WO2001005847A1 - Procede et appareil de production de polyvinylamine - Google Patents

Procede et appareil de production de polyvinylamine Download PDF

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Publication number
WO2001005847A1
WO2001005847A1 PCT/JP2000/004682 JP0004682W WO0105847A1 WO 2001005847 A1 WO2001005847 A1 WO 2001005847A1 JP 0004682 W JP0004682 W JP 0004682W WO 0105847 A1 WO0105847 A1 WO 0105847A1
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Prior art keywords
reactor
polymer
vinylformamide
pressure
water
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PCT/JP2000/004682
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English (en)
Japanese (ja)
Inventor
Takeshi Yamashita
Kiyoshi Onishi
Yoshiyuki Nagase
Ryuichi Fukuzato
Original Assignee
Kabushiki Kaisha Kobe Seiko Sho
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Application filed by Kabushiki Kaisha Kobe Seiko Sho filed Critical Kabushiki Kaisha Kobe Seiko Sho
Priority to AU58529/00A priority Critical patent/AU5852900A/en
Publication of WO2001005847A1 publication Critical patent/WO2001005847A1/fr

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    • 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
    • C08F26/02—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 single or double bond to nitrogen

Definitions

  • the present invention relates to a method for producing polyvinylamine used as an additive for papermaking and a flocculant for treating wastewater, and an apparatus for producing the same. is there.
  • BACKGROUND ARTPolyvinylamine is a basic polymer that exhibits outstanding effects compared to conventional products as an additive for papermaking and a flocculant for wastewater treatment, and is expected to have future potential.
  • As a method for producing polyvinylamine for example, N-vinylformamide is polymerized, and a part of the formamide group in the obtained N-vinylformamide polymer is subjected to an acidic condition or a base.
  • a method that can be achieved by hydrolysis under neutral conditions is known (JP-B-63-92523).
  • the conventional method has the following problems.
  • an acidic catalyst e.g., hydrochloric acid or bromide
  • Hydrohalic acid such as hydroacid, phosphoric acid, sulfuric acid, etc.
  • the acid catalyzed hydrolysis produces the corresponding polymer acid salt.
  • Has a free amino group from this acid salt When polyvinylamine alone is obtained, it is neutralized by adding a base (sodium hydroxide, potassium hydroxide, etc.). It is necessary to remove lithium and calcium salts.
  • the base e.g., sodium hydroxide, potassium hydroxide, ammonia, amide, hydroxylamine
  • the base is equivalent to the formamide group in the N-vinylformamide polymer. (Such as calcium).
  • a basic catalyst a large amount of a salt of the basic catalyst and formic acid is generated, and a post-treatment process for removing these is complicated.
  • An object of the present invention is to solve these problems and to provide a method capable of efficiently producing polyvinylamine with a small number of steps.
  • the method for producing a polyvinylamine of the present invention which has achieved the above object, refers to a method for producing an N-vinylformamide polymer in the presence of water at a pressure of 10 o or more and a pressure of a saturated vapor pressure or more. It is characterized by being hydrolyzed in the absence of a catalyst. The above hydrolysis is preferably carried out under the conditions of 100 to 300 t: and the pressure of 0.3 to 28 MPa.
  • the present invention provides a method for synthesizing an N-vinylformamide polymer starting from N-vinylformamide, which is a raw material monomer, by adding water and a polymerization initiator, and subsequently synthesizing the N-vinylformamide. It includes a method of hydrolyzing a polymer.
  • the above method involves the use of N-vinylformamide in a reactor. After synthesizing the union, the method includes subsequently hydrolyzing the N-pinyl formamide polymer in the same reactor.
  • the apparatus for producing a polyvinylamine according to the present invention comprises the steps of: preparing an N-vinylformamide polymer in the coexistence of water at a pressure of 100 or more and a saturated water vapor pressure or more, preferably 100 to 300: 0; A reactor capable of being hydrolyzed without a catalyst at 3 to 28 MPa, means for heating the reactor, means for stirring the inside of the reactor, and N-vinylformamide Means for supplying an aqueous solution containing the polymerized N-vinylformamide polymer.
  • the present invention is preferably capable of synthesizing an N-vinylformamide polymer, and is preferable to have the N-vinylformamide polymer in a coexistence of water of 100 or more and a saturated steam pressure or more.
  • a reactor capable of reacting at 100 to 300, 0.3 to 28 MPa in the absence of a catalyst, a means for heating the reactor, and a means for stirring the inside of the reactor.
  • a polyvinylamine production apparatus comprising: means for supplying water, N-vinylformamide and a polymerization initiator to the reactor; and means for introducing an inert gas to the reactor. Is included.
  • the N-vinylformamide polymer is not catalyzed in the presence of water at a temperature of 100 or more and a saturated water vapor pressure or more, preferably 100 to 300, preferably 0.3 to 28 MPa.
  • the present invention also includes a polyvinylamine production apparatus provided with a means for separating water from a effluent containing polyvinylamine discharged from the reactor.
  • FIG. 1 is a schematic configuration diagram showing a first specific example of a polyvinylamine batch production apparatus according to the present invention.
  • FIG. 2 is a schematic configuration diagram showing a second specific example of a continuous production apparatus for polyvinylamine according to the present invention.
  • BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
  • the N-vinylformamide polymer includes not only homopolymers of N-vinylformamide but also copolymers with other vinyl monomers.
  • a water-soluble vinyl monomer is preferable.
  • radical polymerization is initiated after a monomer aqueous solution is aerated according to a known method. This can be done by adding an agent. This polymerization or copolymerization
  • radical polymerization initiator examples include a peroxide such as hydroperoxide, a redox catalyst, and an azo compound that decomposes into radicals.
  • a peroxide such as hydroperoxide
  • a redox catalyst such as an azo compound that decomposes into radicals.
  • azo compounds is preferred.
  • 2,2'-azobis (2-amino diprono ⁇ ° norl) hydrochloride, 4,4'-azobis (4-cyanovaleric acid) and the like are preferred. used.
  • the amount of the azo compound to be used is usually 0.1 to 0.1 parts by mass of the monomer. 110 parts by mass, preferably 1-5 parts by mass.
  • the polymerization is carried out using an aqueous monomer solution having a monomer concentration of 5 to 60% by mass, preferably 10 to 50% by mass.
  • the polymerization time is usually 0.5 to 10 hours, and the polymerization initiation temperature is usually It is about 20 to 80.
  • This reaction is usually carried out in an aqueous solution, but by solution polymerization in water, in a solvent soluble in water, in a mixed solvent of water and a solvent soluble in water, or in a water-in-oil emulsion polymerization.
  • the polymerization can also be carried out.
  • inverted suspension polymerization for producing a fine polymer is also possible. Adjusting the pH during polymerization to 4 to 9, preferably 5 to 7, is recommended for producing a high quality polymer.
  • the present invention is to obtain a polyvinylamine by hydrolyzing an N-vinylformamide polymer under specific conditions.
  • the temperature at which the N-vinylformamide polymer is hydrolyzed is at least 100 ° C., preferably at least 140 ° C., more preferably at least 160 ° C. C or more is recommended, and a preferable upper limit is 30 O: or less, and more preferably, a value of 280 or less is recommended.
  • the temperature is above 160 ° C, the formic acid generated will be decomposed and the burden on the subsequent purification process will be reduced, thus producing cheap and safe polyvinylamine for diapers and the like. it can.
  • it is less than 280 the thermal decomposition of polyvinylamine is suppressed.
  • the pressure is higher than the saturated water vapor pressure, preferably 0.3 to 28 MPa, particularly preferably 0.5 to 25 MPa.
  • the product in the reactor generated by the hydrolysis reaction may be taken out as it is to obtain a product.
  • the product in the reactor may be introduced into a separation device to separate water, and may be taken out as a highly concentrated product.
  • the production apparatus of the present invention makes it possible to produce polyvinylamine more efficiently.
  • FIG. 1 is a schematic configuration diagram showing a first specific example composed of the most basic elements of the manufacturing apparatus of the present invention.
  • the apparatus shown in FIG. 1 is a batch-type apparatus for synthesizing and hydrolyzing N_vinylformamide polymer in one reactor.
  • the reactor is capable of synthesizing an N-vinylformamide polymer and capable of hydrolyzing the N-vinylformamide polymer, and a heating means for heating the reactor 11 1 2, Stirring means 13 for stirring the inside of reactor 1 1, Means 1 for supplying water to reactor 11 1, Means 2 for supplying N-vinylformamide to reactor 11 1, Reactor 1 Means 3 for supplying a polymerization initiator to 1 and means 4 for introducing an inert gas into a reactor 11 are provided.
  • the reactor 11 is a pressure-resistant container that can withstand the production conditions in the polyvinylamine production method of the present invention, and the upper limit of the pressure is not particularly specified.
  • a heat and pressure resistant container that can withstand a pressure of 0.3 to 28 MPa and a temperature of 100 to 30 or more, preferably 100 to 30 is desired.
  • the heating means 12 include a heater for heating the reactor 11 from the outside and Z or from the inside, and a method of heating the reactor 11 with another heat medium.
  • the stirring means 13 in addition to stirring by means of a stirring blade having a shape such as an impeller as shown in FIG. 1, a circulating pump or the like is provided outside the reactor 11 to form a reactor. 1 1
  • the symbol M indicates a motor for driving the stirrer.
  • a vessel such as a tank is installed at a higher position than reactor 11 and gravity is used. There are a method of supply, a method of supply by a pump, and a method of supply using gas pressure. If the supply means 2 for N-vinylformamide and the supply means for the polymerization initiator 3 can be supplied dropwise, the control of the polymerization reaction becomes easy.
  • a means 4 for introducing an inert gas there is a method of directly supplying the gas by a cylinder or the like.
  • the reactor 11 be provided with a thermometer and a cooling pipe.
  • an N-vinylformamide polymer is produced in a reactor 11. That is, water is supplied into the reactor 11, the temperature is raised to the polymerization reaction temperature, and N-vielformamide and the polymerization initiator are supplied preferably or dropwise while maintaining the temperature. . From the time before the supply of N — vinyl formamide and the polymerization initiator to the end of the polymerization, an inert gas such as nitrogen gas is supplied into the reactor 11. In this way, the N — vinyl form in the reactor 11 is supplied. After synthesizing the amide polymer, the N-vinylformamide polymer is subsequently hydrolyzed in the reactor 11 to produce polyvinylamine.
  • the supply of the inert gas is stopped, water is added to the reactor 11 after the production of the N-vinyl formamide polymer, if necessary, and the reactor 11 is heated to 10 o or more and the internal pressure is increased. Pressure should be higher than the saturated steam pressure. In addition, the pressure inside the reactor 11 can be adjusted by an inert gas.
  • the N-vinylformamide polymer is hydrolyzed by reacting with water under a condition of 100 ⁇ or more, a saturated steam pressure or more, and no catalyst, to produce polyvinylamine. .
  • N_vinyl formamide and another vinyl monomer are used, respectively.
  • the mixture may be supplied to the reactor 11.
  • the hydrolysis reaction is performed in one reactor 11 following the synthesis of N-viel formamide polymer.
  • Polyvinylamine can be produced.
  • polymerization and amination are performed in one reactor, there is no need to transfer products for batch change, no energy loss occurs, and both energy and equipment can be used efficiently. It is possible to produce polyvinylamine.
  • Fig. 1 shows a batch-type apparatus for synthesizing and hydrolyzing N-vinylformamide polymer in one reactor. However, the synthesis and hydrolysis of N-vinylformamide polymer are shown in Fig. 1. It is also possible to use different reactors.
  • the reactor for hydrolyzing the N-vinylformamide polymer has a pressure resistance not less than the saturated steam pressure, preferably not less than the pressure of the production condition of 0.3 to 28 MPa. And a pressure-resistant container capable of withstanding a temperature of 100 O or more, preferably 100 and up to 30 O.
  • the reactor for hydrolyzing the N-vinyl formamide polymer is equipped with the same heating means and stirring means as in the example of Fig. 1 above.
  • FIG. 2 shows a second specific example of the production apparatus of the present invention, and is a schematic configuration diagram of a continuous apparatus for continuously producing polyvinylamine from an N-vinylformamide polymer. is there.
  • the apparatus shown in Fig. 2 has a reactor 21 capable of hydrolyzing N-vinylformamide polymer and a N-vinylformamide polymerizer. Means for continuously supplying an aqueous solution containing the polymer or N-vinylformamide polymer to the reactor 21, heating means 23 for heating the reactor 21, and discharged from the reactor 21. A separation means 22 for separating water from the effluent containing polyvinylamine is provided.
  • the means 30 for continuously supplying an aqueous solution containing an N-vinylformamide polymer or an N-vinylformamide polymer to the reactor 21 is composed of N-vinylformamide.
  • the apparatus shown in Fig. 2 is used for the case where the concentration of the aqueous solution containing N-vinylformamide polymer or N-vinylformamide polymer supplied to the reactor 21 is low or the product concentration is controlled.
  • a supply means 25 for controlling the amount of water supplied to the reactor 21 as required is preferably provided.
  • a tank 24 for temporarily storing the water separated by the separation means 22 is preferably provided, and the water in the tank 24 is supplied through the supply means 25 and 26. It is configured such that it can be supplied to the reactor 21 and the polymerization tank 31 respectively.
  • the reactor 21 is a pressure-resistant container capable of withstanding the production conditions in the method for producing polyvinylamine of the present invention, and is capable of performing a hydrolysis reaction of the N-vinylformamide polymer therein. I just need. Specifically, a heat-resistant material capable of withstanding a pressure higher than the saturated water vapor pressure, preferably 0.3 to 28 MPa, and a temperature of 100 or more, preferably 100 to 300 MPa. A pressure vessel is desired.
  • the heating means 23 in the apparatus shown in FIG. 2 the reactor 21 has a heat insulating structure and a heater or another heating medium is provided before entering the reactor 21. However, a method in which the reactor 21 is heated from the outside and Z or from the inside or from outside or from another heating medium may be used.
  • pumps are preferably used for the supply means 32 for supplying the liquid in the polymerization vessel 31 to the reactor 21 and the water supply means 25 and 26. It is also possible to use a method of supplying using gravity or a method of supplying using gas pressure.
  • the means 22 for separating water from the effluent containing polyvinylamine discharged from the reactor 21 is a flash distillation method, a thin film distillation method, a simple distillation method performed by reducing the reaction pressure. Such a method can be used.
  • the polymerization tank 31 may have any suitable structure as long as it can synthesize an N—vinylformamide polymer.
  • N— A means for supplying vinyl formamide, a means for supplying a polymerization initiator, a means for introducing an inert gas, a heating means, a stirring means, a thermometer, and a cooling pipe may be provided.
  • an N-vinylformamide polymer is produced in a polymerization vessel 31. That is, water is supplied from the supply means 26 into the polymerization tank 31, the temperature is raised to the polymerization reaction temperature, and N-vinylformamide and the polymerization initiator are supplied while maintaining the temperature.
  • an inert gas such as nitrogen gas is supplied into the polymerization tank 31 from before the supply of N-vinylformamide and the polymerization initiator until the end of the polymerization.
  • the aqueous solution containing the N-vinylformamide polymer in the polymerization tank 31 is introduced into the reactor 21 via the supply means 32, but before being introduced into the reactor 21, the heating means 2 Heat to 100 or more in 3 and adjust so that the inside of the reactor 21 becomes saturated steam pressure or more.
  • water is added via the supply means 25 as necessary.
  • the N-bielformamide polymer is hydrolyzed under the condition of 100 or more, the saturated steam pressure or more, and no catalyst, to produce polyvinylamine.
  • the pressure inside the reactor 21 can be adjusted by an inert gas.
  • the discharged liquid containing the produced polyvinylamine is taken out of the reactor 21 and introduced into the separation means 22 to be separated into water and polyvinylamine to obtain a product.
  • the separated water is temporarily stored in the tank 24 and used as necessary for the polymerization reaction or the hydrolysis reaction as needed.
  • N_vinyl formamide polymer When a copolymer of N-vinyl formamide and another vinyl monomer is used as the N_vinyl formamide polymer, N-vinyl formamide and another vinyl monomer are used, respectively. Separately or in advance, the mixture may be supplied to the polymerization tank 31.
  • the N-vinylformamide polymer produced in the polymerization tank 31 can be continuously supplied to the reactor 21 to be converted into polyvinylamine. Then, if water is separated from the reactor 21 by the above-mentioned distillation method or the like and only the produced polyvinylamine is taken out, the unreacted N-vinylformamide polymer can be further subjected to the reaction. So, The amine conversion can be improved, and the productivity is improved. In addition, it is preferable that the water separated by the separator 22 be recycled for polymerization or hydrolysis, because the production efficiency can be improved.
  • the production of the N-vinylformamide polymer in the polymerization tank 31 is a batch operation, so if a plurality of polymerization tanks 31 are provided, the supply to the reactor 21 can be achieved. There is no interruption and productivity can be further improved.
  • EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to the following Examples, and may conform to the purpose described above. It is also possible to carry out the present invention with appropriate changes within the scope, and all of them are included in the technical scope of the present invention. In the following examples, “parts” means “parts by mass”.
  • a polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen introduction tube, and a dropping vessel was charged with 450 parts of water, and the temperature was raised to 60 parts. Then, while introducing nitrogen gas into the reaction tank and maintaining the temperature at 60, 50 parts of NVF (manufactured by Mitsubishi Chemical: N-vinylformamide) and another part were added from the drip tank. V-50 (Wako Pure Chemical: 2,2'-azobis (2_aminodipropanol) hydrochloride) from a drip tank was added dropwise over 10 hours in 10 parts of a 10% by mass aqueous solution of 10% by mass. For 2 hours. Obtained N— The vinylformamide polymer had a viscosity of 10% by mass and a viscosity (gas donor viscosity) of Z 2.
  • a polymerization reactor equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen introduction tube and a dropping tank was charged with 445 parts of water, and the temperature was raised to 60. Then, while introducing nitrogen gas into the reaction tank and maintaining the temperature at 60, a mixture of 40 parts of NVF and 10 parts of N-vinylpyrrolidone and another dropping tank were added from the dropping tank. 5 parts of a 10% by mass aqueous solution of V-50 were added dropwise over 4 hours, and the mixture was kept at 60 at 2 hours.
  • the obtained N-vinylformamide polymer had a viscosity of 10% by mass and a viscosity (Gardner viscosity) of Z5.
  • a small stainless steel pressure vessel was used for the reactor, and the separation means was used. Used a thin-film distillation apparatus.
  • the polymer obtained in Polymer Production Example 1 was dissolved in water and adjusted to a concentration of 3% by mass, and was used in a batch-type apparatus in the same manner as in Examples 1 to 9 above. An experiment was carried out to produce The obtained reaction products were analyzed in the same manner as in Examples 1 to 9 above. The results are shown in Table 1. From Table 1, it was confirmed that when the concentration of the polymer used was reduced, the amine conversion rate was improved. Table 1
  • the polymer obtained in Polymer Production Example 1 was dissolved in water
  • the aqueous solution adjusted to a concentration of mass% was continuously supplied to the reactor by a pump, and was hydrolyzed in the reactor.
  • the reaction conditions are as shown in Table 2.
  • the collected product was analyzed in the same manner as in Example 19 above.
  • Table 2 shows the results. Table 2 shows that while the batch type had an amine conversion of about 80 mol%, the continuous method improved the amine conversion to almost 100 mol%. Was allowed to do so.
  • Table 2 shows that while the batch type had an amine conversion of about 80 mol%, the continuous method improved the amine conversion to almost 100 mol%. Was allowed to do so.
  • a notch type apparatus was used in the same manner as in Example 4 except that 5 g of the aqueous polymer solution (concentration of 10% by mass) of Polymer Production Example 2 was used instead of the polymer of Polymer Production Example 1.
  • An experiment was conducted to produce polyvieramine. The experiment was carried out at a reaction temperature of 200: pressure and a pressure of lOMPa. The obtained reaction product was analyzed in the same manner as in Example 19, and as a result, the amine conversion was as high as 70 mol%.

Abstract

L'invention concerne un appareil de production comprenant une cuve à réaction (11), un moyen (12) pour chauffer la cuve à réaction (11), un moyen (13) pour agiter l'intérieur de la cuve à réaction (11), des moyens (1, 2, 3) pour alimenter la cuve à réaction (11) respectivement en eau, en N-vinylformamide et en amorceur de polymérisation, et un moyen (4) pour introduire un gaz inerte dans la cuve à réaction (11). Ledit appareil est utilisé pour la production d'un polymère de N-vinylformamide dans une cuve à réaction (11). Le polymère de N-vinylformamide est ensuite hydrolysé dans la cuve à réaction (11) en présence d'eau, à au moins 100 °C et à une pression non inférieure à la pression de la vapeur d'eau saturée de l'eau en l'absence de catalyseur. Ainsi, une polyvinylamine est produite.
PCT/JP2000/004682 1999-07-16 2000-07-13 Procede et appareil de production de polyvinylamine WO2001005847A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58529/00A AU5852900A (en) 1999-07-16 2000-07-13 Process for producing polyvinylamine and production apparatus

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JP11/203946 1999-07-16
JP11203946A JP2001031717A (ja) 1999-07-16 1999-07-16 ポリビニルアミンの製造法および製造装置

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1582537A1 (fr) * 2004-03-24 2005-10-05 Nippon Shokubai Co., Ltd. Polymère de N-vinyl amide et procédé de sa préparation.
WO2010052179A1 (fr) * 2008-11-05 2010-05-14 Basf Se Procédé d'hydrolyse de polymères contenant des unités amide d'acide carboxylique vinylique

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015156251A1 (fr) * 2014-04-08 2015-10-15 三菱レイヨン株式会社 Procédé de production d'un polymère contenant des unités vinyle-amine, et produit de polymérisation

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US4880497A (en) * 1985-09-26 1989-11-14 Basf Aktiengesellschaft Preparation of water-soluble copolymers containing vinylamine units, and their use as wet strength agents and dry strength agents for paper
JPH03190908A (ja) * 1989-12-20 1991-08-20 Mitsubishi Kasei Corp 水溶性ポリマーの製法
JPH03195704A (ja) * 1989-12-22 1991-08-27 Mitsubishi Kasei Corp 水溶性ポリマーの製法
JPH05125109A (ja) * 1990-03-08 1993-05-21 Basf Ag Ｎ−ビニルホルムアミドの加水分解された粉末状重合体の製法及び製紙用の脱水剤、保持剤及び凝結剤

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4880497A (en) * 1985-09-26 1989-11-14 Basf Aktiengesellschaft Preparation of water-soluble copolymers containing vinylamine units, and their use as wet strength agents and dry strength agents for paper
US4978427A (en) * 1985-09-26 1990-12-18 Basf Aktiengesellschaft Water-soluble copolymers containing vinylamine units as wet strength and dry strength agent for paper
JPH03190908A (ja) * 1989-12-20 1991-08-20 Mitsubishi Kasei Corp 水溶性ポリマーの製法
JPH03195704A (ja) * 1989-12-22 1991-08-27 Mitsubishi Kasei Corp 水溶性ポリマーの製法
JPH05125109A (ja) * 1990-03-08 1993-05-21 Basf Ag Ｎ−ビニルホルムアミドの加水分解された粉末状重合体の製法及び製紙用の脱水剤、保持剤及び凝結剤

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1582537A1 (fr) * 2004-03-24 2005-10-05 Nippon Shokubai Co., Ltd. Polymère de N-vinyl amide et procédé de sa préparation.
US7214753B2 (en) 2004-03-24 2007-05-08 Nippon Shokubai Co., Ltd. N-vinyl amide polymer and production method thereof
WO2010052179A1 (fr) * 2008-11-05 2010-05-14 Basf Se Procédé d'hydrolyse de polymères contenant des unités amide d'acide carboxylique vinylique
US8575267B2 (en) 2008-11-05 2013-11-05 Basf Se Process for hydrolyzing polymers containing vinylcarboxamide units

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