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WO1999002577A1 - Resine de phenol-formaldehyde modifiee et procede de preparation correspondant - Google Patents

Resine de phenol-formaldehyde modifiee et procede de preparation correspondant Download PDF

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Publication number
WO1999002577A1
WO1999002577A1 PCT/SE1998/001281 SE9801281W WO9902577A1 WO 1999002577 A1 WO1999002577 A1 WO 1999002577A1 SE 9801281 W SE9801281 W SE 9801281W WO 9902577 A1 WO9902577 A1 WO 9902577A1
Authority
WO
WIPO (PCT)
Prior art keywords
formaldehyde
phenol
resin
aracterised
formaldehyde resin
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.)
Ceased
Application number
PCT/SE1998/001281
Other languages
English (en)
Inventor
Stig Ohlsson
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.)
Perstorp AB
Original Assignee
Perstorp AB
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 Perstorp AB filed Critical Perstorp AB
Priority to AU83623/98A priority Critical patent/AU8362398A/en
Publication of WO1999002577A1 publication Critical patent/WO1999002577A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
    • C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
    • C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
    • C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates

Definitions

  • the present invention relates to a modified phenol-formaldehyde resin comprising cationic groups, and in a further aspect to a process of making said resin.
  • Phenol-formaldehyde resins, resoles as well as novolacs, are since the beginning of this century well known in the art. Phenolic resins are disclosed and discussed inter alia in Kirk-Othmer "Encyclopedia of Chemical Technology", vol. 17, 1982, pp. 384-416. Normally, phenol-formaldehyde resins do not comprise cationic groups. Said resins include for instance moulding compound resins, laminate resins, foundry resins and resins for coatings and glues as well as a large number of speciality applications as disclosed in for instance the Canadian Patent no. 1 ,044,782.
  • Said Patent discloses the use of a combination of a phenol-formaldehyde resin and a polyethylene oxide for improved retention in dewatering of cellulose fibre slurries.
  • Swedish Patent Application no. 8604975-6 teaches improved filling retention in dewatering of cellulose fibre slurries by addition of a phenol-formaldehyde resins and a high molecular polyethylene oxide in combination with a cationic derivative of starch or cellulose.
  • Improved filling retention is also known from the U.S. Patent no. 5,516,405, which teaches a method of improving the first pass filler retention of a papermaking pulp slurry.
  • the method comprises adding an organic cationic fixative, a promoter and a polyethylene oxide to a filler containing slurry to increase the first pass retention of said filler.
  • the organic fixative is selected from the group consisting of polyethylene amides, polydiallyl dimethylammonium chlorides and polyethylene imines and the promoter consists of for instance a phenol-formaldehyde resin.
  • the present invention relates to a modified phenol-formaldehyde resin which can be used for instance in combination with polyethylene oxide to improve, compared to ordinary phenol-formaldehyde resins as discussed above, the retention in dewatering of cellulose fibre slurries.
  • the resin of the present invention is characterised in that it comprises cationic groups and that it has a cationicity of approximately 2-95%, such as 5-85% or preferably 15-60%.
  • the phenol-formaldehyde resin corresponds, besides the content of cationic groups, to ordinary phenol-formaldehyde resins used in retention systems within the papermaking and pulp industry.
  • the resin is accordingly a condensation product obtained by subjecting at least one phenolic compound and formaldehyde to a condensation reaction.
  • the resin of the present invention is preferably a resole, which is a reaction product between a phenolic compound and formaldehyde in excess. Novolacs can of course also be prepared and used.
  • the resin is in suitable or preferred embodiments a water diluted or waterborne cationic phenol-formaldehyde resins.
  • the cationic groups in the phenol-formaldehyde resin of the invention can either be introduced during the condensation or by addition to a processed resin.
  • the invention is not limited to any specific cationic group.
  • the cationic group is, however, in preferred embodiments an amine group derived from ammonia or a primary, secondary or tertiary amine.
  • the amine group can in certain embodiments be attached to the resin by means of a linking group.
  • Preferred amines include for instance ethanolamine, «-propylamine, dibutylamine, triethylamine and diethylethanolamine.
  • the phenolic compound is in various embodiments a phenol, a cresol, an alkylphenol, such as nonylphenol, or a combination thereof.
  • the phenolic compound can also suitably be a sulphur derivatised phenol, cresole, alkylphenol or a combination thereof, such as a pre-condensate between sulphur and for instance said phenol, cresole, alkylphenol or said combination thereof.
  • the cationicity is the ratio between the cationic groups and the anionic groups (phenolic groups). The latter is normally a part of the resin.
  • a cationicity of 0% means that the phenol-formaldehyde resin only contains the normally present anionic phenolic groups and that it does not contain any cationic groups.
  • the concentration of anionic phenolic groups can in many resins be exemplified by the figure « 24 ⁇ equivalents/g dry resin.
  • a cationicity of 20% means that the concentration of cationic groups corresponds to 20% of the anionic groups, which using above figure corresponds to « 5 ⁇ equivalents/g dry resin.
  • a cationicity of 35% accordingly corresponds to « 8 ⁇ equivalents/g dry resin.
  • a suitable method for determination of cationicity is disclosed in "Charge Titration for Selection and Dosage of Flocculants" by Lydia Bley, published March 1994 in Miitek Application 1501 -e, Miitek
  • the present invention relates to a process of making a modified phenol-formaldehyde resin as disclosed above.
  • the process comprises subjecting a number of monomers consisting of or comprising at least one phenolic compound and formaldehyde to a condensation reaction at a molar ratio phenolic compound to formaldehyde of 1 : 1 to 1 :3.5, preferably 1.2, at a reaction temperature of 40-100°C, preferably 50-90°C, at atmospheric or reduced pressure and at a pH exceeding « 8.
  • the condensation reaction is performed in an aqueous medium in the presence of ammonia, a primary, secondary or tertiary amine or a mixture thereof as combined catalyst and reactant introducing cationic amino groups into the phenol-formaldehyde resin.
  • the condensation reaction is, furthermore, maintained until a high molecular resin having a cationicity of 5-85%, preferably 15-60% is obtained.
  • the condensation reaction is suitably maintained until all monomers are consumed.
  • Obtained resin is subsequently treated with an aqueous solution of at least one alkali or alkaline earth metal hydroxide, such as sodium, potassium and/or calcium hydroxide, whereby a resin solution comprising a cationic phenol-formaldehyde resin, which resin at a pH of less than » 7 can be precipitated as small particles, is yielded.
  • the formaldehyde is suitably employed as an aqueous solution having a formaldehyde content of 30-55% by weight.
  • the phenolic compound is in various embodiments preferably a phenol, a cresol, an alkylphenol, such as nonylphenol, or a combination thereof.
  • the phenolic compound can, furthermore, be a sulphur derivatised phenol, cresole, alkylphenol or a combination thereof, such as a pre-condensate between sulphur and for instance said phenol, cresole, alkylphenol or said combination thereof.
  • the process of the present invention can advantageously commence with a mixing and pre-heating of the phenol and the ammonia or amine, which mixing and pre-heating is followed by a gradual addition of the formaldehyde.
  • ammonia or amine compound can in alternative embodiments of the process be mixed into a finished phenol-formaldehyde resin, thus providing a certain cationicity in said resin.
  • Example 6 Comparative example beyond the scope of the invention. Preparation of a reference resole resin without amino groups.
  • Example 1 1 Preparation of a novolac resins, in accordance with the invention, wherein amino groups are reacted into said resin.
  • Example 12 Evaluation of the resins according to Example 5 compared to a conventional resin as retention agent in dewatering of a cellulose fibre slurry. The resins were used together with polyethylene oxide.
  • reaction mixture was now cooled and 3.56 moles (310 g) of an aqueous sodium hydroxide solution (46% by weight of sodium hydroxide) was added to yield a water soluble resin. 15.28 moles (275 g) of water was also added.
  • the cationicity of obtained resole was determined to be 27% in comparison to a standard resole resin prepared without amino groups (Example 6).
  • the cationicity of obtained resole was determined to be 40% in comparison to a standard resole resin prepared without amino groups (Example 6).
  • the cationicity of obtained resole was determined to be 36% in comparison to a standard resole resin prepared without amino groups (Example 6).
  • the reaction mixture was after determination of completed condensation cooled and 2.97 moles (258 g) of an aqueous sodium hydroxide solution (46% by weight of sodium hydroxide) and 38.89 moles (700 g) of water were added.
  • the cationicity of obtained resole was determined to be 42% in comparison to a standard resole resin prepared without amino groups (Example 6).
  • the cationicity of obtained resole was determined to be 28% in comparison to a standard resole resin prepared without amino groups (Example 6).
  • the cationicity of obtained resole was determined to be 50% in comparison to a standard resole resin prepared without amino groups (Example 6).
  • the cationicity of obtained resole was determined to be 20% in comparison to a standard resole resin prepared without amino groups (Example 6).
  • a phenol-sulphur pre-condensate was prepared by reacting 4.53 moles (426 g) of phenol with 1.69 mole (54 g) of sulphur at a temperature of 1 15°C and in the presence of NaOH (aq) as catalyst.
  • the pre-condensate according to above and 0.66 mole (77.1 g) of the tertiary amine diethylethanolamine were charged in a 2 litres reaction flask.
  • the mixture was heated to « 75°C and 8.72 moles (524 g) of an aqueous methanol free formaldehyde solution (50% by weight of formaldehyde) was gradually, under stirring and controlled cooling, added during « 20 minutes (exothermic reaction).
  • the reaction temperature was raised to 100°C and the reaction was allowed to continue for a further 15 minutes.
  • the reaction mixture was after determination of completed condensation cooled and 2.97 moles (258 g) of an aqueous sodium hydroxide solution (46% by weight of sodium hydroxide) and 38.89 moles (700 g) of water were added.
  • the cationicity of obtained resole was determined to be 10% in comparison to a standard resole resin prepared without amino groups (Example 6).
  • reaction mixture was after determination of completed condensation cooled and 0.98 mole (58 g) of an aqueous sodium hydroxide solution (46% by weight of sodium hydroxide) and 16.67 moles (300 g) of water were added. 16.2 moles (190.8 g) diethylethanoamine was now mixed into obtained resin.
  • the cationicity of obtained resole mixed with amine was determined to be 10.8% in comparison to a standard resole resin prepared without amino groups (Example 6).
  • Obtained product was a novolac wherein the molar ration phenol:formaldehyde:diethylethanolamine was 1 :0.75 :0.1 1.
  • the cationicity of obtained novolac was determined to be 27% in comparison to a standard resin prepared without amino groups (Example 6).
  • thermomechanic pulp made from coniferous wood was when required diluted with tap water. The non-volatile content, pH and temperature of the furnish were adjusted to the processing conditions of used paper maker machine. The diluted furnish was pre-heated to correct temperature and pH was adjusted prior to use.
  • Used polyethylene (PEO) had a molecular weight of 7 x 10 , a density of 1210 kg/m 3 and a viscosity of 6000-10000 mPas at 25°C.

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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)
  • General Chemical & Material Sciences (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

L'invention concerne de la résine de phénol-formaldéhyde modifiée et son procédé de préparation. La résine comporte des groupes cationiques et a une cationisation de 2-95 %, de préférence, 15-60 %. La résine est, de façon adéquate, un résole modifié obtenu à partir d'un composé phénolique, tel qu'un phénol, un crésol, un alkylphénol et/ou un dérivé de soufre, et du formaldéhyde dans un rapport molaire de 1:1 à 1:3,5, à une température de 40 à 100 °C et avec un pH supérieur à environ 8. Le procédé est exécuté dans un agent aqueux et en présence d'ammoniac ou d'une amine comme catalyseur et réactif combinés, les groupes anioniques étant introduits dans la résine.
PCT/SE1998/001281 1997-07-07 1998-06-30 Resine de phenol-formaldehyde modifiee et procede de preparation correspondant Ceased WO1999002577A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU83623/98A AU8362398A (en) 1997-07-07 1998-06-30 Modified phenol-formaldehyde resin and process of making the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9702606A SE509778C2 (sv) 1997-07-07 1997-07-07 Modifierat fenolformaldehydharts innehållande katjoniska grupper samt sätt att framställa detsamma
SE9702606-6 1997-07-07

Publications (1)

Publication Number Publication Date
WO1999002577A1 true WO1999002577A1 (fr) 1999-01-21

Family

ID=20407658

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1998/001281 Ceased WO1999002577A1 (fr) 1997-07-07 1998-06-30 Resine de phenol-formaldehyde modifiee et procede de preparation correspondant

Country Status (3)

Country Link
AU (1) AU8362398A (fr)
SE (1) SE509778C2 (fr)
WO (1) WO1999002577A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130310612A1 (en) * 2011-01-14 2013-11-21 Sumitomo Bakelite Co., Ltd. Liquid resol-type phenolic resin

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DIALOG INFORMATION SERVICES, File 351, Dialog Accession No. 004487204, WPI Accession No. 85-314082/198550, NIPPON SHOKUBAI KAGAKU KOGYO CO. LTD., "Cationic Resin Prodn. - by Reacting Polyphenol-Polyformaldehyde Precondensate with Aziridine Cpd."; & JP,A,60 219 212 (01-11-85). *
DIALOG INFORMATION SERVICES, File 351, Dialog Accession No. 010079456, WPI Accession No. 94-347169/199443, SHIN KOBE ELECTRIC MACHINERY, "Prepn. of Polyphenol Resin for Laminating Materials - by Reacting Polyphenol and Polyformaldehyde in Presence of Alkali Catalysts"; & JP,A,06 271 633 (27-09-94). *
DIALOG INFORMATION SERVICES, File 351, Dialog Accession No. 010127949, WPI Accession No. 95-029200/199504, TOKEM FIRM., "Prepn. of Resol. Poly-Polyphenolformaldehyde Resin Used as Binder in mfr. of Textolite - by Condensing Polyphenol and Polyformaldehyde in Presence of Triethylamine with Subsequent addn. of *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130310612A1 (en) * 2011-01-14 2013-11-21 Sumitomo Bakelite Co., Ltd. Liquid resol-type phenolic resin
US9657139B2 (en) 2011-01-14 2017-05-23 Sumitomo Bakelite Co., Ltd. Liquid resol-type phenolic resin

Also Published As

Publication number Publication date
SE9702606D0 (sv) 1997-07-07
SE509778C2 (sv) 1999-03-08
AU8362398A (en) 1999-02-08
SE9702606L (sv) 1999-01-08

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