US2980641A - Solutions of polypyrrolidone in aqueous phytic acid and process for making same - Google Patents

Solutions of polypyrrolidone in aqueous phytic acid and process for making same Download PDF

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Publication number
US2980641A
US2980641A US763198A US76319858A US2980641A US 2980641 A US2980641 A US 2980641A US 763198 A US763198 A US 763198A US 76319858 A US76319858 A US 76319858A US 2980641 A US2980641 A US 2980641A
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Prior art keywords
nitrite
acid
polypyrrolidone
percent
solvent
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US763198A
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English (en)
Inventor
Jr Paul R Cox
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Solutia Inc
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Chemstrand Corp
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Priority to NL120097D priority Critical patent/NL120097C/xx
Priority to BE582868D priority patent/BE582868A/xx
Priority to NL243723D priority patent/NL243723A/xx
Priority to US763198A priority patent/US2980641A/en
Application filed by Chemstrand Corp filed Critical Chemstrand Corp
Priority to CH7796759A priority patent/CH405704A/fr
Priority to GB31911/59A priority patent/GB908771A/en
Priority to FR805849A priority patent/FR1244472A/fr
Priority to DEC19851A priority patent/DE1121325B/de
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Publication of US2980641A publication Critical patent/US2980641A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/095—Oxygen containing 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/24—Pyrrolidones or piperidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
    • C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
    • C08J3/098—Other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof

Definitions

  • Polypyrrolidone possesses many excellent properties which make it desirable for utilization in the manufacture of end products, such as ribbons, films, fibers, filaments, rods,'bristles, lacquers, coatings, shaped articles and the like.
  • Polypyrrolidone can be converted into shaped articles in many ways. For example, it may be cast into films or forced through multi-hole spinnerets to form fibers or filaments. Regardless of the end use to which the polypyrrolidone is to be put, it is generally more convenient and efficient to employ the polymer in a solution. This is well illustrated in the textile industry where polypyrrolidone is employed in the formation of fibers and filaments, which are manufactured by several methods of spinning, such as melt spinning, dry spinning, and wet spinning.
  • the polymer In the melt spinning method, the polymer is heated to a high temperature until it becomes molten and is thereafter forced through sand packs and the like, and thence through a spinneret from which it is extruded in filamentary form.
  • This method has, however, many disadvantages, although it is widely used in the industry at the present time in the production of synthetic fibers and filaments.
  • the high temperatures used in melt spinning require the exercise of extreme care in order to prevent decomposition of the polymer.
  • the high temperatures also affect the chemical and physical characteristics of the polymer and thereby result in a product of inferior quality.
  • it is extremely difficult to add to the molten polymer at such high temperatures compounds such as dyes, antistatic agents, plasticizers and the like.
  • the wet spinning method obviates many of the disadvantages of both melt spinning and dry spinning.
  • the polymer is dissolved in a suitable solvent and extruded from a spinneret into a coagulating bath capable of leaching the solvent from the fiber. Normally, this method may be carried out at temperatures much lower than either the melt spinning or dry spinning methods.
  • additives such as dyes, anti-static agents, fire-retarding agents, plasticizers and the like
  • they may be incorporated therein without the danger of decomposition or seriously affecting the properties of the end product where the wet spinning method of filamentary formation is employed.- Furthermore, it is much easier to introduce such addi tives into a solution than to introduce them into a molten composition. Then again, solutions are much easier to handle during processing, and in many cases may be stored for long periods of time without a change in physical and chemical properties. It is much easier to cast a film from a solution than to cast it from a molten composition. It is readily apparent, therefore, that solutions of polypyrrolidone present many distinct advantages over molten compositions in the manufacture of end products.
  • the objects of the present invention are accomplished by dissolving polypyrrolidone in aqueous phytic acid or aqueous solutions of the water-soluble alkali metal acid salts, alkaline earth metal acid salts or the mixed alkali and alkaline earth metal acid salts thereof.
  • the phytic acid compounds utilized in the practice of this invention are normally employed in aqueous solutions.
  • the water is generally present in a range of 5 to 50 percent, based on the total weight of the solvent. However, less than 5 percent or more than 50 percent water may be employed with consequent loss of solvent power and in such cases the water and phytic acid mixture is an excellent plasticizer for polypyrrolidone. It is preferred, however, that the water be employed in a range of 30 to 50 percent, based on the total weight of the solvent.
  • the water-soluble alkali metal acid salts, alkaline earth metal acid salts and the mixed acid salts of the alkali metals and alkaline earth metals of phytic acid which are useful as solvents in this invention include lithium acid phytate, potassium acid phytate, sodium acid phytate, strontium acid phytate, calcium acid phytate, magnesium acid phytate, lithium calcium acid phytate, sodium magnesium acid phytate,
  • Polypyrrolidone soluble in the solvents of this invention may be prepared by various processes. Generally, however, polymeric pyrrolidone is prepared by polymerizing monomeric pyrrolidone in the presence of a catalyst or a catalyst and activator at temperatures in the range of 70 C. to C. However, since the polymerization reaction proceeds well in the range 20 C. and 70 C., these temperatures are preferred in carrying out a polymerization procedure.
  • hydrides, hydroxides, oxides and salts of the alkali metals that is, such salts as sodium, lithium and potassium pyrrolidone.
  • Organic metallic compounds preferably those which are strongly basic, may also be used as catalysts. Examples of such compounds are lithium, potassium and sodium alkyls and aryls of the alkali metals, such as sodium phenyl.
  • Another suitable catalyst is sodium amide.
  • the alkali hydrides are the preferred catalysts, since a distinct advantage is obtained by their use.
  • Sodium hydride for example, does not react in the polymerization mixture to form water which, as'is well known, has a deleterious etfect upon pyrrolidone polymerization.
  • a waterforming catalyst such as sodium hydroxide
  • all water of reaction must be removed from the reaction mixture by vacuum distillation or other means in order to promote polymerization.
  • the catalyst may be employed in a rangeof 0.002 to 0.25 chemical equivalents based upon one mole of monomeric pyrrolidone in carrying out a polymerization reaction.
  • polypyrrolidone having acceptable properties can be prepared by using a catalyst alone, it is preferable to employ an activator in conjunction with any of the catalysts mentioned above, since the polymer prepared in the presence of both a catalyst and activator has greatly improved properties over polypyrrolidone prepared in the presence of a catalyst alone.
  • acyl compounds such as acetyl pyrrolidone, acetyl morpholone, and the like; lactones, such as gamma butyrolactone, and the like; alkyl esters of monoand dicarboxylic acids, such as ethyl acetate, ethyl oxalate, and the like; the esters of polyhydric alcohols such as ethylene glycol diacetate, and the like; and nitrogen dioxide and organic nitrites having the general formula:
  • R is selected from the group consisting of alkyl groups containing 1 to 10 carbon atoms, haloalkyl groups containing 2 to 10 carbon atoms, nitroalkyl groups containing 2 to 10 carbon atoms, aralkyl groups containing 7 to 10 carbon atoms, and alkoxy alkyl groups containing 3 to 12 carbon atoms.
  • nitrites falling into the general formula set out above there are methyl nitrite, ethyl nitrite, n-propyl nitrite, iso-propyl nitrite, n-butyl nitrite, iso-butyl nitrite, amyl nitrite, iso-amyl nitrite, hexyl nitrite, heptyl nitrite, octyl nitrite, nonyl nitrite, decyl nitrite, and their isomeric forms, and the like; haloalkyl nitrites such as 2,2,2-trichloroethyl nitrite; the dihaloalkyl nitrites, such as 2,2-dichloroethyl nitrite, 2,2-dichloropropyl nitrite, 2,2-dichlorobutyl nitrite, 2,2- dichloroamyl n
  • Silicon halides and organic silicon halides having the general formula:
  • aromatic hydrocarbon radical containing 1 to 10 carbon atoms a saturated or unsaturated aliphatic or aromatic halogenated hydrocarbon radicals contining l to 18 carbon atoms, and X is a halogen
  • z is an integer from 1 to 4 inclusive
  • y is equal to 4-2, wherein R may be similar or dissimilar radicals, may also be employed to activate polymerization of pyrrolidone.
  • silicon halides and organic silicon halides there may be named tetrachlorosilane, a,fi-dichloroethyltrichlorosilane, bis(chloromethyl)methylchlorosilane, butyltrichlorosilane, ch10romethylmethyldichlorosilane, dichloromethyldimethylchlorosilane, diethyldichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, ethyltrichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, propyltrichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, the iodoand bromo-forms of the above compounds, and many others.
  • the trihalides of phosphorous, aluminum, bismuth and antimony, the tetrahalides of titanium, tin, zirconium and lead, and the pentahalides of antimony and phosphorous are also useful as activators in the polymerization of pyrrolidone.
  • Such compounds include aluminum trichloride, aluminum tribromide, aluminum triiodide, stannic tetrachloride, stannic tetrabromide, lead tetrachloride, zirconium tetrachloride, bismuth trichloride, bismuth tribromide, antimony trichloride, antimony tribromide, antimony triiodide, antimony pentachloride, antimony pentaiodide, antimony pentafluoride, and the like.
  • the phosphorous halides include phosphorous tribromide, phosphorous pentabromide, phosphorous trichloride, phosphorous pentachloride, phosphorous trifluoride, phosphorous pentafluoride, r phosphorous triiodide, and the like.
  • the activator is utilized in a range of 0.0001 to 0.075 chemical equivalents of activator, based upon one mole of monomeric pyrrolidone.
  • the polypyrrolidone soluble in the solvents of this invention is prepared by simple polymerization methods. It can be prepared readily by well-known solution, emulsion, suspension or bulk polymerization procedures; The solution and emulsion polymerizations may be either batch, semi-continuous or continuous methods. When solution polymerization is employed, the monomer is'dissolved in a solvent such as 1,4-dioxane, the desired catalyst or activator, or both, added to the solution and the polymerization carried out under the proper conditions.
  • a solvent such as 1,4-dioxane, the desired catalyst or activator, or both
  • the monomer containing the catalyst is dispersed in a known solvent, such as petroleum ether, and an emulsifying agent then added to the dispersion. Subsequently, the desired activator is injected into the mixture and the dispersion is polymerized until the reaction is complete.
  • a known solvent such as petroleum ether
  • suitable coagulant is added to the polymerization mixture in order to precipitate the polymer.
  • A'suitable emulsifying agent is sodium lauryl sulfate, and a suitable coagulant is phosphorous acid.
  • Polypyrrolidone prepared in accordancewiththe procedures set forth hereinabove has a melting point of about 260 C. and .a specific viscosity of .from about 0.3 to 4.5 or more. Itis thus particularly adapted .for :the menu ifacture ofj shaped articles suchv asfilaments, fibers, films, rods,f bristles," and the like. Lower molecularweight polymers prepared in the same manner are. suitable for the: preparation of coatings or. lacquers. I
  • concentration of the polymer in the solvent depends upon the nature of the polymer, the solvent employed andthe temperature, which in turn afiect'the visc'o'sity of the solution.
  • concentration of the polymer in the solvent depends upon the nature of the polymer, the solvent employed andthe temperature, which in turn afiect'the visc'o'sity of the solution.
  • the solution is toli be employed in the manufacture of fibers and filaments, as'n'iu'ch as'50 percent of the polymer, based on the total weight of the solution, may be dissolved in the phytic acid solvents.
  • 'IIhe solvents of this invention readily dissolve polypyr rolidone within a'wide range of temperature depending upon. the nature of the polymer, the concentration thereofiin. the solvent; and the nature of the solvent itself.
  • temperatures within the range of C. to 120 C. are preferred in bringing about the solution, temperaturesaslow: as 5 C..and ashigh as the boiling point of thelpolymer/solvent mixture may be employed where necessary to, bring about dissolution.
  • Heating of the polymer/solvent mixture is preferably accomplished on a; water, glycerine or oil bath. However, other means may be employed. If desired, agitation or stirring of the mixture may be employed during heating or when a solution is being formed at lowtemperatures, although it is to. be understood that it is not always necessary'or critical.
  • compositions of the present invention which have .a. modified appearance and modified properties, various agents to accomplish these eifects may be added to the polymer solutions priorto fabrication of the articles without having any ill etfectsthereon.
  • Such addedw agents may' b alastiei zers, pigments, dyes, anti-static. agents, fire-retarding agents, and, the like. 5 1
  • the polymer had ,aspecific viscosity of;-0.7 6'1 @(Qlet'eiiii dd 0.5 percent solutions, of the polyineriu-QQ hydroxide solution.
  • Example II To a 25 gram (0.294 mole) sample of essentially anhydrous pyrrolidone, there was added under a nitrogen atmosphere 0.75 gram (0.0315 mole) of sodium hydride catalyst. When the evolution of hydrogen gas was completed, 039 gram (0.00293 mole) of anhydrous aluminum chloride was added to the reaction mixture. This mixture was stoppered to protect it against the atmosphere and permitted to standfor 25 hours at about 25 C.v . The polymer was recovered as in the foregoing example and had a specific viscosity, determined on 0.5 percent solutionsof the polymer in 90 percentformic acid at 25 C., of 3.9114.
  • Example III 5.25 parts of phyt'ic' acid and 2.25 parts of water thereafter subme'rsing .the' rod covered with the solution in a bath containing 15 percent aqueous sodium 7 7
  • Example I V To a 25 gram 0.294 mole) sample of essentially an; hydrous pyrrolidone, there wasiadded under a nitrogen atmosphere075 gram (0.0315 mole) of sodium hydride on a glycerine'ibath at 6'0' C.--for 45 minutes with o e The solution formed was clear and slightly'viscousj ItwasYstable at 25 C. Fibers drawn, therefro'rnwere washed in l 5. percent aqueouss'odiurn.
  • Example Vl To a 25 gram (0.294 mole) sample of essentially anhydrous pyrrolidone, there was added under a nitrogen atmosphere 0.75 gram (0.0315 mole) of sodium hydride catalyst. When theevolution of hydrogen gas was completed, 0.88 gram (0.00294 mole) of antimony pentachloride was added to the reaction mixture. The mixture was stoppered to protect it against the atmosphere and was permitted to stand for 25 hours at about 25 C. The polymer was recovered by the procedure disclosed in the foregoing examples and had a specific viscosity of 3.024, determined on 0.5 percent solutions of the polymer in 90 percent formic acid at 25 C.
  • Example Vll sodium hydroxidesolution These fibers were cold drawable and had good tensile strength.
  • a clear film was made from thesolution by dipping a glass rodrcoated therewith into a. bath containing 15 percent aqueous sodium hydroxide solution. The film was clear and had good strength.
  • Example 111 7. 75 parts of calcium acid-phytate andf4.75 parts of water were precooled to C. and mixedwith 0.50 part of the polypyrrolidone prepared in accordance with the procedure of-Example -II., The mixture went into, solution with occasional stirring at a temperatureina range of 5 to 20. C. in 4 hours. Thesolution was clear, viscous, and stable at temperatures as low as 5? C. Fibers drawn therefrom were washed in 15 percent aqueous sodium hydroxidesolution. These fibers were colddrawable and had good tensile strength; Aclea'r filr'n was madeby dipping a glass rod coated with. the solution into a bath containing 15 percent aqueous sodium hydroxide solution. a Q Example 1X 7,
  • the new compositions of this invention present many advantages. For example, solutions of polypyrrolidone may. be easily prepared on existing equipmentywithout detailed and elaborate procedures.
  • the phytic acid solvents of this invention are inexpensive and readily available.
  • the new solvents of this inven tion are entirely harmless, since they are neither toxic nor explosive and, therefore, may be employed without extraordinary precaution.
  • Polymeric solutions made with the new solvents of this invention are clear and colorless, and products or shaped articles prepared from such solutions exhibit superiorcolor characteristics.
  • the solvents of this invention are further advantageous in that they have noeftect upon the desirable chemical and physical properties of thepolymers dissolved therein. Numerous other advantages of the new compositions of this inventionwill be readily apparent to those skilled in the art.
  • a new, composition of matter comprising polypyrrolidone dissolved in a solvent containing 5 to 50 percent by weight of water, based on the total weight of the s lvent, and 95 to 50 percent of a compound selected from the group consisting of phytic acid, the watersoluble alkali metal acid salts of phytic acid, the alkaline earth metal acid salts of'phytic acid, and the mixed alkali and alkaline earth metal acid salts of phytic acid. 2.
  • alkaline earth metal acid salts otphytic acid andthe mixed alkali and alkaline earth'metal acid salts of phytic .
  • a r V V. v V I 8 A new fiber'forming composition ofmatte r com prising 20 to 40 percent, based on the total weightofthe composition, of polypyrrolidone, having a specific cosity of atleast 0.3, dissolved in a solvent'containing 30 to 50 percent byweig'htaof water, based "on the total weight of the solvent, and to 50 percent of ia com-,
  • a process lfor preparing. a newr composition, matter comprising mixing polypyrrolidoneand a solvent containing 5 to50 percent byweight of water, based on In addition 9 the total weight of the solvent, and 95 to 50 percent of a compound selected from the group consisting of phytic acid, the water-soluble alkali metal acid salts of phytic acid, the alkaline earth metal acid salts of phytic acid, and the mixed alkali and alkaline earth metal acid salts of phytic acid, and subjecting the mixture to a temperature in a range of 5 C. to the boiling point of the mixture to form a homogeneous solution.
  • solvent contains magnesium acid phytate.
  • a process 'for preparing a new fiberforming composition of matter comprising mixing 30 percent, based on the total weight of the composition, of polypyrrolidonc, having a specific viscosity of 3.914, and a solvent containing 50 percent of phytic acid and 50 percent of water, based on the total weight of the solvent, and heating the mixture to a temperature of 107 C. to form a homogeneous solution.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
US763198A 1958-09-25 1958-09-25 Solutions of polypyrrolidone in aqueous phytic acid and process for making same Expired - Lifetime US2980641A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
NL120097D NL120097C (en, 2012) 1958-09-25
BE582868D BE582868A (en, 2012) 1958-09-25
NL243723D NL243723A (en, 2012) 1958-09-25
US763198A US2980641A (en) 1958-09-25 1958-09-25 Solutions of polypyrrolidone in aqueous phytic acid and process for making same
CH7796759A CH405704A (fr) 1958-09-25 1959-09-08 Solution de polypryrrolidone et procédé de préparation de celle-ci
GB31911/59A GB908771A (en) 1958-09-25 1959-09-18 Phytic acid solvent for polypyrrolidone
FR805849A FR1244472A (fr) 1958-09-25 1959-09-23 Solutions de polypyrrolidone susceptibles d'être filées au mouillé
DEC19851A DE1121325B (de) 1958-09-25 1959-09-23 Verwendung von waessrigen Loesungen als Loesungsmittel fuer Polypyrrolidon

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US763198A US2980641A (en) 1958-09-25 1958-09-25 Solutions of polypyrrolidone in aqueous phytic acid and process for making same

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US (1) US2980641A (en, 2012)
BE (1) BE582868A (en, 2012)
CH (1) CH405704A (en, 2012)
DE (1) DE1121325B (en, 2012)
FR (1) FR1244472A (en, 2012)
GB (1) GB908771A (en, 2012)
NL (2) NL243723A (en, 2012)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3076774A (en) * 1959-09-21 1963-02-05 Monsanto Chemicals Solution of polypyrrolidone in superheated water
US3119396A (en) * 1961-05-24 1964-01-28 Minnesota Mining & Mfg Tobacco smoke filter
US3324061A (en) * 1962-01-15 1967-06-06 Minnesota Mining & Mfg Preparing aqueous solutions of polypyrrolidone
US4185063A (en) * 1975-02-04 1980-01-22 Chute Challoner R Shaping and stretching aqueous formic acid solutions of polypyrrolidone, filament and film products
US4263187A (en) * 1977-06-08 1981-04-21 Chute Challoner R Shaped articles of polypyrrolidone and method of preparation thereof
US4340440A (en) * 1977-09-22 1982-07-20 Chute Challoner R Coating and/or adhesive composition and method for preparation thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2638463A (en) * 1951-12-07 1953-05-12 Arnold Hoffman & Co Inc Polymers from pyrrolidone
US2734004A (en) * 1952-08-25 1956-02-07 Water soluble n-methylol polypyrroli-

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2638463A (en) * 1951-12-07 1953-05-12 Arnold Hoffman & Co Inc Polymers from pyrrolidone
US2734004A (en) * 1952-08-25 1956-02-07 Water soluble n-methylol polypyrroli-

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3076774A (en) * 1959-09-21 1963-02-05 Monsanto Chemicals Solution of polypyrrolidone in superheated water
US3119396A (en) * 1961-05-24 1964-01-28 Minnesota Mining & Mfg Tobacco smoke filter
US3324061A (en) * 1962-01-15 1967-06-06 Minnesota Mining & Mfg Preparing aqueous solutions of polypyrrolidone
US4185063A (en) * 1975-02-04 1980-01-22 Chute Challoner R Shaping and stretching aqueous formic acid solutions of polypyrrolidone, filament and film products
US4263187A (en) * 1977-06-08 1981-04-21 Chute Challoner R Shaped articles of polypyrrolidone and method of preparation thereof
US4340440A (en) * 1977-09-22 1982-07-20 Chute Challoner R Coating and/or adhesive composition and method for preparation thereof

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Publication number Publication date
NL243723A (en, 2012)
GB908771A (en) 1962-10-24
FR1244472A (fr) 1960-10-28
BE582868A (en, 2012)
DE1121325B (de) 1962-01-04
NL120097C (en, 2012)
CH405704A (fr) 1966-01-15

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