EP0179133A4 - PROCESS FOR THE PREPARATION OF ION EXCHANGE RESINS USING GERM POLYMERIZATION TECHNOLOGY. - Google Patents
PROCESS FOR THE PREPARATION OF ION EXCHANGE RESINS USING GERM POLYMERIZATION TECHNOLOGY.Info
- Publication number
- EP0179133A4 EP0179133A4 EP19850902287 EP85902287A EP0179133A4 EP 0179133 A4 EP0179133 A4 EP 0179133A4 EP 19850902287 EP19850902287 EP 19850902287 EP 85902287 A EP85902287 A EP 85902287A EP 0179133 A4 EP0179133 A4 EP 0179133A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- monomer
- seed
- swollen
- employed
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C08F2/00—Processes of polymerisation
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- 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
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
Definitions
- the present invention relates to ion exchange resin particles, and in particular, to those particles that are prepared using seeded polymerization technology-
- Ion exchange resins are typically prepared by providing functional groups which have the capacity for ion exchange to crosslinked copolymer particles or beads.
- the copolymer beads provide a strong, insoluble and rigid substrate for carrying the ion exchange functional groups.
- the durability and hydraulic characteristics of the ion exchange resin are generally limited by those characteristics of the copolymer from which it is derived.
- ion exchange copolymers are prepared using a batch process whereby monomer droplets are formed and suspended in an aqueous phase, and polymerized.
- a process can provide a wide distri ⁇ bution of bead particle sizes.
- it becomes neces ⁇ sary to mechanically screen the beads and/or ion exchange resin particles in order to obtain a desirable product having a relatively uniform or narrow distribution of bead size.
- a lightly crosslinked copolymer seed can be swelled in the presence of a monomer mix containing an initiator and a crosslinker.
- the imbibed monomer mixture is polymerized in situ by a standard suspension polymeri ⁇ zation process.
- Such particles have very high physical strengths.
- the copolymer particles are then function- alized by chemically treating the insoluble, crosslinked bead in order to attach an ion exchange group thereto.
- the particles so prepared can exhibit several disadvantages.
- an ion exchange resin which is prepared using the batch seeded process may not provide sufficient ion exchange properties, or bed operation time before breakthrough may be very short.
- ion exchange resins are stirred in relatively pure water, a cloudy aqueous suspension may be observed to form. It is believed that insoluble organic materials which leach out of the resin particle provide this undesirable contamination of the water.
- the resin particles which have highly desirable physical characteristics are not acceptable for use in applications such as water treatment.
- This invention is a seed process for preparing improved crosslinked copolymer particles capable of being functionalized to provide ion exchange copolymer particles having a high capability of withstanding osmotic shock during use, which process comprises:
- this invention is a seed process for preparing improved crosslinked copolymer particles capable of being functionalized to provide ion exchange copolymer particles having a high capability of withstanding osmotic shock during use, which process comprises:
- the copolymer particles prepared via the process of this invention can be functionalized to provide ion exchange resin beads, which resin beads have good osmotic shock and mechanical resistances to breaking. That is, for example, functionalized copolymer p rticles prepared via the process of this invention possess crush strengths (i.e., mechanical load required to break individual resin beads) of at least 500 g/bead crush strength and a resistance to osmotic shock such that when said particles are contacted with 10 cycles of alternating treatments with 8 molar sodium hydroxide and 8 molar hydrochloric acid, separated by backwashings with deionized water, fewer than about 15 percent by number of the particles are broken.
- crush strengths i.e., mechanical load required to break individual resin beads
- a resistance to osmotic shock such that when said particles are contacted with 10 cycles of alternating treatments with 8 molar sodium hydroxide and 8 molar hydrochloric acid, separated by backwashings with deionized water, fewer than about
- One full cycle of said treatment comprises (a) immersing a quantity of beads into 8 M HC1 for one minute, (b) washing with deionized water until the wash water is neutral, (c) immersing the beads in 8 M NaOH for one minute and (d) washing the beads with deionized water until the ' wash water is neutral.
- All references to alternating treatments with 8 M HCl and 8 M NaOH contained herein refer to repeating cycles of this test.
- the resistance to osmotic shock of the beads is measured by the number of beads which remain unbroken after 10 cycles of the test. Typically, at least 85 percent of the function ⁇ alized beads of this invention will remain unbroken after 10 cycles of the osmotic shock test.
- Ion exchange resins can be either anionic or cationic in nature.
- Such ion exchange resins are useful for a wide variety of applications known in the art. Of particular interest is the treatment of aqueous fluids in order to obtain highly pure water.
- the monoethylenically unsaturated monomers useful herein are those commonly employed in the produc ⁇ tion of ion exchange resins.
- suitable mono ⁇ mers are disclosed in US 4,419,245. Reference is made to Polymer Processes, edited by Calvin E. Schildknecht, published in 1956 by Interscience Publishers, Inc., New York, Chapter III, "Polymerization in Suspension" by E. Trommsdoff and ⁇ C. E. Schildknecht, pp. 69-109 for purposes of illustration. In Table II on pp. 78-81 of Schildknecht are listed diverse kinds of monomers which can be employed in the practice of this invention. Styrene is the most preferred monomer.
- Suitable crosslinking monomers are preferably those polyethylenically unsaturated monomers including those listed in U.S. Patent No. 4,419,245.
- the preferred polyethylenically unsaturated monomer is divinylbenzene.
- the crosslinked seed particles useful in this invention are those which are lightly crosslinked in order to achieve the degree of swelling required to produce the final copolymer products of the desired size.
- the seed particles are spheroidal beads derived from polymerized monoethylenically unsat ⁇ urated monomer(s) and a crosslinking agent therefor.
- the crosslinking agent is preferably a polyethylenically unsaturated monomer.
- the amount of cross ⁇ linking agent in the seed can range from about 0.1 to about 3 weight percent, based on the weight of total monomer used in preparing the seed.
- the amounts of each of the mono- and polyethylenically unsaturated monomers most advan ⁇ tageously employed in the preparation of the seed and seeded bead depend on a variety of factors including the type of each monomer employed and the desired size of the seed, seeded bead and resulting ion exchange bead.
- the amount and type of the mono- and polyethylenically unsaturated monomers employed.in preparing the seeded bead from the seed bead (i.e., those monomers imbibed by the seed bead) most advantageously employed herein will also vary depending on the size
- the seed and seeded beads are advantageously prepared using amounts of the mono- and polyethylenic monomers such that the seeded beads can be converted into ion exchange resin beads via techniques such as sulfonation, chloro- methylation, amination, and the like.
- the resulting functionalized beads when completely saturated with water preferably have a particle size of 0.3 mm to 1.0 mm and exhibit improved integrity (i.e., spheroidal character) and increased resistance to osmotic shock when compared to a conventionally prepared copolymer bead functionalized using similar conditions.
- the size of the seed can vary.
- the size varies from 100 ⁇ to 600 ⁇ m, preferably from about 200 ⁇ m to about 400 ⁇ m.
- the seed is generally swelled from about 1.5 to about 2.2 times its original diameter. It is imbibed with monomer to about 3 to about 10 times its original weight.
- Polymerization initiators useful herein include those initiators useful in the preparation of the seed bead.
- the aqueous suspension of seed particles is contacted with the initiator along with the first monomer mixture comprising the minor -amount of polyvinyl crosslinking monomer.
- the initiator is a conventional chemical initiator useful as a free radical generator in the polymerization of ethylenically unsaturated monomers.
- UV radiation and chemical initiators including azo compounds such as azobisiso- butyronitrile; peroxygen compounds such as benzoyl peroxide, t-butyl peroctoate, t-butyl perbenzoate and isopropylpercarbonate; and the like.
- the initiator is employed in an amount sufficient to cause the copolymerization of the monomeric components in the monomer mixture. Such amount will generally vary depending on a variety of factors including the type of initiator employed, reaction temperature, the composition of the seed bead and the type and proportion of monomers in the monomer mixture imbibed thereby. Generally, the initiator is employed in amounts from 0.02 to 1, preferably from 0.05 to 0.5, weight percent based on the total weight of the monomer mixture.
- the seed beads are advantageously suspended, using relatively high agitation rates, in a suitable suspending medium such as water or other aqueous liquid.
- Suspending agents are most preferably added after the first monomer mixture has been allowed to imbibe into the seed.
- Suspending agents useful herein are those materials which assist in maintaining a more uniform dispersion of the swollen seed beads in the aqueous liquid.
- the suspending agents most advan- tageously employed herein are dependent on the type and amount of monomers employed in preparing the swollen seed bead, in general, suspending agents conventionally employed hereto in the suspension polymerization of mono- and polyethylenically unsaturated monomers are advantageously employed.
- suspending agents are gelatin, polyvinyl alcohol, sodium, dodecyl sulfonate, sodium methacrylate, magnesium silicate, sodium cellulose glycolate, hydroxyethylcellulose, methylcelluloses and the like.
- Suitable suspending agents are disclosed in U.S. Patent No. 4,419,245.
- the amount of the suspending agent employed is dependent on a variety of factors and is advantageously that amount which prevents agglomeration of the swollen seed beads but does not prevent further imbibition of monomers.
- from 0.05 to 1.0 weight percent, of the suspending agent, based on the weight of the aqueous phase is advantageously employed.
- the suspending medium is employed in amounts from 30 to 70, preferably from 40 to 60, weight percent based on the weight of the swollen seed beads, i.e., the weight of the seed bead and monomer mixture.
- the process of this invention involves two critical stages in the preparation of the copolymer bead.
- the first stage involves suspending the seed under conditions such that imbibition of monomers which are contacted with the seed can occur. That is, upon contacting the seed bead with the monomer mixture, the seed bead swells, which swelling is believed to be due generally to the absorption of monomer mixture by the seed bead.
- the monomer can be added continuously or batchwise.
- the initiator can be added to the medium or added along with the monomer.
- the seed bead can be suspended during imbibition using suitable agitation conditions.
- the monomer mixture includes a minor amount of the crosslinking agent which is employed. That is, 1 to 15, preferably 1 to 10, most preferably 1 to 5, weight percent of the total amount of cross ⁇ linking agent which is employed is added in the first stage.
- the temperature employed to polymerize the imbibed monomers in the first stage can vary depending upon the choice of initiator. Polymerization is generally conducted at temperatures between 50°C and 100°C, pre ⁇ ferably between 60°C and 90°C, most preferably 80°C. In one aspect of this invention, before the second stage of process is commenced, it is necessary to remove the reaction mixture from a state of polymer ⁇ ization conditions. In addition, it is highly desirable that polymerization conditions be ceased before total polymerization has occured. If desired, polymerization of imbibed monomer can be substantially completed. This typically occurs when the seeded, swollen bead reaches its gel point.
- polymerization in the first stage should continue until 40 to 80 per ⁇ cent monomer conversion to polymer.
- This typically means lowering the temperature of the reaction mixture such that the second mixture of monomers can be con ⁇ tacted and imbibed into the swollen seeds without significant latex formation.
- the second stage monomer mixture can include a suitable amount of initiator.
- the second stage of the polymerization process is commenced after the second monomer mixture has been contacted with the partially polymerized bead. This is believed necessary in order to allow the second monomer mixture to be imbibed into said bead.
- the second stage monomer mixture includes a major amount of the cross ⁇ linking agent which is employed. That is, 85 to 99, preferably 90 to 99, most preferably 95 to 99, weight percent of the total amount of crosslinking agent which is employed is added in the second stage.
- the reaction mixture is subjected to polymerization conditions until essentially total polymerization of the monomer has been achieved.
- the polymerization reaction is then finished, for example, by raising the reactor temperature.
- the second stage of the process involves a continuous feed of the second monomer mixture to the suspended swollen, partially polymerized seeds. It is not necessary to remove the reaction mixture from a state of polymerization conditions. That is, by controlling the feed rate of the addition of the second monomer mixture, the suspension conditions, the rate of reaction, and the like, it is possible to continuously imbibe the second stage monomer mixture into the swollen bead, which is subjected to polymerization conditions where the imbibed monomers continue to undergo polymerization.
- the amount of various monomeric components in the first stage monomer mix can range from 0.5 to 5 weight percent crosslinking agents, and from 95 to 99.5 weight percent monethylenically unsaturated monomer(s).
- the amount of various monomeric components in the second stage monomer mix can range from 5 to 20 weight percent crosslinking agent, and from 80 to 95 weight percent monoethylenically unsaturated monomer(s).
- the amount of second stage monomer mixture relative to the first stage monomer mixture can range from 50 to 80 weight percent based on the total weight of the monomer mixtures, subject to the limitation that the amount of crosslinking agent employed in the second stage mixture is a major amount based on the total amount of crosslinking agent which is employed.
- the amount of crosslinking monomer employed in preparing the final resin is 2 to 18, pre ⁇ ferably 5 to 15 percent based on the total amount of organic material (i.e., seed plus polymerizable monomer).
- the time periods over which each of the two (i.e., first or second) polymerization stages occur can vary as long as the desired species are obtained in each case.
- the first stage monomer mixture can be added to the seed suspension either batchwise or continuously and subjected to polymerization conditions over a period ranging from 2 to 8 hours.
- the second stage monomer mixture is added either batchwise or con ⁇ tinuously, preferably over a period ranging from 3 to 5 hours.
- the imbibition is preferably carried out at 20°C to 50°C and is allowed to occur, preferably with suitable mixing, for a period of 1 to 3 hours.
- the polymerization conditions are maintained in the second stage polymerization step for 8 to 14 hours. Finishing the reaction is performed for 1 to 3 hours, preferably at temperatures from 90°C to 120°C.
- the resulting seeded beads are recovered from the reaction media using con ⁇ ventional techniques, such as filtration, and the recovered beads are washed and dried. Functional groups are provided to the beads using known techniques. That is, copolymer beads are converted to anion and cation exchange beads. Beads can be fractionated into various size ranges using techniques such as screening.
- Example 1 Into a 1-gallon (3.79 x 10 -3 m3) stainless steel reactor equipped with an agitator were loaded 875 grams (g) deionized water, 130 g of 0.3 percent cross ⁇ linked styrene/divinylbenzene copolymer seed of -50+70 mesh (from 210 ⁇ m to 297 ⁇ m) particle size with agitation, and 300 g of monomer I, comprising styrene and 1.3 percent active divinylbenzene, 0.05 percent active t-butylper- octoate ' (TBPO) and 0.16 active percent t-butylperbenzoate (TBPB) based on monomer I.
- TBPO active t-butylper- octoate '
- TBPB active percent t-butylperbenzoate
- the copolymer thus, made after appropriate screening was checked for crosslink density and then converted into a strong acid cation exchange resin. Fifty grams of the copolymer thus obtained was sulfonated to a cation exchange resin. The resin after appropriate washing was tested for capacity, crush strength, osmotic shock resistance, and water quality. A mixture of 50 ml each of resin and water was vigorously stirred magnetically for 30 minutes and the aqueous layer examined for clarity.
- Example 2 Into a reactor as described in Example 1 was charged 850 g deionized water, 215 g of 0.3 percent crosslinked styrene/divinylbenzene copolymer seed of -50+60 mesh (from 210 ⁇ m to 297 ⁇ m) particle size with agitation, and 215 g of monomer I containing styrene and 1.7 percent active divinylbenzene, 0.036 active percent TBPO and 0.05 percent active TBPB. After 30 to 60 minutes of swelling time, 325 g of an aqueous solution of the previously described stabilizers and latex inhibitor was added.
- the reactor was sealed, purged with nitrogen and the temperature of the mixture was raised to 80°C, 95°C and 110°C for 8, 1.5 and 1.5 hours, respectively.
- the reaction mixture was cooled to 40°C, and 995 g of monomer II containing styrene and 13.9 percent divinylbenzene, 0.015 percent TBPO and 0.05 percent TBPB was added to the reactor.
- the mixture was allowed 60 to 120 minutes swelling time.
- the reaction mixture was heated at 85°C, 95°C and 110°C for 10, 1.5 and 1.5 hours, respectively.
- the copolymer beads were isolated and converted to strong acid cation exchange resins.
- Example 3 Into a 20 gallon (75.7 x 10 m ) stainless steel reactor equipped with an agitator were charged 70 lbs. (31.75 kg) of deionized water and with stirring, 13.3 lbs. (6.03 kg) of 0.3 percent divinylbenzene cross ⁇ linked polystyrene seed of -50+60 mesh (from 210 ⁇ m to 297 ⁇ m). Also charged was 20 lbs. (9.07 kg) of monomer I containing styrene, 1.44 percent active divinylbenzene, 0.26 percent active TBPO and 0.22 percent TBPB. After 30 to 60 minutes of imbibing time, 20 lbs.
- Copolymer particles were prepared employing the procedures generally described in Example Nos. 1-3. These samples were compared to beads prepared using a conventional methods of preparation as follows:
- Example 5 Into a 1 gallon (3.79 x 10 -3 m3) stainless steel reactor, equipped with an agitator, were loaded 750 g deionized water, 215 g of 0.3 percent crosslinked styrene/divinylbenzene copolymer seed of -50+60 mesh (from 210 ⁇ m to 297 ⁇ m) particle size with agitation and 215 g of monomer I, containing styrene and 1.7 percent active divinylbenzene, 0.075 percent active TBPO and 0.25 percent active TBPB. After 30-60 minutes of swelling time, 325 g of an aqueous solution of stabilizer and latex inhibitor was added. The reactor temperature was raised to and maintained at 80°C for 6 hours.
- the reactor mass was cooled to 40°C and 640 g of monomer II containing styrene and 8.8 percent active divinylbenzene was added to the reactor. After 60 to 90 minutes of swelling time, the reactor mass was heated to 85°, 95° and 110°C for 10, 1.5 and 1.5 hours, each successively.
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Graft Or Block Polymers (AREA)
- Polymerisation Methods In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US60278784A | 1984-04-23 | 1984-04-23 | |
US602787 | 1990-10-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0179133A1 EP0179133A1 (en) | 1986-04-30 |
EP0179133A4 true EP0179133A4 (en) | 1986-09-15 |
Family
ID=24412808
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19850902287 Withdrawn EP0179133A4 (en) | 1984-04-23 | 1985-04-16 | PROCESS FOR THE PREPARATION OF ION EXCHANGE RESINS USING GERM POLYMERIZATION TECHNOLOGY. |
Country Status (17)
Country | Link |
---|---|
EP (1) | EP0179133A4 (no) |
JP (1) | JPS61501096A (no) |
KR (1) | KR860700037A (no) |
AU (1) | AU565577B2 (no) |
BR (1) | BR8506719A (no) |
CA (1) | CA1277064C (no) |
CS (1) | CS253725B2 (no) |
DD (1) | DD234871A5 (no) |
ES (1) | ES8608012A1 (no) |
FI (1) | FI855062A (no) |
GR (1) | GR850968B (no) |
HU (1) | HUT39194A (no) |
IL (1) | IL74893A0 (no) |
NO (1) | NO855199L (no) |
PL (1) | PL253047A1 (no) |
WO (1) | WO1985004885A1 (no) |
ZA (1) | ZA852961B (no) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4952651A (en) * | 1988-03-30 | 1990-08-28 | Japan Synthetic Rubber Co., Ltd. | Highly crosslinked polymer particles and process for producing the same |
DE69314606T2 (de) | 1992-12-10 | 1998-05-07 | Mitsubishi Chem Corp | Verfahren zur Herstellung eines kugelförmigen Ionen-Austauscherharzes |
DE19634393A1 (de) * | 1996-08-26 | 1998-03-05 | Bayer Ag | Verfahren zur Herstellung vernetzter Polymerisate |
US7022744B2 (en) * | 2002-04-11 | 2006-04-04 | Mitsubishi Chemical Corporation | Ion exchanger for lipoproteins separation and lipoproteins separation method using the same |
DE112015001834T5 (de) | 2014-04-15 | 2017-01-05 | Rohm And Haas Company | Sulfonierung von Aromatischen Polymeren unter Verwendung einer fluorierten Benzolverbindung als Quellmittel |
US20180001228A1 (en) | 2015-02-27 | 2018-01-04 | Dow Global Technologies Llc | Chromatographic separation of saccharides using whole cracked beads of gel-type strong acid exchange resin |
WO2016137787A1 (en) | 2015-02-27 | 2016-09-01 | Rohm And Haas Company | Chromatographic separation of saccharides using cation exchange resin beads with rough outer surface |
US20180001313A1 (en) | 2015-03-12 | 2018-01-04 | Dow Global Technologies Llc | Chromatographic separation of saccharides using strong acid exchange resin incorporating precipitated barium sulfate |
WO2016178842A1 (en) | 2015-05-04 | 2016-11-10 | Dow Global Technologies Llc | Removal of phosphorous from water using weak base anion exchange resin loaded with alumina |
BR112018011184B1 (pt) | 2015-12-01 | 2022-09-06 | Dow Global Technologies Llc | Método para separar cromatograficamente ácido propiônico de uma mistura de alimentação líquida |
WO2017095686A1 (en) | 2015-12-01 | 2017-06-08 | Dow Global Technologies Llc | Chromatographic separation of organic acids using resin having strong and weak base anion exchange capacity |
CN105367689B (zh) * | 2015-12-22 | 2017-07-25 | 漂莱特(中国)有限公司 | 凝胶型强碱性阴离子交换树脂 |
CN105524202A (zh) * | 2015-12-22 | 2016-04-27 | 漂莱特(中国)有限公司 | 吸铀树脂的制备方法 |
CN105418819B (zh) * | 2015-12-22 | 2017-07-21 | 漂莱特(中国)有限公司 | 凝胶型强碱性阴离子交换树脂的制备方法 |
CN105399888A (zh) * | 2015-12-22 | 2016-03-16 | 漂莱特(中国)有限公司 | 吸铀树脂 |
WO2019118282A1 (en) | 2017-12-13 | 2019-06-20 | Dow Global Technologies Llc | Regeneration process of an anionic exchange resin used for mercaptans removal |
CN116762803B (zh) * | 2023-08-24 | 2023-11-03 | 广州巴宝莉化妆品有限公司 | 一种鲜花冷冻保鲜方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0101943A2 (en) * | 1982-08-02 | 1984-03-07 | The Dow Chemical Company | Ion exchange resins |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1292226A (en) * | 1970-03-17 | 1972-10-11 | Permutit Co Ltd | Production of copolymers |
US4085169A (en) * | 1973-07-23 | 1978-04-18 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Process for preparing styrenic polymer particles |
US4091054A (en) * | 1973-07-23 | 1978-05-23 | Sekisui Kagaku Kogyo Kabushiki Kaisha | Process of preparing styrenic polymer particles |
DD158907A1 (de) * | 1981-05-04 | 1983-02-09 | Georgi Popov | Verfahren zur herstellung von grobkoernigen ionenaustauscherharzen |
US4419245A (en) * | 1982-06-30 | 1983-12-06 | Rohm And Haas Company | Copolymer process and product therefrom consisting of crosslinked seed bead swollen by styrene monomer |
-
1985
- 1985-04-14 IL IL74893A patent/IL74893A0/xx unknown
- 1985-04-16 EP EP19850902287 patent/EP0179133A4/en not_active Withdrawn
- 1985-04-16 WO PCT/US1985/000673 patent/WO1985004885A1/en not_active Application Discontinuation
- 1985-04-16 JP JP60501875A patent/JPS61501096A/ja active Granted
- 1985-04-16 HU HU852155A patent/HUT39194A/hu unknown
- 1985-04-16 AU AU42353/85A patent/AU565577B2/en not_active Ceased
- 1985-04-16 BR BR8506719A patent/BR8506719A/pt unknown
- 1985-04-18 CA CA000479434A patent/CA1277064C/en not_active Expired - Fee Related
- 1985-04-19 ZA ZA852961A patent/ZA852961B/xx unknown
- 1985-04-22 PL PL25304785A patent/PL253047A1/xx unknown
- 1985-04-22 ES ES542449A patent/ES8608012A1/es not_active Expired
- 1985-04-22 GR GR850968A patent/GR850968B/el unknown
- 1985-04-23 CS CS852985A patent/CS253725B2/cs unknown
- 1985-04-23 DD DD85275466A patent/DD234871A5/de unknown
- 1985-12-18 FI FI855062A patent/FI855062A/fi not_active Application Discontinuation
- 1985-12-20 NO NO855199A patent/NO855199L/no unknown
- 1985-12-23 KR KR1019850700401A patent/KR860700037A/ko not_active IP Right Cessation
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0101943A2 (en) * | 1982-08-02 | 1984-03-07 | The Dow Chemical Company | Ion exchange resins |
Also Published As
Publication number | Publication date |
---|---|
CS253725B2 (en) | 1987-12-17 |
KR860700037A (ko) | 1986-01-31 |
EP0179133A1 (en) | 1986-04-30 |
HUT39194A (en) | 1986-08-28 |
ES542449A0 (es) | 1986-06-01 |
IL74893A0 (en) | 1985-07-31 |
NO855199L (no) | 1985-12-20 |
DD234871A5 (de) | 1986-04-16 |
BR8506719A (pt) | 1986-09-23 |
JPH0426321B2 (no) | 1992-05-07 |
AU4235385A (en) | 1985-11-15 |
CA1277064C (en) | 1990-11-27 |
FI855062A0 (fi) | 1985-12-18 |
JPS61501096A (ja) | 1986-05-29 |
AU565577B2 (en) | 1987-09-17 |
ES8608012A1 (es) | 1986-06-01 |
WO1985004885A1 (en) | 1985-11-07 |
GR850968B (no) | 1985-11-25 |
ZA852961B (en) | 1986-12-30 |
FI855062A (fi) | 1985-12-18 |
PL253047A1 (en) | 1985-12-17 |
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