US20010053829A1 - Continuous, solvent-free process for making copolymers of maleic anhydride and C1-4 alkyl vinyl ether - Google Patents

Continuous, solvent-free process for making copolymers of maleic anhydride and C1-4 alkyl vinyl ether Download PDF

Info

Publication number
US20010053829A1
US20010053829A1 US09/861,044 US86104401A US2001053829A1 US 20010053829 A1 US20010053829 A1 US 20010053829A1 US 86104401 A US86104401 A US 86104401A US 2001053829 A1 US2001053829 A1 US 2001053829A1
Authority
US
United States
Prior art keywords
vinyl ether
alkyl vinyl
solvent
reactor
maleic anhydride
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.)
Granted
Application number
US09/861,044
Other versions
US6451944B2 (en
Inventor
Russell Biss
Jeffrey Cohen
John Zamora
Krystyna Plochocka
Jeffrey Lynn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ISP CAPITAL Inc
Original Assignee
ISP Investments LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ISP Investments LLC filed Critical ISP Investments LLC
Priority to US09/861,044 priority Critical patent/US6451944B2/en
Assigned to ISP INVESTMENTS INC. reassignment ISP INVESTMENTS INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LYNN, JEFFREY A., COHEN, JEFFREY, ZAMORA, JOHN, BISS, RUSSELL, PLOCHOCKA, KRYSTYNA
Assigned to ISP CAPITAL, INC. reassignment ISP CAPITAL, INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: ISP INVESTMENTS, INC.
Assigned to CHASE MANHATTAN BANK, THE reassignment CHASE MANHATTAN BANK, THE SECURITY AGREEMENT Assignors: ISP CAPITAL, INC.
Publication of US20010053829A1 publication Critical patent/US20010053829A1/en
Application granted granted Critical
Publication of US6451944B2 publication Critical patent/US6451944B2/en
Assigned to THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT reassignment THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT SECURITY AGREEMENT Assignors: AQUALON COMPANY, ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC, HERCULES INCORPORATED, ISP INVESTMENT INC.
Assigned to VERONA, INC., ISP CHEMICAL PRODUCTS, INC., ISP CAPITAL, INC. reassignment VERONA, INC. PATENT RELEASE Assignors: JPMORGAN CHASE BANK, N.A. (F/K/A THE CHASE MANHATTAN BANK)
Assigned to ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC, AQUALON COMPANY, HERCULES INCORPORATED, ISP INVESTMENTS INC. reassignment ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC RELEASE OF PATENT SECURITY AGREEMENT Assignors: THE BANK OF NOVA SCOTIA
Assigned to THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT reassignment THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT SECURITY AGREEMENT Assignors: AVOCA, INC., HERCULES LLC, ISP INVESTMENTS LLC, PHARMACHEM LABORATORIES, INC.
Assigned to PHARMACHEM LABORATORIES LLC, AVOCA LLC, ISP INVESTMENTS LLC, HERCULES LLC reassignment PHARMACHEM LABORATORIES LLC RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: THE BANK OF NOVA SCOTIA
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • 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
    • C08F2/02—Polymerisation in bulk
    • 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
    • C08F216/12—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 ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/16—Monomers containing no hetero atoms other than the ether oxygen
    • C08F216/18—Acyclic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • This invention relates to copolymers of maleic anhydride and a C 1 -C 4 alkyl vinyl ether, and, more particularly, to a continuous, solvent-free process for making solvent-free, fine white powders of such copolymers having advantageous properties useful for oral care compositions.
  • excess AVE monomer is present over a 1:1 molar ratio of monomers, to function both as reactant and solvent in the system. No other solvent is present in the reactor. Accordingly, after stripping the excess AVE from the reaction product, a solvent-free copolymer is obtained.
  • a batch process requires an extended amount of time to effect the reaction, usually necessitating about 9-13 hours to complete each batch.
  • the process herein comprises feeding continuously alkyl vinyl ether as monomer reactant and solvent in excess of the desired 1:1 mole ratio of A:B in the copolymer, molten maleic anhydride and a free radical initiator, at predetermined feeding rates, into a reactor heated at a reaction temperature of about 50° to 100° C., charging the reactor and withdrawing reaction product, residual alkyl vinyl ether and initiator from the reactor at the same rate as the feed rate of reactants into the reactor simultaneously thereby maintaining a constant volume in the reactor, stripping residual alkyl vinyl ether from the reaction product, drying the copolymer obtained of any remaining traces of alkyl vinyl ether, and recycling recovered alkyl vinyl ether back into reactor.
  • the alkyl vinyl ether is methyl vinyl ether
  • the mole ratio of methyl vinyl ether to molten maleic anhydride is about 25:1 to 5:1, most preferably 12:1 to 7:1.
  • the initiator concentration is 0.01 to 0.2% based on the weight of copolymer
  • the % copolymer solids removed from the polymerization reactor is about 10 to 40%.
  • FIGURE is a schematic drawing for making solvent-free copolymers of maleic anhydride (MAN) and C 1-4 alkyl vinyl ethers (AVE) by a continuous, solvent-free process.
  • the continuous solvent-free process of the invention consists of the solvent feed system 100 , the molten maleic anhydride feed system 200 , the catalyst or initiator feed system 300 , the reactor system 400 , the product recovery and drier systems 500 and 600 , and the solvent recovery system 700 and 800 .
  • the average residence time* of the monomers in the reactor system should be sufficient to completely react MAN, e.g. from 0.5 to 5 hours.
  • higher temperature and/or initiator booster can be used at the end of reaction zone.
  • the specific viscosity (SV) of the copolymer is controlled by adding a chain transfer agent, preferably acetaldehyde, to the AVE and/or by controlling the reaction temperature and/or the amount of initiator.
  • the liquified solvent monomer (methyl vinyl ether) is pressurized and fed at a constant flow to the reactor system 400 which may consist of a Continuous Stirred Tank Reactor (CSTR) or of two or more CSTRs in series, or an agitated back mixed reactor, or a plug flow tubular reactor, which is maintained at a constant temperature between about 40° C. to 120° C., preferably 60-90° C.
  • Molten maleic anhydride (MAN) in 200 , also pressurized, is fed and mixed well with the solvent monomer at a constant rate in the reactor; where, with a constant addition of an initiator having a half-life of 2 to 10 hours, e.g.
  • lauroyl or decanoyl peroxide (or any other radical initiator) from 300 can rapidly react to form a slurry of the desired solid product (10-40% by weight) in the excess of liquid solvent monomer.
  • the molar ratio of AVE/MAN in the reactor is about 25:1 to 5:1, preferably about 12:1 to 7:1.
  • the slurry mixture is continually withdrawn and fed to a low pressure drier system 500 ; where, with the addition of heat, the excess solvent monomer is vaporized and the solid product is separated and removed. The recovered monomer is then cooled and re-pressurized in the recovery system 800 . Following compositional adjustments, the monomer solvent is returned to the solvent feed system 100 .
  • AVE may be separated from polymer by continuous drying or by filtration, and recycled after continuous purification e.g. by continuous distillation, washing with water of pH>9, and drying.

Landscapes

  • 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

A continuous, solvent-free process for obtaining solvent-free, fine white powders of high molecular weight alternating copolymers of maleic anhydride and a C1-C4 alkyl vinyl ether, without odor or taste, having the molecular structure (A-B)n, where A is maleic anhydride, B is an alkyl vinyl ether and n is an integer indicative of the molecular weight of the copolymer, which comprises feeding alkyl vinyl ether as reactant and solvent in excess over the desired 1:1 mole ratio of A:B in the copolymer, molten maleic anhydride and a free radical initiator, continuously at predetermined feeding rates into a reactor heated at a reaction temperature of about 50° to 100° C., charging the reactor and withdrawing reaction product, residual alkyl vinyl ether and initiator from the reactor at the same rate as the feed rate of reactants into the reactor simultaneously thereby maintaining a constant volume in the reactor, stripping residual alkyl vinyl ether from the reaction product, drying the copolymer obtained of any remaining traces of alkyl vinyl ether, and recycling recovered alkyl vinyl ether back into reactor as reactant and solvent.

Description

    CROSS REFERENCE TO RELATED PATENT APPLICATION
  • This application is a continuation-in-part of pending U.S. patent application Ser. No. 09/596,297, filed Jun. 15, 2000.[0001]
    • DESCRIPTION OF RELATED U.S. PATENTS
  • This invention is related to U.S. Pat. Nos. 5,959,053 and 5,939,506 assigned to the same assignee as herein. [0002]
    • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention [0003]
  • This invention relates to copolymers of maleic anhydride and a C[0004] 1-C4 alkyl vinyl ether, and, more particularly, to a continuous, solvent-free process for making solvent-free, fine white powders of such copolymers having advantageous properties useful for oral care compositions.
  • 2. Description of the Prior Art [0005]
  • A batch, solvent-free process (i.e. no solvent other than reactants themselves) for making fine powders of high molecular alternating copolymers of maleic anhydride (MAN) and a C[0006] 1-C4 alkyl vinyl ether (AVE) having a molecular structure of (A-B)n where A=MAN, B=AVE and n is an integer which is indicative of its molecular weight, is described in U.S. Pat. Nos. 5,959,053 and 5,939,506. In such process, excess AVE monomer is present over a 1:1 molar ratio of monomers, to function both as reactant and solvent in the system. No other solvent is present in the reactor. Accordingly, after stripping the excess AVE from the reaction product, a solvent-free copolymer is obtained. However, a batch process requires an extended amount of time to effect the reaction, usually necessitating about 9-13 hours to complete each batch.
  • Accordingly, it is an object of this invention to provide a continuous, solvent-free process for making solvent-free, fine white powders of copolymers of MAN and AVE having advantageous properties useful for oral care compositions. [0007]
    • SUMMARY OF THE INVENTION
  • What is described herein is a continuous, solvent-free process for obtaining solvent-free, fine white powders of high molecular weight alternating copolymers of maleic anhydride and a C[0008] 1-C4 alkyl vinyl ether, without odor or taste, having the molecular structure (A-B)n, where A is maleic anhydride, B is an alkyl vinyl ether, and n is an integer indicative of the molecular weight of the copolymer. The process herein comprises feeding continuously alkyl vinyl ether as monomer reactant and solvent in excess of the desired 1:1 mole ratio of A:B in the copolymer, molten maleic anhydride and a free radical initiator, at predetermined feeding rates, into a reactor heated at a reaction temperature of about 50° to 100° C., charging the reactor and withdrawing reaction product, residual alkyl vinyl ether and initiator from the reactor at the same rate as the feed rate of reactants into the reactor simultaneously thereby maintaining a constant volume in the reactor, stripping residual alkyl vinyl ether from the reaction product, drying the copolymer obtained of any remaining traces of alkyl vinyl ether, and recycling recovered alkyl vinyl ether back into reactor.
  • In the preferred embodiments of the continuous solvent-free process of the invention, the alkyl vinyl ether is methyl vinyl ether, the mole ratio of methyl vinyl ether to molten maleic anhydride is about 25:1 to 5:1, most preferably 12:1 to 7:1. The initiator concentration is 0.01 to 0.2% based on the weight of copolymer, and the % copolymer solids removed from the polymerization reactor is about 10 to 40%.[0009]
    • DETAILED DESCRIPTION OF THE INVENTION
  • Referring now to the FIGURE, which is a schematic drawing for making solvent-free copolymers of maleic anhydride (MAN) and C[0010] 1-4 alkyl vinyl ethers (AVE) by a continuous, solvent-free process. The continuous solvent-free process of the invention consists of the solvent feed system 100, the molten maleic anhydride feed system 200, the catalyst or initiator feed system 300, the reactor system 400, the product recovery and drier systems 500 and 600, and the solvent recovery system 700 and 800.
  • The average residence time* of the monomers in the reactor system should be sufficient to completely react MAN, e.g. from 0.5 to 5 hours. To ensure complete reaction of MAN, higher temperature and/or initiator booster can be used at the end of reaction zone. The specific viscosity (SV) of the copolymer is controlled by adding a chain transfer agent, preferably acetaldehyde, to the AVE and/or by controlling the reaction temperature and/or the amount of initiator. [0011]
  • In [0012] system 100, the liquified solvent monomer (methyl vinyl ether) is pressurized and fed at a constant flow to the reactor system 400 which may consist of a Continuous Stirred Tank Reactor (CSTR) or of two or more CSTRs in series, or an agitated back mixed reactor, or a plug flow tubular reactor, which is maintained at a constant temperature between about 40° C. to 120° C., preferably 60-90° C. Molten maleic anhydride (MAN), in 200, also pressurized, is fed and mixed well with the solvent monomer at a constant rate in the reactor; where, with a constant addition of an initiator having a half-life of 2 to 10 hours, e.g. lauroyl or decanoyl peroxide (or any other radical initiator) from 300, can rapidly react to form a slurry of the desired solid product (10-40% by weight) in the excess of liquid solvent monomer. In this continuous process, the molar ratio of AVE/MAN in the reactor is about 25:1 to 5:1, preferably about 12:1 to 7:1.
  • With the maintenance of a constant volume in the reactor, the slurry mixture is continually withdrawn and fed to a low [0013] pressure drier system 500; where, with the addition of heat, the excess solvent monomer is vaporized and the solid product is separated and removed. The recovered monomer is then cooled and re-pressurized in the recovery system 800. Following compositional adjustments, the monomer solvent is returned to the solvent feed system 100.
  • AVE may be separated from polymer by continuous drying or by filtration, and recycled after continuous purification e.g. by continuous distillation, washing with water of pH>9, and drying. [0014]
  • While the invention has been described with particular reference to certain embodiments thereof, it will be understood that changes and modifications may be made which are within the skill of the art. Accordingly, it is intended to be bound only by the following claims, in which: [0015]

Claims (5)

What is claimed is:
1. A continuous, solvent-free process for obtaining solvent-free, fine white powders of high molecular weight alternating copolymers of maleic anhydride and a C1-C4 alkyl vinyl ether, without odor or taste, having the molecular structure (A-B)n, where A is maleic anhydride, B is an alkyl vinyl ether and n is an integer indicative of the molecular weight of the copolymer, which comprises feeding alkyl vinyl ether as reactant and solvent in excess over the desired 1:1 mole ratio of A:B in the copolymer, molten maleic anhydride and a free radical initiator, continuously at a predetermined feeding rate into a reactor heated to a reaction temperature of about 50° to 100° C., charging the reactor and withdrawing reaction product, residual alkyl vinyl ether and initiator from the reactor at the same rate as the feed rate of reactants into the reactor, simultaneously, thereby maintaining a constant volume in the reactor, stripping residual alkyl vinyl ether from the reaction product, drying the copolymer there-obtained of any remaining traces of alkyl vinyl ether, and recycling recovered alkyl vinyl ether back into reactor as reactant and solvent, wherein the mole ratio of alkyl vinyl ether to molten maleic anhydride is about 25:1 to 5:1, wherein the initiator concentration is 0.01 to 0.2% based on copolymer, wherein the % copolymer solids in the reaction product removed from the polymerization reactor is about 10 to 40%.
2. A continuous, solvent-free process according to
claim 1
 wherein said alkyl vinyl ether is methyl vinyl ether.
3. A continuous, solvent-free process according to
claim 1
 wherein said mole ratio is 12:1 to 7:1.
4. A continuous, solvent-free process according to
claim 1
 wherein the drying step is carried out at 40° to 100° C. under vacuum or atmospheric pressure.
5. A continuous, solvent-free process according to
claim 1
 wherein the average residence time of reactants in the reactor during the process is about 0.5 to 5 hours.
US09/861,044 2000-06-15 2001-05-18 Continuous, solvent-free process for making copolymers of maleic anhydride and C1−4 alkyl vinyl ether Expired - Lifetime US6451944B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US09/861,044 US6451944B2 (en) 2000-06-15 2001-05-18 Continuous, solvent-free process for making copolymers of maleic anhydride and C1−4 alkyl vinyl ether

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59629700A 2000-06-15 2000-06-15
US09/861,044 US6451944B2 (en) 2000-06-15 2001-05-18 Continuous, solvent-free process for making copolymers of maleic anhydride and C1−4 alkyl vinyl ether

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US59629700A Continuation-In-Part 2000-06-15 2000-06-15

Publications (2)

Publication Number Publication Date
US20010053829A1 true US20010053829A1 (en) 2001-12-20
US6451944B2 US6451944B2 (en) 2002-09-17

Family

ID=24386759

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/861,044 Expired - Lifetime US6451944B2 (en) 2000-06-15 2001-05-18 Continuous, solvent-free process for making copolymers of maleic anhydride and C1−4 alkyl vinyl ether

Country Status (8)

Country Link
US (1) US6451944B2 (en)
EP (1) EP1299425B1 (en)
JP (1) JP4820044B2 (en)
CN (1) CN1232541C (en)
AT (1) ATE306505T1 (en)
AU (1) AU2001257480A1 (en)
DE (1) DE60114009T2 (en)
WO (1) WO2001096410A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107805290A (en) * 2017-12-05 2018-03-16 博爱新开源制药股份有限公司 A kind of tert-Butyl vinyl ether/copolymer-maleic anhydride and preparation method thereof

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6365691B1 (en) * 2000-07-06 2002-04-02 Isp Investments Inc. Continuous, solvent-free process for making terpolymers of maleic anhydride, C1-4 alkyl vinyl ether and isobutylene
US6692725B2 (en) * 2001-02-19 2004-02-17 Daicel Chemical Industries, Ltd. Composition for oral care
FR2884253B1 (en) * 2005-04-08 2007-06-22 Univ Lille Sciences Tech FUNCTIONALIZABLE MONOLITHIC MATERIALS
CN102030856B (en) * 2009-09-25 2012-05-30 博爱新开源制药股份有限公司 Method for devolatilizing vinyl methyl ether/maleic anhydride copolymer

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3108100A1 (en) * 1981-03-04 1982-09-16 Basf Ag, 6700 Ludwigshafen METHOD FOR THE PRODUCTION OF COPOLYMERISATEN OF MALEINSAEUREANHYDRID
DE3712265A1 (en) * 1987-04-10 1988-10-20 Giulini Chemie METHOD FOR PRODUCING HIGH POLYMERIZATION COPOLYMERS
US5034488A (en) * 1990-01-11 1991-07-23 Gaf Chemicals Corporation Slurry polymerization of crosslinked maleic anhydride-alkyl vinyl ether copolymers in a solvent system comprising a carboxylic acid ester and a saturated hydrocarbon
US5064897A (en) * 1990-08-30 1991-11-12 Isp Investments Inc. Process for making ethanol solutions of alkyl half-esters of copolymers of maleic anhydride and a C1 -C4 alkyl vinyl ether
US5874510A (en) * 1997-09-18 1999-02-23 Isp Investments Inc. Process for making crosslinked copolymers of maleic anhydride and methyl vinyl ether
US5939506A (en) * 1997-10-02 1999-08-17 Isp Investments Inc. Solvent-free process for making high molecular weight terpolymers of maleic anhydride, C1 -C4 alkyl vinyl ether and isobutylene

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107805290A (en) * 2017-12-05 2018-03-16 博爱新开源制药股份有限公司 A kind of tert-Butyl vinyl ether/copolymer-maleic anhydride and preparation method thereof

Also Published As

Publication number Publication date
JP4820044B2 (en) 2011-11-24
WO2001096410A1 (en) 2001-12-20
JP2004503617A (en) 2004-02-05
EP1299425B1 (en) 2005-10-12
EP1299425A4 (en) 2004-10-27
DE60114009D1 (en) 2006-02-23
CN1443202A (en) 2003-09-17
CN1232541C (en) 2005-12-21
EP1299425A1 (en) 2003-04-09
AU2001257480A1 (en) 2001-12-24
US6451944B2 (en) 2002-09-17
ATE306505T1 (en) 2005-10-15
DE60114009T2 (en) 2006-06-22

Similar Documents

Publication Publication Date Title
EP0040992B1 (en) Process for multi-step gas-phase polymerization of olefins
US3729451A (en) Process for copolymerization of maleic anhydride with 1-olefins
US5034487A (en) Process for making copolymers of maleic anhydride and a C1 -C4 alkyl vinyl ether having a high specific viscosity
USRE28475E (en) Process for copolymerization of maleic anhydride with 1-olefins
EP0275081B1 (en) Copolymers of vinyl alcohol and acrylates
KR100630887B1 (en) A method of ethylene polymerization for producing products having various properties with high productivity and a tubular reactor for the same
EP1299425B1 (en) Continuous, solvent-free process for making copolymers of maleic anhydride and c 1-4? alkyl vinyl ether
US6365691B1 (en) Continuous, solvent-free process for making terpolymers of maleic anhydride, C1-4 alkyl vinyl ether and isobutylene
US4948848A (en) Solution feed, slurry polymerization process for the production of copolymers of maleic anhydride and an alkyl vinyl ether having predetermined specific viscosities
JPH0841135A (en) Process for producing styrene-acrylonitrile copolymer
JPH1045838A (en) Manufacture of ethylene/vinyl acetate copolymer
AU648318B2 (en) Process for making copolymers of maleic anhydride and a C1-C4 alkyl vinyl ether having a predetermined specific viscosity
JP2004503617A5 (en)
NO784226L (en) PROCEDURE FOR POLYMERIZATION OF ETHYLENE
US5874510A (en) Process for making crosslinked copolymers of maleic anhydride and methyl vinyl ether
WO1993001220A1 (en) Benzene-free maleic anhydride/vinyl ether polymers
EP1198483B1 (en) Process for the production of solvent-free, fine white powders of high molecular weight copolymers of maleic anhydride and a c1-c4 alkyl vinyl ether without odor or taste

Legal Events

Date Code Title Description
AS Assignment

Owner name: ISP INVESTMENTS INC., DELAWARE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BISS, RUSSELL;COHEN, JEFFREY;ZAMORA, JOHN;AND OTHERS;REEL/FRAME:011829/0979;SIGNING DATES FROM 20010510 TO 20010516

AS Assignment

Owner name: CHASE MANHATTAN BANK, THE, NEW YORK

Free format text: SECURITY AGREEMENT;ASSIGNOR:ISP CAPITAL, INC.;REEL/FRAME:012124/0001

Effective date: 20010627

Owner name: ISP CAPITAL, INC., DELAWARE

Free format text: CHANGE OF NAME;ASSIGNOR:ISP INVESTMENTS, INC.;REEL/FRAME:012124/0351

Effective date: 20010627

STCF Information on status: patent grant

Free format text: PATENTED CASE

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

AS Assignment

Owner name: THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT,

Free format text: SECURITY AGREEMENT;ASSIGNORS:ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC;HERCULES INCORPORATED;AQUALON COMPANY;AND OTHERS;REEL/FRAME:026918/0052

Effective date: 20110823

AS Assignment

Owner name: ISP CHEMICAL PRODUCTS, INC., NEW JERSEY

Free format text: PATENT RELEASE;ASSIGNOR:JPMORGAN CHASE BANK, N.A. (F/K/A THE CHASE MANHATTAN BANK);REEL/FRAME:026930/0774

Effective date: 20110823

Owner name: ISP CAPITAL, INC., NEW JERSEY

Free format text: PATENT RELEASE;ASSIGNOR:JPMORGAN CHASE BANK, N.A. (F/K/A THE CHASE MANHATTAN BANK);REEL/FRAME:026930/0774

Effective date: 20110823

Owner name: VERONA, INC., NEW JERSEY

Free format text: PATENT RELEASE;ASSIGNOR:JPMORGAN CHASE BANK, N.A. (F/K/A THE CHASE MANHATTAN BANK);REEL/FRAME:026930/0774

Effective date: 20110823

AS Assignment

Owner name: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC, OHIO

Free format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:030025/0320

Effective date: 20130314

Owner name: AQUALON COMPANY, DELAWARE

Free format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:030025/0320

Effective date: 20130314

Owner name: ISP INVESTMENTS INC., DELAWARE

Free format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:030025/0320

Effective date: 20130314

Owner name: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC, O

Free format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:030025/0320

Effective date: 20130314

Owner name: HERCULES INCORPORATED, DELAWARE

Free format text: RELEASE OF PATENT SECURITY AGREEMENT;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:030025/0320

Effective date: 20130314

FPAY Fee payment

Year of fee payment: 12

AS Assignment

Owner name: THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT, CANADA

Free format text: SECURITY AGREEMENT;ASSIGNORS:AVOCA, INC.;HERCULES LLC;ISP INVESTMENTS LLC;AND OTHERS;REEL/FRAME:043084/0753

Effective date: 20170630

Owner name: THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT,

Free format text: SECURITY AGREEMENT;ASSIGNORS:AVOCA, INC.;HERCULES LLC;ISP INVESTMENTS LLC;AND OTHERS;REEL/FRAME:043084/0753

Effective date: 20170630

AS Assignment

Owner name: PHARMACHEM LABORATORIES LLC, NEW JERSEY

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:051557/0504

Effective date: 20200110

Owner name: HERCULES LLC, DELAWARE

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:051557/0504

Effective date: 20200110

Owner name: AVOCA LLC, NORTH CAROLINA

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:051557/0504

Effective date: 20200110

Owner name: ISP INVESTMENTS LLC, NEW JERSEY

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:THE BANK OF NOVA SCOTIA;REEL/FRAME:051557/0504

Effective date: 20200110