WO1998017697A2 - Process for making vinyl aromatic/allylic alcohol copolymers - Google Patents
Process for making vinyl aromatic/allylic alcohol copolymersInfo
- Publication number
- WO1998017697A2 WO1998017697A2 PCT/EP1997/005730 EP9705730W WO9817697A2 WO 1998017697 A2 WO1998017697 A2 WO 1998017697A2 EP 9705730 W EP9705730 W EP 9705730W WO 9817697 A2 WO9817697 A2 WO 9817697A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- range
- styrene
- free
- radical initiator
- allyl alcohol
- Prior art date
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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- 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
- C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/08—Allyl alcohol
Definitions
- the invention relates to vinyl aromatic/allylic alcohol copolymers such as styrene-allyl alcohol copolymers.
- the invention is an improved process that gives high yields of these copolymers, which are especially valuable as hydroxy-functional resins in the coatings industry.
- Vinyl aromatic/allylic alcohol copolymers are well known (see U.S.).
- Copolymers of styrene and allyl alcohol are resinous polyols that are particularly useful for polyesters, fatty ester emulsions, alkyd and uralkyd coatings, melamines, and polyurethanes.
- Styrene-allyl alcohol copolymers can be made in a batch process by charging a reactor with styrene, allyl alcohol, and a free-radical initiator, and heating the mixture at a temperature effective to polymerize the monomers (usually 100-300°C). While SAA copolymers having relatively low hydroxyl contents
- hydroxy-functional resins with lower hydroxyl numbers are actually an advantage.
- Some coating components are incompatible with SAA copolymers that have a high content of hydroxyl groups.
- Low hydroxyl content can also be an advantage in reducing the amount of relatively expensive crosslinking agent (e.g., polyisocyanate) required.
- an improved process for making vinyl aromatic/allylic alcohol copolymers, especially styrene-allyl alcohol copolymers is needed.
- Coating applications that could benefit from a low hydroxyl group content resin are evolving, and suitable resins are needed for these applications.
- a process for making the resins is therefore also of interest.
- the process would be easy to perform, would use conventional equipment, and would be cost-effective.
- a preferred process would give favorable yields of SAA copolymers having hydroxyl numbers within the 50 to 150 mg KOH/g range.
- the invention is a semi-batch process for making vinyl aromatic/allylic alcohol copolymers.
- the process comprises charging a reactor with an allylic alcohol, 10-30% of the total amount to be used of a vinyl aromatic monomer, and 45-75% of the total amount to be used of a free-radical initiator.
- the mixture is heated at a temperature within the range of about 125°C to about 185°C.
- the remaining 70-90% of the vinyl aromatic monomer and 25-55% of the free-radical initiator are added gradually to the reaction mixture at a decreasing rate.
- the mole ratio of vinyl aromatic monomer to allylic alcohol used in the process is within the range of about 0.6 to about 5.
- the resulting product is a vinyl aromatic/allylic alcohol copolymer having a number average molecular weight within the range of about 2000 to about 10,000 and a hydroxyl number within the range of about 50 mg KOH/g to about 150 mg KOH/g.
- selection of these conditions which include a gradual addition of the free-radical initiator during the course of the polymerization, results in a substantial increase in the yield of vinyl aromatic/allylic alcohol copolymer compared with the yield obtained from a conventional process in which all of the free-radical initiator is charged initially to the reactor.
- the mole ratio of vinyl aromatic monomer to allylic alcohol used in the process is adjusted in a manner effective to give products having the required hydroxyl numbers and number average molecular weights.
- Copolymers prepared by the process are valuable for polyesters, fatty ester emulsions, alkyd and uralkyd coatings, melamines, and polyurethanes. These coating systems have many end uses, including, e.g., wood finishes, industrial coatings, and automotive coatings.
- the process of the invention is well-suited for the manufacture of SAA copolymers having relatively low hydroxyl content, copolymers which are gaining acceptance in the coatings industry because of the compatibility or cost advantages they offer.
- DETAILED DESCRIPTION OF THE INVENTION The invention is a semi-batch process for making copolymers derived from vinyl aromatic monomers and allylic alcohols.
- Suitable vinyl aromatic monomers include, but are not limited to, styrene, alkyl-substituted styrenes (e.g., 4-methylstyrene, 4-tert-butylstyrene, 2,6- dimethylstyrene), halogenated styrenes (e.g., 4-chlorostyrene, dichlorostyrenes, dibromostyrenes, tribromostyrenes), vinyl naphthalenes, and the like, and mixtures thereof.
- alkyl-substituted styrenes e.g., 4-methylstyrene, 4-tert-butylstyrene, 2,6- dimethylstyrene
- halogenated styrenes e.g., 4-chlorostyrene, dichlorostyrenes
- a minor proportion of a di- or polyvinyl aromatic monomer such as divinylbenzene can be included if a greater degree of crosslinking is desired, although preferably only a monovinyl aromatic monomer is used.
- a di- or polyvinyl aromatic monomer such as divinylbenzene
- Styrene and halogenated styrenes are preferred vinyl aromatic monomers.
- allylic alcohol is also used in the process.
- Suitable allylic alcohols include, for example, allyl alcohol, methallyl alcohol, 2-ethyl-2-propen-1-ol, 2-pentyl-2- propen-1-ol, and the like, and mixtures thereof. Allyl alcohol and methallyl alcohol are particularly preferred.
- Suitable propoxylated allyl alcohols can be made, for example, by reacting allyl alcohol with up to 5 equivalents of propylene oxide in the presence of a basic catalyst, as is described in U.S. Patent Nos. 3,268,561 and 4,618,703, the teachings of which are incorporated herein by reference.
- propoxylated allyl alcohols for which n has a value within the range of about 1 to about 2.
- the mole ratio of vinyl aromatic monomer to allylic alcohol used in the process is important. It is adjusted to give copolymer products having the desired hydroxyl numbers and number average molecular weights. In contrast to the process of U.S. Pat. No. 5,444,141 , the mole ratio of vinyl aromatic monomer to allylic alcohol in the process of the invention is maintained within the range of about 0.6 to about 5. A more preferred range is from about 0.6 to about 2; most preferred is the range from about 0.7 to about 1.2.
- An excess of vinyl aromatic monomer may be present in the monomer feed; however, an excess of the allylic alcohol is still normally present in the reaction mixture because of the relatively low reactivity of the allylic alcohol and because of the gradual monomer addition.
- a free-radical initiator is included in the process of the invention.
- Suitable free-radical initiators are the peroxide and azo-type initiators well known to those skilled in the art. High-temperature peroxide initiators are preferred. Examples include di-tert-butylperoxide, tert-butylhydroperoxide, tert-butylperbenzoate, cumene hydroperoxide, and the like.
- the free-radical initiator is used in an amount effective to copolymerize the vinyl aromatic monomer and allylic alcohol.
- the actual amount used varies depending upon many factors, including which free- radical initiator is used, which monomers are present, reaction temperature, desired reaction time, the desired molecular weight and functionality of the polymer, and other factors.
- the total amount of free-radical initiator used is greater than about 1 wt.% based on the total weight of monomers.
- an amount within the range of about 2 wt.% to about 25 wt.% based on the total weight of monomers is used; a more preferred range is from about 3 wt.% to about 15 wt.%.
- the process of the invention is practiced as follows.
- a reactor is first charged with the allylic alcohol (preferably allyl alcohol), 10-
- the mixture is heated at a temperature within the range of about 125°C to about 185°C, preferably from about 135°C to about 165°C.
- the remaining 70-90% (preferably 75-80%) of vinyl aromatic monomer and 25-55% (preferably 30-40%) of free-radical initiator are then gradually added to the reaction mixture at a decreasing rate while polymerization proceeds.
- the manner in which the vinyl aromatic monomer and free-radical initiator are introduced is not critical.
- the vinyl aromatic monomer and free-radical initiator can be added to the reactor separately, or the two can be mixed just prior to the reaction and added as a single stream.
- the mole ratio of vinyl aromatic monomer to allylic alcohol is adjusted within the range of about 0.6 to about 5 in a manner effective to produce a copolymer having the desired hydroxyl number and number average molecular weight.
- the resulting vinyl aromatic/allylic alcohol copolymer has a number average molecular weight within the range of about 2000 to about 10,000 and a hydroxyl number within the range of about 50 mg KOH/g to about 150 mg KOH/g. More preferred copolymers have number average molecular weights within the range of about 2,000 to about 4000, and hydroxyl numbers within the range of about 105 mg KOH/g to about 145 mg
- the process of the invention is well-suited to the preparation of styrene-allyl alcohol (SAA) copolymers that have relatively low hydroxyl group contents, i.e., those having hydroxyl numbers within the range of about 50 mg KOH/g to about 150 mg KOH/g.
- SAA styrene-allyl alcohol
- the process resembles the one we described in U.S. Pat. No. 5,444,141 (the teachings of which are incorporated herein by reference) for making "SAA 100" and "SAA 101 " resinous polyols.
- the key difference is adjustment of the mole ratio of vinyl aromatic monomer to allylic alcohol to give a product having the desired hydroxyl number and number average molecular weight.
- a conventional process for making SAA copolymers involves gradually adding styrene at a decreasing rate to a reaction mixture that contains allyl alcohol and a peroxide initiator (see Example I, U.S. Patent No. 2,940,946). All of the peroxide initiator is normally charged to the reactor at the start of the polymerization, and the polymer yield is typically 20% ("SAA 101 " product) to 30% (“SAA 100" product).
- the expected yield of a low hydroxyl content resin made by the conventional process is 45 to 50% or less.
- copolymers improves substantially if both the vinyl aromatic monomer and the free-radical initiator are added gradually at a decreasing rate to the reaction mixture.
- the yield of copolymer is about 67% (see Example 1 below), which is significantly higher than the yield expected from the conventional process in which all of the free-radical initiator is charged to the reactor initially. This substantial yield improvement makes the process much more economically attractive.
- the process of the invention resembles the process described in the '141 patent except for adjusting the styrene to allyl alcohol ratio
- the reference teaches that high- styrene, low OH-content products such as those made by the process of the invention are not particularly useful in the industry.
- the invention allows significantly higher yields (typically 30-50% higher) of styrene-allyl alcohol copolymers than were available from conventional processes in which all of the free-radical initiator is charged to the reactor at the start of the polymerization.
- the yield increases mean higher operating efficiency, less unreacted monomer to recover and recycle, and more product from each cycle.
- the process increases yields without adversely affecting the copolymer structure, molecular weight, or hydroxyl functionality: the products obtained meet the target specifications for a variety of end uses.
- the vinyl aromatic/allylic alcohol copolymers made by the process of the invention are useful intermediates for preparing a variety of derivatives.
- Copolymers made using the process of the invention can be used in alkyd resins.
- the copolymer, optionally combined with glycerin or another polyol, is partially or fully esterified with a fatty acid to give an alkyd resin.
- the copolymers are useful in uralkyd compositions, melamine- based coatings, polyurethanes, and unsaturated polyester resins.
- Copolymers made by the process of the invention are valuable for many end uses, including, e.g., wood finishes, industrial coatings, and automotive coatings.
- Copolymers made by the process of the invention offer solubility advantages over other SAA copolymers.
- Example 5 shows, relatively low hydroxyl group content SAA resinous polyols are much more soluble in aromatic hydrocarbons than commercially available "SAA 100" and "SAA 101 " resinous polyols.
- Aromatic hydrocarbons are commonly used in many coating applications. The process of the invention therefore provides a convenient way to make SAA copolymers that are useful in coatings that use aromatic hydrocarbons.
- hydroxy-functional resins with low hydroxyl numbers are an advantage.
- Some coating components are incompatible with SAA copolymers that have a high content of hydroxyl groups.
- Example 6 shows, a two-component poiyurethane coating based on AIRTHANE ASN-540M NCO-terminated polyester prepolymer (product of Air Products) and a low hydroxyl content SAA copolymer made by the process of the invention has excellent properties.
- Comparative Example 7 shows, an "SAA 100" resinous polyol is not compatible with the prepolymer, and a satisfactory coating cannot be made.
- Copolymers made by the process of the invention also offer a potential cost advantage.
- the crosslinker is the most expensive coating component. Because the copolymers of the invention have relatively low hydroxyl numbers, they require reduced proportions of expensive crosslinkers such as polyisocyanates or melamines. Thus, the cost of the formulation is reduced if an SAA resinous polyol having a relatively low hydroxyl content can be used.
- SAA resinous polyol having a relatively low hydroxyl content can be used.
- Allyl alcohol (1000 g), styrene (353 g), and di-tert-butylperoxide (76 g) are charged to a five-liter stainless-steel reactor equipped with addition pumps for monomer and initiator, agitator, oil heating jacket, temperature controller, and inlets for nitrogen or vacuum. After purging three times with nitrogen, the reactor is sealed, and the contents are heated to 145°C.
- Styrene (1225 g) is charged to the monomer addition pump; di-tert- butylperoxide (35.8 g) is charged to the initiator addition pump.
- Styrene and di-tert-butylperoxide are added gradually to the reactor over 7 h at 145°C at a decreasing rate.
- the mole ratio of styrene to allyl alcohol used is 0.88.
- the addition rates are as follows.
- styrene 246 g/h for the first hour, 235 g/h for the second hour, 207 g/h for the third hour, 179 g/h for the fourth hour, 150 g/h for the fifth hour, 129 g/h for the sixth hour, and 89 g/h for the seventh hour.
- di-tert-butylperoxide 8.0 g/h for the first hour, 6.5 g/h for the second hour, 6.0 g/h for the third hour, 5.0 g/h for the fourth hour, 4.5 g/h for the fifth hour, 3.5 g/h for the sixth hour, and 2.5 g/h for the seventh hour.
- Allyl alcohol (500 g), styrene (67 g), and di-tert-butylperoxide (16 g) are charged to a one-liter stainless-steel reactor equipped with addition pump, agitator, steam heating jacket, temperature controller, and inlets for nitrogen or vacuum. After purging three times with nitrogen, the reactor is sealed, and the contents are heated to 145°C. Di-tert-butylperoxide (8 g) is mixed with styrene (234 g), and this mixture is pumped into the reactor over 7 h at 145°C at a decreasing rate. The mole ratio of styrene to allyl alcohol used is 0.34.
- the addition rates are as follows: 48 g/h for the first hour, 32 g/h for the second hour, 24 g/h for the third hour, 18 g/h for the fourth hour, and 12 g/h for the fifth hour. Heating continues at 135°C for an additional 0.5 h.
- Comparative Examples 2 and 3 show that a 33% increase in yield (from about 30% to 40%) is available from a process in which the di-tert- butylperoxide is added gradually during the course of the polymerization
- Comparative Example 2 compared with the process in which all of the free- radical initiator is charged at the start of the polymerization (Comparative Example 3).
- the target in both comparative examples is an "SAA 100" product, i.e., a styrene-allyl alcohol copolymer having a hydroxyl number of about 200 mg KOH/g, and a number average molecular weight of about
- the mole ratio of styrene to allyl alcohol used is 0.22.
- the addition rates are as follows: 34 g/h for the first hour, 29 g/h for the second hour, 26 g/h for the third hour, 23 g/h for the fourth hour, 19 g/h for the fifth hour, 15 g/h for the sixth hour, and 11 g/h for the seventh hour. Heating continues at 145°C for an additional 0.5 h.
- Example 1 and Comparative Examples 2-4 show that gradual addition of the free-radical initiator generally improves yield (Comparative Examples 2 and 3), and that a high yield of copolymer (67%) is available from the gradual addition process when the target is a styrene-allyl alcohol copolymer having a hydroxyl number within the range of about 50 to about 150 mg KOH/g.
- EXAMPLE 5 shows that gradual addition of the free-radical initiator generally improves yield (Comparative Examples 2 and 3), and that a high yield of copolymer (67%) is available from the gradual addition process when the target is a styrene-allyl alcohol copolymer having a hydroxyl number within the range of about 50 to about 150 mg KOH/g.
- Example 1 (892.5 g of 70% solution in propylene glycol methyl ether acetate), methyl isobutyl ketone (125 g), BYK 300 silicone surface additive
- Part of this mixture (100 g) is diluted with more methyl isobutyl ketone (40 g), and this solution is then mixed with Part B, which is AIRTHANE ASN-540M NCO-terminated polyester prepolymer (88.8
- the clearcoat solution is clear and has a viscosity of 68 s (EZ Cup
- Comparative Example 2 (790 g of 70% solution in propylene glycol methyl ether acetate), methyl isobutyl ketone (75 g), BYK 300 flow aid (1.71 g), and METACURE T-120 catalyst (0.85 g). Part of this mixture (100 g) is diluted with more methyl isobutyl ketone (40 g), and this solution is then mixed with Part B, which is AIRTHANE ASN-540M NCO-terminated polyester
- the clearcoat solution turns cloudy and phase separates immediately after Parts A and B are mixed. This mixture is not suitable for making a coating.
- Example 6 and Comparative Example 7 show that SAA resinous polyols made by the process of the invention can give excellent coatings in a two-component polyurethane coating formulation, while commercially available SAA resins such as "SAA 100" resinous polyol may not always be compatible.
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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)
- Polymerisation Methods In General (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69704370T DE69704370T2 (en) | 1996-10-21 | 1997-10-17 | METHOD FOR PRODUCING COPOLYMERS OF VINYLAROMATIC MONOMERS AND ALLYL ALCOHOL |
JP51894098A JP4024863B2 (en) | 1996-10-21 | 1997-10-17 | Method for producing vinyl aromatic monomer / allylic alcohol copolymer |
AU51200/98A AU5120098A (en) | 1996-10-21 | 1997-10-17 | Process for making vinyl aromatic/allylic alcohol copolymers |
EP97945853A EP0932630B1 (en) | 1996-10-21 | 1997-10-17 | Process for making vinyl aromatic/allylic alcohol copolymers |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US73428496A | 1996-10-21 | 1996-10-21 | |
US08/888,489 | 1997-07-08 | ||
US08/888,489 US5886114A (en) | 1996-10-21 | 1997-07-08 | Process for making vinyl aromatic/allyl alcohol copolymers |
US08/734,284 | 1997-07-08 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1998017697A2 true WO1998017697A2 (en) | 1998-04-30 |
WO1998017697A3 WO1998017697A3 (en) | 1998-07-09 |
Family
ID=27112704
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1997/005730 WO1998017697A2 (en) | 1996-10-21 | 1997-10-17 | Process for making vinyl aromatic/allylic alcohol copolymers |
Country Status (7)
Country | Link |
---|---|
US (1) | US5886114A (en) |
EP (1) | EP0932630B1 (en) |
JP (1) | JP4024863B2 (en) |
AU (1) | AU5120098A (en) |
DE (1) | DE69704370T2 (en) |
ES (1) | ES2154910T3 (en) |
WO (1) | WO1998017697A2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE60100395T2 (en) | 2000-05-10 | 2004-04-22 | Rohm And Haas Co. | Hotmelt adhesive |
US6455657B1 (en) | 2001-02-14 | 2002-09-24 | Arco Chemical Technology, L.P. | Preparation of vinyl aromatic-allylic alcohol copolymers |
KR102645385B1 (en) * | 2020-11-19 | 2024-03-11 | 한국화학연구원 | Polymer composition, shape memory polymer formed therefrom, and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2894938A (en) * | 1955-01-12 | 1959-07-14 | Monsanto Chemicals | Copolymer of a styrene compound and an unsaturated alcohol |
US5444141A (en) * | 1994-07-06 | 1995-08-22 | Arco Chemical Technology, L.P. | Process for making vinyl aromatic/allylic alcohol copolymers |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2630430A (en) * | 1948-04-05 | 1953-03-03 | Shell Dev | Allyl alcohol-styrene copolymers |
US2940946A (en) * | 1956-09-04 | 1960-06-14 | Shell Oil Co | Allyl alcohol-vinyl aromatic copolymers |
US3268561A (en) * | 1963-12-24 | 1966-08-23 | Jefferson Chem Co Inc | Glycidyl ethers |
US4618703A (en) * | 1985-09-13 | 1986-10-21 | Atlantic Richfield Company | Production of the acrylates and methacrylates of oxyalkylated allyl alcohol |
JPS62174214A (en) * | 1986-01-28 | 1987-07-31 | Daicel Chem Ind Ltd | Production of copolymer |
US5382642A (en) * | 1993-07-28 | 1995-01-17 | Arco Chemical Technology, L.P. | Copolymers of allyl alcohol propoxylates and vinyl aromatic monomers |
-
1997
- 1997-07-08 US US08/888,489 patent/US5886114A/en not_active Expired - Lifetime
- 1997-10-17 ES ES97945853T patent/ES2154910T3/en not_active Expired - Lifetime
- 1997-10-17 EP EP97945853A patent/EP0932630B1/en not_active Expired - Lifetime
- 1997-10-17 DE DE69704370T patent/DE69704370T2/en not_active Expired - Lifetime
- 1997-10-17 AU AU51200/98A patent/AU5120098A/en not_active Abandoned
- 1997-10-17 WO PCT/EP1997/005730 patent/WO1998017697A2/en active IP Right Grant
- 1997-10-17 JP JP51894098A patent/JP4024863B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2894938A (en) * | 1955-01-12 | 1959-07-14 | Monsanto Chemicals | Copolymer of a styrene compound and an unsaturated alcohol |
US5444141A (en) * | 1994-07-06 | 1995-08-22 | Arco Chemical Technology, L.P. | Process for making vinyl aromatic/allylic alcohol copolymers |
Non-Patent Citations (1)
Title |
---|
CHEMICAL ABSTRACTS, vol. 107, no. 20, 16 November 1987 Columbus, Ohio, US; abstract no. 177156, OKITSU KIYOSHI: "MANUFACTURE OF ALLYL ALCOHOL-STYRENE COPOLYMERS" page 45; column 2; XP002063602 & JP 62 174 214 A (DAICEL CHEM. IND.) * |
Also Published As
Publication number | Publication date |
---|---|
US5886114A (en) | 1999-03-23 |
DE69704370D1 (en) | 2001-04-26 |
EP0932630B1 (en) | 2001-03-21 |
ES2154910T3 (en) | 2001-04-16 |
AU5120098A (en) | 1998-05-15 |
WO1998017697A3 (en) | 1998-07-09 |
DE69704370T2 (en) | 2001-08-23 |
JP2002514237A (en) | 2002-05-14 |
JP4024863B2 (en) | 2007-12-19 |
EP0932630A2 (en) | 1999-08-04 |
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