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WO1995011341A1 - Solution polymere amelioree utilisee pour l'encollage de papier - Google Patents

Solution polymere amelioree utilisee pour l'encollage de papier Download PDF

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Publication number
WO1995011341A1
WO1995011341A1 PCT/US1994/011531 US9411531W WO9511341A1 WO 1995011341 A1 WO1995011341 A1 WO 1995011341A1 US 9411531 W US9411531 W US 9411531W WO 9511341 A1 WO9511341 A1 WO 9511341A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
polymer
sizing
styrene
paper
Prior art date
Application number
PCT/US1994/011531
Other languages
English (en)
Inventor
Kang In Lee
Original Assignee
Monsanto Company
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 Monsanto Company filed Critical Monsanto Company
Publication of WO1995011341A1 publication Critical patent/WO1995011341A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof

Definitions

  • This invention relates to paper sizing formulations and more particularly to aqueous alkaline solutions of polymers of styrene and maleate half esters for such applications.
  • Alkaline salt solutions of high molecular weight styrene-maleic half ester copolymers for sizing paper are known. See, for example US. 5,237,024, issued August 17, 1993 where C-_ - C 18 alcohols are used in forming the aleic half ester. Ease of synthesis of these polymers without loss of sizing properties is of continuing interest in the paper sizing art.
  • a principal object of this invention is to provide an improved aqueous alkaline paper sizing solution of styrene-maleate half ester polymers.
  • an aqueous solution of polymer for sizing paper wherein the polymer has a weight average molecular weight of at least 100,000 Daltons, preferably 150,000 to 250,000 Daltons, and comprising the following recurring units of formula: CH,
  • n and m are each from 1 to 10 and o from 1 to 4.
  • Preferred ranges of m and n are 1 to 4 and of o, either 1 or 2.
  • component C of the polymer enhance the flexibility of such side chains to preserve polymer solubility in the final solution while at the same time providing alkylene (CH 2 ) groups to promote hydrophobicity of the polymer which aids in helping keep water from the sizing solution and ink from smearing on the surface of the paper to which the formulation is applied.
  • alkylene (CH 2 ) groups to promote hydrophobicity of the polymer which aids in helping keep water from the sizing solution and ink from smearing on the surface of the paper to which the formulation is applied.
  • mixtures of the latter with one or more primary or secondary C 1 -C 18 alcohols can be used.
  • Usable primary alcohols include methanol, ethanol, n-propanol, n-butanol, isobutanol, n-pentanol, n-hexanol, n-heptanol, n- octanol, n-decanol and higher alcohols up to n- octadecanol.
  • Usable secondary alcohols include isopropanol, secondary-butanol etc.
  • the molar ratio of oxyalkylene- alkyl maleate to C ⁇ - C 18 maleate should be 0.5:1 to 4:1, preferably 1:1 to 2:1.
  • Optionally includable with the styrene and maleate half ester components of the polymer is copolymerizable monomer of the formula: CH,
  • R is C ⁇ to C 3 alkyl and R 1 is H or C 2 to C 3 alkyl.
  • Representative compounds satisfying this formula include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methyl maleate, ethyl maleate, propyl maleate and butyl maleate. Inclusion of such copolymerized monomer can further improve the sizing properties of the solutions of the invention.
  • the weight fractions i.e.
  • weight of the constituents in the polymer per 100 parts of polymer) of the polymerized monomers are 40 to 70 (preferably 50 to 60) styrene, 20 to 60 (preferably 30 to 40 maleic half ester) and 2 to 30 (preferably 5 to 15) acrylate or methacrylate component.
  • the polymers of styrene-oxyalkylene-alkyl maleate half ester are prepared by any conventional free radical process providing relatively high molecular weight polymers of at least a molecular weight of 100,000 (weight average) determined by size exclusion chromatography using tetrahydrofuran as solvent and low angle laser light scattering with a Waters Model 401 Differential Refractive Index Detector instrument.
  • the polymers are prepared by in situ esterification of maleic anhydride with oxyalkylene-alkyl alcohol followed by solution polymerization of the mixture with styrene at a temperature in the range of 70 to 150"C using peroxide or hydroperoxide initiators or mixtures thereof, such as t-butyl peroctoate, benzyl peroxide, t-butyl hydroperoxide, t-butyl peroxide, cumene hydroperoxide and cumene peroxide or azo-dinitriles such as azo-di(isobutyronitrile) and azo-di cyclohexanecarbonitrile.
  • peroxide or hydroperoxide initiators or mixtures thereof such as t-butyl peroctoate, benzyl peroxide, t-butyl hydroperoxide, t-butyl peroxide, cumene hydroperoxide and cumene peroxide or azo-dinitriles such as azo
  • the polymeric salt is formed by mixing the polymer in aqueous alkaline solution, preferably without the presence of additional components. In doing so, the acid component reacts with the alkaline metal or ammonium of the polymer providing an ester group attached to one C atom and an alkali metal or ammonium cation associated with a carboxylic group.
  • the concentration of polymer salt in solution is 5 to 20 weight percent.
  • the agitated kettle containing the above polymer solution was fitted with a distillation apparatus was charged concentrated 30% ammonium hydroxide (10.65 gm) and 85°C tap water (425.6 gm) was charged over a 10 min period. Since xylene is essentially immiscible in water, after agitation was stopped a two layer mixture was formed of the solvent and water solution. The xylene layer was decanted off and the residual xylene was further removed from the water solution layer by distillation at 100 ⁇ C. The resulting aqueous ammonium salt solution was cooled to 25"C and pH adjusted to 9.2. The solution was water clear to the eye and had a Brookfield viscosity of 30 cps (0.03 Pa.s). Residual xylene in the solution was less than 0.01 wt. % by gas chromatography.
  • A) Hercules Sizing Test Ten gm of corn starch in 100 gm of water were heated at 90°C for 30 minutes. To aid miscibility the starch solution was diluted with an additional 100 gm of water. Then the pH of the solution was adjusted with caustic soda to 8. 10 gms of the ester/ammonium salt of the polymer of Examples 1A and IB above as a 10% solids concentration in water were mixed with the starch solution to prepare the surface sizing formulations. The surface sizing solution was held in a 55°C water bath until used in the size press.
  • the press used was a horizontal size press which is a two roll metering device which applied the surface sizing solution to paper sheet as the latter passes downwardly through a nip defined between a sheet contact surface of a first roll and a sheet contact surface of a second roll. The rolls turn in opposite direction in the horizontal plane.
  • the above-prepared surface sizing solutions were applied to the paper stock (alkaline paper containing 12% precipitate calcium carbonate, 0.5 % alum and 0.03% alkyl ketene dimer) through the horizontal size press at 90 ⁇ C.
  • the amount of sizing solution taken up by the paper was 0.09 gm per square meter.
  • the paper was redried after application of the alkaline sizing solution.
  • the sized paper was tested for ink penetration using a Hercules sizing test apparatus. In this test (conducted at 23 ° C) , the change is noted in light reflection from the surface of one side of the sized paper sample as ink or a colored solution of naphthol green dye (to simulate ink) is allowed to penetrate from the other side.
  • the naphthol green dye is confined within a ring on the tope side of a section of sized paper and the change in light reflectance from the bottom side is measured photoelectrically. An end point of 80% reduction in reflected light is chosen.
  • the reflectance measuring system includes a timer measuring seconds which stops automatically when the reflected light falls below 80%.
  • a terpolymer of styrene, maleic anhydride and methyl methacrylate was prepared as disclosed in Example 1, page 4 of the subject application as was the amide/ammonium salt solution of such terpolymer, as disclosed on page 5 of said application, the content of which is incorporated herein by reference.
  • the rate of decrease of the contact angle with time is undesirably much faster than that of invention Examples 1A and IB.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

On améliore les propriétés d'encollage du papier de solutions aqueuses constituées de polymères de demi-ester de styrène-maléate de masse molaire élevée (en moyenne au moins 100 000 dalton en poids) en formant ledit demi-ester de maléate avec de l'alcool d'oxyalkylène-alkyle, de préférence de l'alcool de 2-(n-butoxy)éthyle.
PCT/US1994/011531 1993-10-18 1994-10-12 Solution polymere amelioree utilisee pour l'encollage de papier WO1995011341A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13733393A 1993-10-18 1993-10-18
US137,333 1993-10-18

Publications (1)

Publication Number Publication Date
WO1995011341A1 true WO1995011341A1 (fr) 1995-04-27

Family

ID=22476915

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/011531 WO1995011341A1 (fr) 1993-10-18 1994-10-12 Solution polymere amelioree utilisee pour l'encollage de papier

Country Status (1)

Country Link
WO (1) WO1995011341A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0930395A1 (fr) * 1998-01-20 1999-07-21 Dow Europe S.A. Composition de collage de papier peu moussante
WO2000063264A1 (fr) * 1999-04-16 2000-10-26 Henkel Kommanditgesellschaft Auf Aktien Copolymeres avec sous-unites amphiphiles, leur procede de production et leur utilisation
CN101225623B (zh) * 2008-01-09 2010-06-16 杨春先 造纸用表面施胶剂

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2206406A1 (fr) * 1972-11-15 1974-06-07 Sanyo Chemical Ind Ltd

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2206406A1 (fr) * 1972-11-15 1974-06-07 Sanyo Chemical Ind Ltd

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0930395A1 (fr) * 1998-01-20 1999-07-21 Dow Europe S.A. Composition de collage de papier peu moussante
WO1999036619A1 (fr) * 1998-01-20 1999-07-22 The Dow Chemical Company Composition peu moussante pour l'encollage de surface de papier
US6310159B1 (en) * 1998-01-20 2001-10-30 The Dow Chemical Company Low foaming paper surface sizing composition
WO2000063264A1 (fr) * 1999-04-16 2000-10-26 Henkel Kommanditgesellschaft Auf Aktien Copolymeres avec sous-unites amphiphiles, leur procede de production et leur utilisation
US6653428B1 (en) 1999-04-16 2003-11-25 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Copolymers with amphiphilic sub-units, a method for producing the same and the use thereof
CN101225623B (zh) * 2008-01-09 2010-06-16 杨春先 造纸用表面施胶剂

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