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WO1991005813A1 - Procede de production d'une matiere blanche a grain fin d'une resine d'uree-formaldehyde ou d'une resine uree-formaldehyde modifiee - Google Patents

Procede de production d'une matiere blanche a grain fin d'une resine d'uree-formaldehyde ou d'une resine uree-formaldehyde modifiee Download PDF

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Publication number
WO1991005813A1
WO1991005813A1 PCT/SE1990/000650 SE9000650W WO9105813A1 WO 1991005813 A1 WO1991005813 A1 WO 1991005813A1 SE 9000650 W SE9000650 W SE 9000650W WO 9105813 A1 WO9105813 A1 WO 9105813A1
Authority
WO
WIPO (PCT)
Prior art keywords
urea
formaldehyde
resin
formaldehyde resin
particles
Prior art date
Application number
PCT/SE1990/000650
Other languages
English (en)
Inventor
Stig Ohlsson
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
Publication of WO1991005813A1 publication Critical patent/WO1991005813A1/fr

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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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/10—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with acyclic compounds having the moiety X=C(—N<)2 in which X is O, S or —N
    • C08G12/12—Ureas; Thioureas
    • 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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
    • C08G12/36—Ureas; Thioureas
    • C08G12/38—Ureas; Thioureas and melamines

Definitions

  • the present invention relates to a white fine-grained material of urea-formaldehyde resin or a modified urea-formaldehyde resin.
  • urea-formaldehyde resins can be produced in many different ways and at different conditions depending on types of equipment and desired properties of the resin.
  • a process for the production of a white fine-grained material of urea-formaldehyde resin or a modified urea-formaldehyde resin has been brought about.
  • the process comprises reacting urea and formaldehyde in an aqueous solution at a molar ratio of urea*.formaldehyde between 1:0.4 and 1:2.5 at a temperature between 15°C and 100°C and at a pH between about 0.5 and 3.0, preferably between 0.8 and 2.0.
  • precipitated particles of urea resin being insoluble in the reaction mixture are formed as a slurry.
  • this slurry is neutralized.
  • there is a subsequent filtering step where the particles are filtered off. Possibly, there are also further steps where the particles are washed with water and ground.
  • the urea-formaldehyde resin or resin material is produced directly in an average particle size of about 10-60 micron.
  • the fine-grained urea-formaldehyde material can be used as an organic filler or whitening agent (colour pigment) in such connections where there is a demand thereof, for example at the production of white paper having good lithographic printing properties etc.
  • whitening agent colour pigment
  • Another field of use is as a fertilizer.
  • a further fine grinding can be made by wet grinding or alternatively by dry grinding of a dried product.
  • the urea-formaldehyde resin is produced by adding a small amount of acid, for.example sulphuric acid to a heated aqueous solution of urea and mixing while stirring with a heated aqueous solution of formaldehyde.
  • a small amount of acid for.example sulphuric acid
  • the formaldehyde with the acidified urea solution, particles of urea resin which are insoluble in the water containing reaction mixture are rapidly precipitated. During the reaction heat is generated. Therefore, sometimes cooling is suitable.
  • the resin in the particles contain a smaller or larger amount of cross linkings between the polymer chains depending on the reaction conditions. However, normally the resin can be regarded as cured.
  • the acid is suitably neutralized with alkali to a pH of 7 in such a manner that a water soluble salt is formed.
  • the fine-grained urea-formaldehyde resin material is filtered and washed to remove salts and possible rests of the raw materials used. Then the resin is ready to be used. A further mechanical fine grinding may be necessary depending on the application.
  • the urea-formaldehyde resin can be produced by using a large number of variations such as different molar ratios, the concentration of the solutions used, acids or acid salts, neutralization agents and temperatures. According to one possible variation the slurry is not neutralized to a pH of 7 but to a lower pH such as 3-6.
  • reactants for example dicyandiamide, melamine, thiourea, benzoguanamine, aniline, phenol or alkylphenol.
  • polymers of formaldehyde such as paraformaldehyde or other substances which can split off formaldehyde can be used instead of or as an addition to formaldehyde.
  • suitable aldehydes are for instance acetaldehyde, iso-butyraldehyde, acrolein, crotonaldehyde, furfural and glyoxal.
  • parts of the urea and formaldehyde used consist of a water soluble urea-formaldehyde precondensate, preferably produced by reaction of an aqueous solution of urea with an aqueous solution of formaldehyde at a molar ratio of urea:formaldehyde between 1:3 and 1:6 at a temperature of 15-100°C, preferably 70-100°C and at a pH of 0.5-5.
  • parts of the formaldehyde used are added as a melamine-formaldehyde precondensate or a melamine-urea-formaldehyde precondensate.
  • the urea or melamine respectively in the precondensate should make a minor proportion of the total amount of urea.
  • the amount of urea or melamine respectively in the precondensate is at most 25%, preferably at most 15% of the total amount of urea at the production of the resin particles.
  • the precipitation reaction is carried out at a molar ratio of urea:formaldehyde between 1:1.0 and 1:1.8.
  • the resin is used as a fertilizer the most preferred molar ratio is between 1:0.5-1:0.9.
  • organic and inorganic acids can be used such as sulphuric acid, sulfamic acid and/or phenolsulfonic acid.
  • the precipitation temperature is preferably between 60 C and 100°C.
  • the invention will be further illustrated in connection with the embodiment examples below, of which examples 1, 2, 3, 4, 6, 7, 8, 9, 10 and 11 show how the reaction conditions can be varied within the scope of the invention.
  • Example 5 is a comparison test outside the scope of the invention with an unsuccessful result.
  • 600 g urea 600 g distilled water and 100 g 20 per cent sulphuric acid were mixed. The mixture was heated while stirring to about 70°C. Thereafter, 600 g of a 50 per cent aqueous solution of formaldehyde was added, which reacted with the acidified urea solution, whereby small particles of insoluble urea resin were formed quickly. Due to the generation of heat, cooling of the flask was necessary.
  • the content of urea resin particles in the flask was neutralized by addition of sodium hydroxide solution to a pH of about 7, whereupon the particles were filtered off and washed carefully with water.
  • the fine-grained material could be used directly as a water containing filler.
  • the material can be fine ground for instance by wet grinding or by normal dry grinding after drying.
  • the precipitation formed did not have the same fine-grained nature.as in Example 1. Instead bigger lump formed particles could be present.
  • the content of suspended urea resin particles in the flask was neutralized to a. pH of 7 by addition of an aqueous solution of sodium hydroxide, whereupon the particles were filtered off and washed carefully with water.
  • the material After a wet grinding to a narrow and very small average particle size the material could be used as a white agent at the production of paper with equivalent properties as those obtained with other pigment materials such as kaolin present on the market.
  • the mixture was heated to about 75°C while stirring. Thereafter, 240 g 50 per cent aqueous solution of formaldehyde was added, whereby a thick slurry of particles of cured resin was formed immediately. In order to get the content more fluent 600 g water was added.
  • the sludge was then neutralized with a sodium hydroxide solution to a pH of 7, whereupon the particles were filtered off and washed carefully with water.
  • the temperature was 18 C when the urea had been dissolved. Thereafter, 570 g 50 per cent aqueous formaldehyde solution was added. The temperature of the mixture then increased to 73 C. At the same time a white precipitation of cured urea resin was formed. In order to decrease the viscosity of the sludge another 200 g of water was added.
  • the slurry was neutralized to a pH of 7 with an aqueous solution of sodium hydroxide.
  • the particles were filtered off and washed carefully with water, whereupn they could be used as a water containing filler.
  • the content of urea resin particles in the reactor was neutralized by addition of sodium hydroxide solution to a pH of 7, whereupon the particles were filtered off and washed carefully with water.
  • the porous fine-grained material had a specific area of
  • the material After a wet grinding in a pearl mill to an average particle size of 1-10 ⁇ m the material had a specific area of 32 m 2 and a pore volume of 1.16 cm3/g.
  • the fine-grained material can be used at the production of paper to increase the brightness and opacity values or the scattering coefficient.
  • a certain thermomechanical paper pulp had a scattering coefficient of 58-60 m 2/kg in newsprint paper.
  • a scattering 2 coefficient of 64 m /kg was obtained and with 6 parts by
  • the mixture was neutralized, washed and filtered to a. white powder.
  • the appearance of the particles formed varied. However, they were all more or less porous. Some looked like a cluster of grapes and others were more rounded.
  • Example 8 (molar ratio 1:1 . .17)
  • the mixture was neutralized, washed and filtered to a white powder.
  • the particles formed were rounded and porous.
  • the mixture was neutralized, washed and filtered to a white powder.
  • the particles formed were porous and round or rounded.
  • the mixture was neutralized, washed and filtered to a white powder.
  • the particles were porous and round and could be wet ground to smaller grain sizes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

Ledit procédé comprend la réaction de l'urée avec du formaldéhyde dans un rapport molaire urée/formaldéhyde compris entre 1 : 0.4 et 1: 2.5 à une température entre 15 et 100 °C et à un pH entre environ 0.5 et 3.0, de préférence entre 0.8 et 2.0. Des particules précipitées de résine d'urée qui sont insolubles dans le mélange de réaction sont ensuite réalisées sous forme de boue.
PCT/SE1990/000650 1989-10-20 1990-10-10 Procede de production d'une matiere blanche a grain fin d'une resine d'uree-formaldehyde ou d'une resine uree-formaldehyde modifiee WO1991005813A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8903470-6 1989-10-20
SE8903470A SE464815B (sv) 1989-10-20 1989-10-20 Foerfarande foer framstaellning av ett finkornigt material bestaaende av ett fullstaendigt uthaerdat urea-formaldehydharts

Publications (1)

Publication Number Publication Date
WO1991005813A1 true WO1991005813A1 (fr) 1991-05-02

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PCT/SE1990/000650 WO1991005813A1 (fr) 1989-10-20 1990-10-10 Procede de production d'une matiere blanche a grain fin d'une resine d'uree-formaldehyde ou d'une resine uree-formaldehyde modifiee

Country Status (3)

Country Link
AU (1) AU6619790A (fr)
SE (1) SE464815B (fr)
WO (1) WO1991005813A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993008954A1 (fr) * 1991-11-07 1993-05-13 Bip Chemicals Limited Composition et procede de decapage
CN102311530A (zh) * 2010-07-05 2012-01-11 天津城市建设学院 一种脲醛树脂原位聚合表面改性空心玻璃微珠的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE391753B (sv) * 1970-07-30 1977-02-28 Cabot Corp Komposition for bestrykning av papper innehallande en pigmentblandning bestaende av ett oorganiskt pigment och pigment av ett vattenolosligt bryggbildat karbamidharts

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE391753B (sv) * 1970-07-30 1977-02-28 Cabot Corp Komposition for bestrykning av papper innehallande en pigmentblandning bestaende av ett oorganiskt pigment och pigment av ett vattenolosligt bryggbildat karbamidharts

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, Vol. 10, No. 287, C375; & JP,A,61 106 616, 24-05-1986, (MITSUI TOATSU CHEM INC). *
PATENT ABSTRACTS OF JAPAN, Vol. 10, No. 321, C382; & JP,A,61 133 218, 20-06-1986, (MITSUI TOATSU CHEM INC). *
PATENT ABSTRACTS OF JAPAN, Vol.10, No. 303, C378; & JP,A,61 115 921, 03-06-1986, (MITSUI TOATSU CHEM INC). *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1993008954A1 (fr) * 1991-11-07 1993-05-13 Bip Chemicals Limited Composition et procede de decapage
CN102311530A (zh) * 2010-07-05 2012-01-11 天津城市建设学院 一种脲醛树脂原位聚合表面改性空心玻璃微珠的方法

Also Published As

Publication number Publication date
AU6619790A (en) 1991-05-16
SE8903470D0 (sv) 1989-10-20
SE8903470L (sv) 1991-04-21
SE464815B (sv) 1991-06-17

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