EP0531313A1 - Solutions aqueuses de copolymeres d'anhydride maleique hydrolyse - Google Patents

Solutions aqueuses de copolymeres d'anhydride maleique hydrolyse

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Publication number
EP0531313A1
EP0531313A1 EP19910908892 EP91908892A EP0531313A1 EP 0531313 A1 EP0531313 A1 EP 0531313A1 EP 19910908892 EP19910908892 EP 19910908892 EP 91908892 A EP91908892 A EP 91908892A EP 0531313 A1 EP0531313 A1 EP 0531313A1
Authority
EP
European Patent Office
Prior art keywords
maleic anhydride
copolymer
aromatic
copolymers
ethylenically unsaturated
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Withdrawn
Application number
EP19910908892
Other languages
German (de)
English (en)
Inventor
Luann Marshall Pugh
Walter Ray Tong
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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 EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0531313A1 publication Critical patent/EP0531313A1/fr
Withdrawn legal-status Critical Current

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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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • 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
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority

Definitions

  • the present invention relates to a process for the preparation of aqueous solutions of hydrolyzed ethylenically unsaturated aromatic/maleic anhydride polymers.
  • the preferred precursor of Fitzgerald et al. is a styrene/ aleic anhydride copolymer.
  • the styrene/maleic anhydride copolymers currently available commercially can be obtained in either of two solid forms, powder and flake.
  • the powder form which is inherently more expensive because it is produced by grinding the flake, is more readily soluble than the flake, probably due to its larger surface area.
  • the powder however, is difficult to charge safely to a reactor because it presents a dust explosion hazard and has a tendency to contaminate the operating area, thereby generating environmental concerns.
  • the Jake on the other hand, reacts more slowly than the powder when treated under the same conditions. It also tends to form lumps due to the
  • the present invention relates to a process for the hydrolysis of ethylenically unsaturated aromatic/maleic anhydride copolymers to form lightly colored solutions of ethylenically unsaturated aromatic/maleic acid salt copolymers, the improvement comprising carrying out the reaction at temperatures above about 100*C at elevated pressure.
  • DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for the reaction of aromatic/maleic anhydride copolymers with aqueous alkaline materials to form clear lightly-colored solutions of aromatic/maleic anhydride copolymers, the improvement comprising carrying out the reaction at temperatures above about 100°C and a pressure above atmospheric in equipment suitable for pressure operation.
  • the clarity and light color of the product aromatic/maleic anhydride copolymer solutions are surprising in view of the recommendations to use temperatures of about 77"C or below and the warning about the deleterious effect of higher temperatures on product color, contained in the trade literature. _
  • aromatic/maleic anhydride polymers suitable as starting materials for this invention contain between about one and three polymer units derived from one or more ethylenically unsaturated aromatic monomers per polymer unit derived from maleic anhydride.
  • a variety of ethylenically unsaturated aromatic compounds can be used for the purpose of preparing these unhydrolyzed polymers. They can be represented by the formula
  • R 1 is H-, CH 3 or C 6 H5-;
  • R 2 is II- or CH 3 -;
  • R 3 is II- or CH 3 O-;
  • O R4 is II-, CH 3 -, or CH 3 C H-0-, and
  • R 3 plus R 4 is -O-CH2-O-.
  • ethylenically unsaturated aromatic compounds suitable as monomers in the preparation of the copolymers used as starting materials in the process of this invention include styrene , alpha-methylstyrene, 4-methylstyrene, stilbene, 4-acetoxystilbene (used to prepare a hydrolyzed polymer from maleic anhydride and 4-hydroxystilbene) , eugenol acetate, isoeugenol acetate, 4-allylphenyl acetate, safrole, mixtures of the same, and the like.
  • copolymerization of any of the above ethylenically unsaturated aromatic monomers with maleic anhydride should be carried out in any of the ways, known to the art, to produce copolymers with a relatively low molecular weight(number average) .
  • the copolymers, used as starting materials for this invention should have a number average molecular weight in the range between about 500 and 4000, preferably between about 800 and 2000.
  • the copolymer is a styrene/maleic anhydride copolymer having a number average molecular weight in the range between about 500
  • Surfactants, antimicrobials, other stabilizers and the like are non-limiting examples of components that could be added to the initial charging.
  • the aromatic/maleic anhydride copolymer, the polymeric sulfonated phenol-formaldehyde condensation product and the aqueous alkaline material to the reactor before carrying out the heating cycle of this invention. Clear dark amber solutions are obtained. Since phenol-formaldehyde solutions are generally darker than aromatic/maleic anhydride copolymer solutions, it is not surprising that solutions containing both of these components are darker than those containing only aromatic/maleic anhydride copolymers.
  • the alkaline materials useful in this invention include alkali metal oxides, hydroxides or salts.
  • Magnesium oxide, hydroxide and alkaline salts of magnesium also lead to clear lightly colored solutions when used in this invention.
  • Calcium derivatives do not. They result in slurries, the calcium salts of the hydrolyzed copolymers evidently being less soluble than the magnesium salts, if soluble at all.
  • Typical examples of alkaline materials that afford clear solutions of the hydrolyzed copolymers of this invention are sodium hydroxide, preferred because of price and ease of availability, potassium hydroxide, magnesium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate, disodium phosphate and trisodium phosphate.
  • the ratio of alkaline material to anhydride units in the polymer can vary over a considerable range in the application of this invention. It is not necessary to use stoichiometric equivalents of alkali to anhydride units in the polymer to obtain complete solution. As little as 25% of the stoichiometric quantity of alkali required to completely neutralize the carboxylic acid groups formed by the hydrolysis of the anhydride, can yield complete solution of the hydrolyzed polymer.
  • the product obtained by the use of less than stoichiometric quantities of alkaline material therefore contains a mixture of maleic acid salt moieties and free maleic acid moieties.
  • the present invention can also be carried out by simply mixing water and the aromatic/maleic anhydride copolymer and heating at the higher temperatures of this invention.
  • An intermediate product mixture is obtained in the form of a slurry which remains quite fluid on cooling to 65-80'C.
  • the solid component of the slurry is the hydrolysed aromatic/maleic anhydride copolymer, the anhydride polymer units now converted to dicarboxylic acid units.
  • the addition of an alkaline material to the slurry results in easy solution as the pll is raised.
  • the process of this invention is conveniently operated by charging the aromatic/maleic anhydride copolymer, preferably in flake form, an alkali or alkaline salt and water to a reactor capable of withstanding moderate pressures and heating the mixture to temperatures above about 100*C at a pressure in excess of atmospheric, preferably autogenous pressure, until solution is complete. Temperatures between 120 to 140 * C are preferred because this range affords complete solution in a reasonable length of time. For example, heating a mixture of 3/1 styrene/maleic anhydride copolymer at 125'C in aqueous caustic soda leads to a lightly colored solution in the course of about two hours. Temperatures in the range of 100 to 120 * C require longer times for complete reaction. Temperatures higher than 140 * C can be used, but they result in correspondingly higher pressures which require more substantial equipment to contain them.
  • the process of this invention is usually run at concentrations of copolymer plus alkaline material of about 10 to 40 weight percent in water, i.e. about 60 to 90% by weight water.
  • concentrations of copolymer plus alkaline material of about 10 to 40 weight percent in water, i.e. about 60 to 90% by weight water.
  • Lower concentrations are uneconomical and higher ones lead to products with increasingly high viscosities which become difficult to handle.
  • the product's pll also has an effect on its viscosity.
  • Table 1 The relationships between concentration, pH and viscosity for aqueous sodium salt solutions of hydrolyzed 1/1 styrene/maleic anhydride copolymer are demonstrated in Table 1.
  • Th €vre were added to a 100 ml stainless steel bomb 24 g of flaked 1/1 styrene/maleic anhydride copolymer with a number average molecular weight of about 1600 and an acid number of about 480 (SMA 1000 from ⁇ tochem Company) , 24 g of 30 weight percent aqueous sodium hydroxide and 32 g of water.
  • the bomb was sealed and heated at 130 * C for two hours with shaking. After cooling, the contents of the bomb were a c ⁇ ear amber solution with no trace- of undissolved starting material.
  • the reactor was sealed and the mass was heated to 120 to 125*C where it was held for 3 hours. The charge was cooled to yield a clear pale yellow solution.
  • Example 3 except that no base was used.
  • the product was a milky white_slurry.
  • the solids showed no anhydride linkages by infra-red analysis and dissolved in aqueous sodium hydroxide at ambient temperature.
  • EXAMPLE 5 A 3/1 styrene/maleic anhydride copolymer with a number average molecular weight of 1900 and an acid number of about 280, (SMA 3000 suplied by Atochem 5 Company) 82.1 g, 53.3 g of 30%, by weight, of aqueous sodium hydroxide and 193 g of water were reacted according to the method descibed in Example 3. The product was a clear light yellow solution.
  • EXAMPLE 7 SMA 1000 flakes, 75 g, and 190 g of water were sealed in a 300 ml bomb and heated at 120-125*C for 4 hrs. with shaking, and the bomb was then cooled 20 to 65'C. The resultant milky white slurry was partially neutralized with 35 g of 20% ammonium hydroxide at 65 ' C to yield a clear light amber solution.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General 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)

Abstract

Procédé consistant à soumettre un mélange d'eau et d'un copolymère d'anhydride aromatique/maléique à insaturation d'éthylène à une température supérieure à 100 °C et à une pression supérieure à la pression atmosphérique, de préférence à une pression autogène. La température préférentielle se situe dans la plage comprise entre environ 120 et 140 °C. Le copolymère préféré a une masse moléculaire moyenne située dans la plage comprise entre environ 500 et 4000. Le monomère préféré dont on dérive le copolymère peut être représenté par la formule (I), dans laquelle R représente alpha ou CH2=CH-CH2-; R1 représente H-, CH3; ou beta; R2 représente H- ou CH3; R3 représente H- ou CH3O-; R4 représente H-, CH3-; ou gamma, et R3 plus R4 représentent -O-CH2-O-. Le copolymère préférentiel est un copolymère d'anhydride styrénique/maléique ayant une masse moléculaire moyenne comprise entre 800 et 2000.
EP19910908892 1990-05-25 1991-04-25 Solutions aqueuses de copolymeres d'anhydride maleique hydrolyse Withdrawn EP0531313A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US52907690A 1990-05-25 1990-05-25
US529076 1990-05-25

Publications (1)

Publication Number Publication Date
EP0531313A1 true EP0531313A1 (fr) 1993-03-17

Family

ID=24108430

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19910908892 Withdrawn EP0531313A1 (fr) 1990-05-25 1991-04-25 Solutions aqueuses de copolymeres d'anhydride maleique hydrolyse

Country Status (2)

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EP (1) EP0531313A1 (fr)
WO (1) WO1991018932A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0659771A1 (fr) * 1993-12-23 1995-06-28 Dsm N.V. Procédé de préparation de polymères thermoplastiques en présence de tels métalliques basiques
US5792818A (en) * 1997-02-05 1998-08-11 Colgate-Palmolive Company Process for hydrolyzing maleic anhydride copolymers
US7550199B2 (en) 2006-07-31 2009-06-23 E.I. Du Pont De Nemours And Company Copolymers for stain resistance
WO2017063188A1 (fr) * 2015-10-16 2017-04-20 Ecolab Usa Inc. Homopolymère d'anhydride maléique et homopolymère d'acide maléique et leur procédé de préparation, et inhibiteur de corrosion non phosphoreux et son utilisation

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2565147A (en) * 1948-12-22 1951-08-21 Quaker Chemical Products Corp Process for hydrolyzing copolymers of maleic acid derivatives
US2712003A (en) * 1949-11-23 1955-06-28 Monsanto Chemicals Manufacture of water-soluble heteropolymers
US3297657A (en) * 1963-03-08 1967-01-10 Deering Milliken Res Corp Styrene-maleic anhydride copolymerization process
GB1369429A (en) * 1970-11-30 1974-10-09 Ciba Geigy Ag Treatment of water or aqueous systems
JPS6016442B2 (ja) * 1976-03-08 1985-04-25 日石三菱株式会社 変性ポリオレフインワツクスの製造法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9118932A1 *

Also Published As

Publication number Publication date
WO1991018932A1 (fr) 1991-12-12

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