WO2009065771A1 - Procédé de fabrication d'une résine de condensation - Google Patents

Procédé de fabrication d'une résine de condensation Download PDF

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Publication number
WO2009065771A1
WO2009065771A1 PCT/EP2008/065540 EP2008065540W WO2009065771A1 WO 2009065771 A1 WO2009065771 A1 WO 2009065771A1 EP 2008065540 W EP2008065540 W EP 2008065540W WO 2009065771 A1 WO2009065771 A1 WO 2009065771A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
anyone
resin
preparation
condensation resin
Prior art date
Application number
PCT/EP2008/065540
Other languages
English (en)
Inventor
Wilhelmus Jacobus Cramer
Bernd Ohlmeier
Theo Karel Schulpen
Original Assignee
Dsm Ip Assets B.V.
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 Dsm Ip Assets B.V. filed Critical Dsm Ip Assets B.V.
Priority to EA201000847A priority Critical patent/EA201000847A1/ru
Priority to EP08852615A priority patent/EP2212361A1/fr
Priority to AU2008328032A priority patent/AU2008328032A1/en
Publication of WO2009065771A1 publication Critical patent/WO2009065771A1/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
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines

Definitions

  • the present invention relates to a process for the preparation of a condensation resin in an aqueous medium at elevated temperature and pressure.
  • Processes for the preparation of condensation resins are either performed batch wise, or in recent days also (semi-) continuous. Examples of batch wise preparation are those which are performed in a stirred tank reactor, or even a combination of several of stirred tank reactors, all operated in batch mode.
  • the present invention recognizes that the use of an extruder is not appropriate for processes for a preparation of a condensation resin in which the process stream has a viscosity well below 50 Pa. s.
  • the present invention also acknowledges that preparation at such low viscosities at more elevated pressures than normally attainable in an extruder are desired, as a result of which the process can be performed at a higher temperature. This all being the consequence of the fact that the resin preparation is performed in an aqueous medium.
  • the ratio of the monomeric ingredients (monomeric ratio) fed to the reactor is crucial, which needs dedicated process control and analysis.
  • the present invention presents a solution for the above indicated items, in that the process comprising a process step in which an aqueous master batch of at least two of the monomeric precursors of the condensation resin is prepared in a continuous loop system at a temperature below 20 0 C, and a consecutive process step in which a portion of the master batch is fed continuously to one or more tubular reactors provided with static mixer elements and positioned parallel to each other, said tubular reactor(s) individually being operated at a temperature between 70 and 200 0 C, and at a pressure between 0.2 and 20 MPa.
  • the process comprises a master batch preparation in combination with one of more continuously operated tubular reactors, said reactors being parallel to each other coupled to the master batch preparation.
  • the process can be performed with process streams that have a significant lower viscosity than those which are suitable for an extruder-operated process.
  • the present process can cope with viscosities up to 10 Pa. s; more preferred the viscosity of the contents of the reactor is at most 1800 mPa.s; the viscosity being determined at the local conditions in the reactor (i.e. at the local pressure and temperature conditions).
  • the master batch is prepared in a continuous process. In such a system one can easily change the monomeric ratio in order to prepare condensation resins with different compositions.
  • the alternative is the use of several master batch containers, each having their own, and from each other, differing monomeric ratios.
  • condensation resin For each condensation resin to be prepared in the process of the present invention, the condition under which essentially no reaction occurs between the monomeric precursors is naturally different. On the other hand, the skilled man wanting to prepare a specific condensation resin is aware of and knowledgeable with conditions under which essentially no condensation occurs. "Essentially no reaction" in the context of this invention means that at least 90 mol.- % of the monomeric precursors are present in unreacted form; preferably this amount is at least 95 mol.- %. Of course the occurrence of a condensation polymerization between the monomeric precursors in the master batch preparation can be avoided by the addition of polymerization inhibitors, but such inhibitors will be of hindrance in the consecutive process step where the condensation polymerization should take place (in the tubular reactor(s)).
  • the temperature of the master batch shall always be a critical factor for avoiding a (start of the) condensation polymerization.
  • the master batch preparation is in the form of a continuous process and this continuous master batch process is performed in a loop system, to which system one or more of the tubular reactors are coupled in parallel. When the master batch is in the form of a dispersion/slurry, care should be taken that the homogeneity of such a dispersion/slurry is secured.
  • the vessel in which the master batch is present can therefore be stirred.
  • the loop can also be provided with means to maintain or secure the homogeneity.
  • static mixers can be used as such means in the loop.
  • Each tubular reactor used in the process is, in the inside of the reactor, provided with one or more static mixer elements.
  • Such a reactor, also named a static mixer can be described as a pipe with immovable internal elements that achieve continuous multiple splitting and recombination, and/or turbulence of streams of material passing through and improve distributive mixing.
  • the tubular reactor can be filled over its full length with the static mixer elements, but also a partially filled tubular reactor (seen in the axial direction) can be applied.
  • the unfilled part of the tubular reactor can be used for e.g. heating or cooling of the mixture.
  • the process of the present invention is suitable for the preparation of any condensation resin, in which said preparation takes place in an aqueous medium; or in other words: in all preparations where water is either a solvent or a dispersion agent. Other solvents or dispersing liquids may be present, next to water, but they are only present in a minor amount compared to water.
  • a condensation resin is any class of polymer formed through a condensation reaction, releasing (or condensing) a small molecule by- - A -
  • Condensation polymerization a form of step-growth polymerization, is a process by which two molecules join together, with the loss of a small molecule which is often water.
  • the type of end product resulting from a condensation polymerization is dependent on the number of functional end groups of the monomer which can react. Monomers with only one reactive group terminate a growing chain, and thus give end products with a lower molecular weight. Linear polymers are created using monomers with two reactive end groups; monomers with more than two end groups give three dimensional polymers when crosslinked.
  • the process of the present invention is, in each tubular reactor, performed at elevated pressure and temperature, which can be selected for the preparation of the desired resin, within the boundaries of the conditions needed for said preparation.
  • the temperature is between 70 and 200 0 C; the pressure is between 0.2 and 20 MPa.
  • the temperature is between 100 and 150 0 C, at a pressure which is at least the corresponding vapor pressure.
  • the skilled man can decide to select his own pressure, deviating from the vapor pressure, for instance by using a pressure control.
  • the dimensions of the tubular reactor can be chosen freely, depending on the desired throughput.
  • the tubular reactor has a circular cross-section.
  • the diameter of the tube will in general be at least 5 mm, and will not exceed 500 mm.
  • the length will in general be at least 25 mm, and will not exceed 100 m.
  • the skilled man is able to select the material of the tubular reactor and the static mixer elements, based on the materials to be processed in the reactor.
  • the process can be applied using an aqueous medium, in which the solids content of the resin is between 15 and 90 wt.%; preferably between 20 and 85 wt.%; more preferred this content is between 45 and 75 wt.%.
  • the process of the present invention is very suitable for the preparation of a condensation resin, wherein said resin is prepared from an aldehyde (preferably (para-)formaldehyde), a triazine (preferably melamine), an aromatic alcohol (preferably phenol), or urea.
  • aldehyde preferably (para-)formaldehyde
  • a triazine preferably melamine
  • an aromatic alcohol preferably phenol
  • urea urea
  • mixtures of said ingredients can be used (like a mixture of melamine, urea and formaldehyde, resulting in a so-called MUF-resin, or a mixture of melamine, urea, phenol, and formaldehyde, resulting in a MUPF-resin).
  • the preparation of the resin according to the present invention can also start with a so-called precondensate, which is a low-molecular precursor of the desired resin, but in which already some degree of condensation between the constituting monomers has taken place.
  • the condensation resin to be prepared according to the process of the present invention is an aminoplast (a condensation resin based on a triazine or urea, and an aldehyde) or a phenolic resin (a condensation resin based on an aromatic alcohol, and an aldehyde).
  • the triazine is preferably melamine
  • the aldehyde is preferably (para-)formaldehyde.
  • the aromatic alcohol is preferably phenol
  • the aldehyde is preferably (para-)formaldehyde
  • condensation resin based on (para-) formaldehyde, melamine and urea.
  • a condensation resin is prepared having melamine and
  • the F/M ratio (being the molar ratio between the (para-)formaldehyde (F) and the melamine (M) in the condensation resin) is generally between 0.25 and 7.5; preferably this ratio is between 0.5 and 6.0. More preferred, this ratio is between 1.0 and 1.8.
  • all the melamine-formaldehyde resins as disclosed in WO 2006/1 19982 can be prepared.
  • the ingredients necessary for the preparation of the condensation resin are metered to the tubular reactor(s) as an aqueous master batch.
  • the master batch is generally fed to the tubular reactor(s) via the front end of that tubular reactor. Between the container/loop of the master batch and said reactor(s) a preheating of the master batch mixture can be performed, to at least partially preheat the mixture from the temperature used in the master batch preparation.
  • Equipment suitable therefore are known to the skilled man.
  • the product resulting from the process of the present invention is a condensation resin in an aqueous medium, at elevated temperature and pressure. This makes this product very suitable for use in an impregnation process, in which a substrate (like paper, wool, etc.) is impregnated with the resin, especially when the impregnation process is also performed under elevated pressure (which results in an improvement of the degree and/or speed of impregnation).
  • the impregnation process can be a one-step process in which only one resin is used for impregnation; or a multi-step process, in which two or more different resins are used.
  • a first impregnation can be performed with a urea/formaldehyde based resin; and a second impregnation with a melamine/formaldehyde based resin.
  • Both feeds can be prepared in one system according to the invention; preferably the resin feeds are prepared in two parallel positioned systems, each comprising a master batch preparation and one or more, static mixer filled, tubular reactors.
  • the impregnation process controls the resin preparation via a process control unit.
  • a control unit can be a computer, which, given the desired conditions of the impregnations, sets and controls the process parameters for the resin preparation (like monomer ratio, temperature, concentration of monomers, etc.).
  • the invention will be elucidated with the following Examples and comparative experiment, which are intended to show the benefits of the invention.
  • the Examples and experiment were performed in one or more heated steel tubular reactor(s) with an internal diameter of 10 mm and a length of 2.0 m.
  • the reactor(s) were provided with 96 SMXL static mixer elements of Sulzer having a diameter of 10 mm.
  • the result of the Examples was determined with respect to the so- called water-tolerance (W.T.) of the obtained resin. This WT. is the amount of resin that can be dissolved in water at room temperature (dimension: gram/gram).
  • W.T. water-tolerance
  • Formalin (with 30 wt. % formaldehyde (F)), melamine (M), di-ethylene glycol (DEG) and caprolactam were mixed with water to obtain as a master batch a dispersion with an F/M-molar ratio of 1.65.
  • Table 1 gives the used recipe (in wt. %).
  • the ingredients were mixed in a storage tank, provided with an external loop with a circulation pump. The temperature in the storage tank was 5 0 C; the pressure in the tank was atmospheric.
  • a feed pump was placed in the loop in order to feed part of the circulating master batch to the tubular reactor.
  • a heat exchanger was present to preheat the feed to the tubular reactor.
  • the feed to the tubular reactor was varied.
  • the temperature of the mixture entering the tubular reactor was 120 0 C.
  • the temperature was 140 0 C; thereafter the mixture was cooled via a water bath to room temperature.
  • the pressure in the tubular reactor was set at 1 MPa.
  • Table 2 gives the realized water tolerances (W.T.) of the produced resin, as a function of the flow through the tubular reactor.
  • Example I was repeated, but now with an F/M molar ratio of 1.4.
  • Table 3 gives the recipe (in wt. %).
  • the flow was set at 5.6 kg/h; it resulted in a water tolerance of 0.6.
  • Example I was repeated, but now in absence of the static mixer elements in the tubular reactor (i.e. with the use of a non-filled tube). After 4 hours of experimentation, the tube appeared to be plugged internally due to the formation of polymer on the internal wall of the tube.
  • Example I was repeated, but now with 3 tubular reactors coupled parallel to each other.
  • three feed pumps were placed in the external loop of the master batch preparation system.
  • Each feed pump provided individual feed to one reactor. Every reactor had individual feed heater and temperature control, so it was possible to produce three resins that differed in WT. at different rates simultaneously.
  • reactor 3 had a feed point for formalin upstream the feed heater where additional formalin was added to increase the F/M-ratio. The results are presented in Table 4.
  • Example 1.4 The resin produced in Example 1.4 was used to continuously and inline impregnate a paper sheet.
  • a master batch preparation system and a reactor were fitted in front of the resin kitchen of an existing paper impregnation line.
  • Resin was produced according to the recipe given in Table 1 and the process conditions of Example 1.4.
  • the resin produced in the continuous reactor was immediately processed in the resin kitchen and fed to the paper impregnation line.
  • the thus produced impregnated paper sheets were used to press test specimens of laminated resin paper on a wood based panel. Test results showed a resin quality equal to commercial product.
  • the resin kitchen can even be omitted by feeding the impregnation ingredients to the reactor, creating a direct coupling from the reactor to the impregnation line, if desired

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)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Abstract

La présente invention porte sur un procédé de fabrication d'une résine de condensation à une température élevée et sous une pression élevée. Le procédé est effectué en continu dans un ou plusieurs réacteurs tubulaires dotés d'éléments mélangeurs statiques. L'alimentation du ou des réacteurs tubulaires provient d'une préparation de mélange maître, préparation dans laquelle pratiquement aucune réaction n'a lieu entre les précurseurs monomères.
PCT/EP2008/065540 2007-11-22 2008-11-14 Procédé de fabrication d'une résine de condensation WO2009065771A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EA201000847A EA201000847A1 (ru) 2007-11-22 2008-11-14 Способ получения кондесационной смолы
EP08852615A EP2212361A1 (fr) 2007-11-22 2008-11-14 Procédé de fabrication d'une résine de condensation
AU2008328032A AU2008328032A1 (en) 2007-11-22 2008-11-14 Process for the preparation of a condensation resin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EPPCT/EP2007/010142 2007-11-22
EP2007010142 2007-11-22

Publications (1)

Publication Number Publication Date
WO2009065771A1 true WO2009065771A1 (fr) 2009-05-28

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PCT/EP2008/065540 WO2009065771A1 (fr) 2007-11-22 2008-11-14 Procédé de fabrication d'une résine de condensation

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AU (1) AU2008328032A1 (fr)
EA (1) EA201000847A1 (fr)
WO (1) WO2009065771A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010149632A1 (fr) * 2009-06-22 2010-12-29 Dynea Oy Procédé de production en continue d'une solution de résine aqueuse de formaldéhyde hydroxyaryle
EP3003549A1 (fr) * 2013-05-29 2016-04-13 Basf Se Procédé continu pour la préparation de polyoxazolines
EP2231735B1 (fr) * 2007-12-21 2016-06-08 Dynea Austria GmbH Procédé de fabrication en continu de solutions aqueuses hautement efficaces de résine d'aminoformaldéhyde
EP4029890A1 (fr) 2021-01-18 2022-07-20 Foresa Technologies S.L.U. Procédé de production de résines d'urée-formaldéhyde, résines ainsi obtenues et applications desdites résines

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB758125A (en) * 1953-04-15 1956-09-26 Spumalit Anstalt Apparatus for the continuous production of aminoplasts
GB1460029A (en) * 1972-12-21 1976-12-31 Perstorp Ab Continuous process for the production of phenolic urea and mela mine resins and apparatus therefor
EP0638599A2 (fr) * 1993-08-13 1995-02-15 Hoechst Aktiengesellschaft Procédé de préparation de polyacétals
JPH10204139A (ja) * 1997-01-17 1998-08-04 Sumitomo Bakelite Co Ltd ノボラック型フェノール樹脂の製造方法
WO2001005725A1 (fr) * 1999-07-16 2001-01-25 Rockwool International A/S Resine destinee a un liant pour laine minerale et comprenant le produit de reaction d'une amine avec un premier et un second anhydride
WO2004092239A1 (fr) * 2003-04-16 2004-10-28 Ami Agrolinz Melamine International Gmbh Procede de synthese d'une resine liquide de melamine en continu
WO2006119982A1 (fr) * 2005-05-10 2006-11-16 Ami Agrolinz Melamine International Gmbh Solution de resine de melamine-formaldehyde et procede de production de cette solution
EP1785438A1 (fr) * 2004-08-19 2007-05-16 Asahi Organic Chemicals Industry Co., Ltd. Procede de fabrication de resine phenolique de type novolak
WO2008128908A1 (fr) * 2007-04-20 2008-10-30 Dsm Ip Assets B.V. Processus de préparation d'une résine de condensation

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB758125A (en) * 1953-04-15 1956-09-26 Spumalit Anstalt Apparatus for the continuous production of aminoplasts
GB1460029A (en) * 1972-12-21 1976-12-31 Perstorp Ab Continuous process for the production of phenolic urea and mela mine resins and apparatus therefor
EP0638599A2 (fr) * 1993-08-13 1995-02-15 Hoechst Aktiengesellschaft Procédé de préparation de polyacétals
JPH10204139A (ja) * 1997-01-17 1998-08-04 Sumitomo Bakelite Co Ltd ノボラック型フェノール樹脂の製造方法
WO2001005725A1 (fr) * 1999-07-16 2001-01-25 Rockwool International A/S Resine destinee a un liant pour laine minerale et comprenant le produit de reaction d'une amine avec un premier et un second anhydride
WO2004092239A1 (fr) * 2003-04-16 2004-10-28 Ami Agrolinz Melamine International Gmbh Procede de synthese d'une resine liquide de melamine en continu
EP1785438A1 (fr) * 2004-08-19 2007-05-16 Asahi Organic Chemicals Industry Co., Ltd. Procede de fabrication de resine phenolique de type novolak
WO2006119982A1 (fr) * 2005-05-10 2006-11-16 Ami Agrolinz Melamine International Gmbh Solution de resine de melamine-formaldehyde et procede de production de cette solution
WO2008128908A1 (fr) * 2007-04-20 2008-10-30 Dsm Ip Assets B.V. Processus de préparation d'une résine de condensation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 199841, Derwent World Patents Index; AN 1998-476788, XP002482370 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2231735B1 (fr) * 2007-12-21 2016-06-08 Dynea Austria GmbH Procédé de fabrication en continu de solutions aqueuses hautement efficaces de résine d'aminoformaldéhyde
WO2010149632A1 (fr) * 2009-06-22 2010-12-29 Dynea Oy Procédé de production en continue d'une solution de résine aqueuse de formaldéhyde hydroxyaryle
EP3003549A1 (fr) * 2013-05-29 2016-04-13 Basf Se Procédé continu pour la préparation de polyoxazolines
EP4029890A1 (fr) 2021-01-18 2022-07-20 Foresa Technologies S.L.U. Procédé de production de résines d'urée-formaldéhyde, résines ainsi obtenues et applications desdites résines
WO2022152941A1 (fr) 2021-01-18 2022-07-21 Foresa Technologies, S.L.U. Procédé de production de résines d'urée-formaldéhyde, résines ainsi obtenues et applications desdites résines

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Publication number Publication date
AU2008328032A1 (en) 2009-05-28
EA201000847A1 (ru) 2010-12-30

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