example a sodium or potassium salt of chloro- or bromo- acetic acid; 3-chloro- or 3-bromo- propionic acid; 4-chloro- or 4-bromo- butyric acid; 4-chloro- or 4-bromo- 2-phenyl butyric acid; 2 ,2-dimethyl-3-chloro propionic acid and the like and mixtures thereof.
- the vinylpyridine monomer in the above polymerization can contain an amount, less than 70 wt.%, of a comonomer for certain applications required by the consumer.
- Suitable comonomers utilized in the polymerization stage of the process include those referred to above in which case the copolymer is recoverable in the same state of purity and small particle size.
- free radical polymerization initiators employed in the process include t-butyl peroxy pivalate (LUPERSOL 11) ; t-amylperoxy pivalate (LUPERSOL 554); t-amyl- (2-ethylhexyl) peroxy carbonate (LUPERSOL TAEC) ; 1,1-di- (t-amylperoxy) cyclohexane (LUPERSOL 531); azo bis (2-methylbutyronitrile (VAZO 67); azo bis (isovaleronitrile (VAZO 52); azo bis (cyclohexane carbonitrile (VAZO 88) and the like and mixtures of the same .
- Low temperature initiators include the diacyl peroxides , diesters and azo compounds .
- High temperature initiators which may be employed in the final stages of polymerization include 2 ,5-dxmethyl-2 ,5-di- (t-butyl- peroxy)hexane (LUPERSOL 101); ethyl-2 ,5-di- (t-butyl- peroxy) hexane; dicumyl peroxide; t-butylcumyl peroxide; t-butylperoxy maleic acid; ethyl-3,3- di (t-butylperoxy) butyrate; di-t-butyl-diperoxy phthalate and the like.
- the polymerization reaction mixture can also contain up to about 10 wt.% of an emulsifier surfactant based on total monomer, including cationic, non-ionic, anionic, amphoteric and zwitterionic emulsifiers , such as one or a mixture of those disclosed at columns 8-16 of U.S. Patent 5,458,809; incorporated herein by reference .
- an emulsifier surfactant based on total monomer, including cationic, non-ionic, anionic, amphoteric and zwitterionic emulsifiers , such as one or a mixture of those disclosed at columns 8-16 of U.S. Patent 5,458,809; incorporated herein by reference .
- water soluble emulsifiers include an alkali metal sulfonate such as sodium or potassium dodecylbenzene sulfonate (LAS) ; coconut trimethyl ammonium chloride or bromide, N-coco-3-aminopropionic acid, triethanol oleate, sodium or potassium oleate, N-cetyl-N-ethyl morpholinium ethosulfate, sodium or potassium lauryl sulfate, lauryl alcohol polyether, polyethoxylated sorbitan monolaurate (TWEEN 20) and the like or a mixture thereof in the presence or absence of a suspension agent.
- alkali metal sulfonate such as sodium or potassium dodecylbenzene sulfonate (LAS) ; coconut trimethyl ammonium chloride or bromide, N-coco-3-aminopropionic acid, triethanol oleate, sodium or potassium oleate, N-cetyl-N-e
- EXAMPLE 1 Into a one liter four-neck resin kettle, fitted with a half-moon Teflon blade agitator, a nitrogen purge adapter and a reflux condenser, a mixture of 60 g. of 4-vinyl pyridine monomer, 3.0 g. of K-30 poly (vinyl- pyrrolidone) and 240 g. of water was charged. The nitrogen purge was begun and continued throughout the experiment. The above mixture at ambient temperature was then gradually heated and held at 85°C for 30 minutes while operating the blade agitator at 350 rpm. An initial charge of 1.0 g.
- t-butyl peroxypivalate Liupersol 11
- Lupersol 11 t-butyl peroxypivalate
- Poly (4-vinylpyridine) of molecular weight about 100,000 was recovered as a water suspension of 95 wt.% microparticles of substantially pure poly (4-vinylpyridine) .
- the polymer was dried overnight in an oven and 30 grams of the dried polymer was then contacted with 94.5 grams of water and 33.0 grams of sodium chloroacetate .
- the reaction mixture was held at 85°C for 2 hours under constant agitation and then recovered as the quatemized product of the process .
- the above water suspension was converted to 40% solids solution by adding 66.4 g. of sodium chloroacetate into the kettle.
- the reaction mixture was held at 85°C for 2 hours under constant agitation and then recovered as the quatemized product of the process .
- Example 3 was repeated except that 5.0 g of Vazo 67 was used in place of 1.0 g of Vazo 67 in the initial charge. The same quatemized polymer was recovered in good yield and high purity.
- EXAMPLE 5 Into a one liter four-neck resin kettle, fitted with a half-moon Teflon blade agitator, a nitrogen purge adapter and a reflux condenser, a mixture of 60 g. of 4-vinyl pyridine monomer, 3.0 g. of K-30 poly (vinyl- pyrrolidone) and 240 g. of water was charged. The nitrogen purge was begun and continued throughout the experiment. The above mixture at ambient temperature was then gradually heated and held at 85°C for 30 minutes while operating the blade agitator at 350 rpm. An initial charge of 1.0 g. of t-butyl peroxypivalate
- the above water suspension was then converted to 40% solids solution by adding 66.4 g. of sodium chloroacetate into the kettle.
- the reaction mixture was held at 85°C for 2 hours under constant agitation and then recovered as the substantially pure quatemized product of the process .
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Abstract
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Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU13386/00A AU1338600A (en) | 1998-12-15 | 1999-11-02 | Quaternized water soluble vinylpyridine carboxylate polymers |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/211,734 | 1998-12-15 | ||
US09/211,734 US6156829A (en) | 1998-12-15 | 1998-12-15 | Product and process for making quaternized, water soluble vinylpyridine carboxylate polymers |
US09/401,112 US6201046B1 (en) | 1998-12-15 | 1999-09-22 | Process for making quaternized vinylpyridine carboxylate polymers using suspension polymerization |
US09/401,112 | 1999-09-22 |
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Publication Number | Publication Date |
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WO2000035881A1 true WO2000035881A1 (en) | 2000-06-22 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/US1999/025797 WO2000035881A1 (en) | 1998-12-15 | 1999-11-02 | Quaternized water soluble vinylpyridine carboxylate polymers |
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AU (1) | AU1338600A (en) |
WO (1) | WO2000035881A1 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4869991A (en) * | 1988-03-24 | 1989-09-26 | Olin Hunt Specialty Products Inc. | Charge director composition for liquid toner formulations |
US5459007A (en) * | 1994-05-26 | 1995-10-17 | Xerox Corporation | Liquid developer compositions with block copolymers |
US5573882A (en) * | 1995-08-25 | 1996-11-12 | Xerox Corporation | Liquid developer compositions with charge director block copolymers |
-
1999
- 1999-11-02 WO PCT/US1999/025797 patent/WO2000035881A1/en active Application Filing
- 1999-11-02 AU AU13386/00A patent/AU1338600A/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4869991A (en) * | 1988-03-24 | 1989-09-26 | Olin Hunt Specialty Products Inc. | Charge director composition for liquid toner formulations |
US5459007A (en) * | 1994-05-26 | 1995-10-17 | Xerox Corporation | Liquid developer compositions with block copolymers |
US5573882A (en) * | 1995-08-25 | 1996-11-12 | Xerox Corporation | Liquid developer compositions with charge director block copolymers |
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AU1338600A (en) | 2000-07-03 |
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