[go: up one dir, main page]

WO2010149632A1 - Procédé de production en continue d'une solution de résine aqueuse de formaldéhyde hydroxyaryle - Google Patents

Procédé de production en continue d'une solution de résine aqueuse de formaldéhyde hydroxyaryle Download PDF

Info

Publication number
WO2010149632A1
WO2010149632A1 PCT/EP2010/058750 EP2010058750W WO2010149632A1 WO 2010149632 A1 WO2010149632 A1 WO 2010149632A1 EP 2010058750 W EP2010058750 W EP 2010058750W WO 2010149632 A1 WO2010149632 A1 WO 2010149632A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
process according
tube
reaction mixture
hydroxy
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/EP2010/058750
Other languages
English (en)
Inventor
Michael Gann
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.)
Dynea Oy
Original Assignee
Dynea Oy
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 Dynea Oy filed Critical Dynea Oy
Publication of WO2010149632A1 publication Critical patent/WO2010149632A1/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
    • 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
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F25/00—Flow mixers; Mixers for falling materials, e.g. solid particles
    • B01F25/40—Static mixers
    • B01F25/42—Static mixers in which the mixing is affected by moving the components jointly in changing directions, e.g. in tubes provided with baffles or obstructions
    • B01F25/43—Mixing tubes, e.g. wherein the material is moved in a radial or partly reversed direction
    • B01F25/431—Straight mixing tubes with baffles or obstructions that do not cause substantial pressure drop; Baffles therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/80—Mixing plants; Combinations of mixers
    • B01F33/81—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles
    • B01F33/811—Combinations of similar mixers, e.g. with rotary stirring devices in two or more receptacles in two or more consecutive, i.e. successive, mixing receptacles or being consecutively arranged
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
    • B01F35/90—Heating or cooling systems
    • B01F35/92—Heating or cooling systems for heating the outside of the receptacle, e.g. heated jackets or burners
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/006—Baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • B01J19/242—Tubular reactors in series
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00054—Controlling or regulating the heat exchange system
    • B01J2219/00056—Controlling or regulating the heat exchange system involving measured parameters
    • B01J2219/00058—Temperature measurement
    • B01J2219/00063—Temperature measurement of the reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00162—Controlling or regulating processes controlling the pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00168—Controlling or regulating processes controlling the viscosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00177—Controlling or regulating processes controlling the pH
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles

Definitions

  • the invention relates to a process for the continuous production of an aqueous hydroxy-aryl formaldehyde resin solution, comprising the steps of preparing a reaction mixture of a hydroxy-aryl compound and aqueous formaldehyde, adding a catalyst to the reaction mixture and reacting the reaction mixture in the presence of the catalyst.
  • the invention further relates to a continuous plug flow polymerisation reactor and to the use of such reactor in a process for preparing a resin solution
  • the invention also relates to the use of a specific continuous mixing device for continuous mixing of catalyst into a reaction mixture.
  • the invention further also relates to the hydroxy-aryl formaldehyde resin solution and to the resin obtainable by the process, to the use thereof for the manufacture of adhesive compositions, to adhesive compositions comprising the hydroxy-aryl formaldehyde resin.
  • US3816376 describes a continuous phenolic resin production process but teaches a cascade of at least three stirred vessels with back mixing of the solution. According to the Bodenstein theory, the back mixing reduces the Bodenstein number (see below) and widens the molecular weight distribution, which gives undesired resin molecules according to the working theory of this invention. Thus, US3816376 has a great disadvantage in the process and the object of the invention is to provide a process that does not have at least one of the mentioned disadvantages of the prior art.
  • US3657188 claims a static mixing device only to mix the formaldehyde and the phenol stream, whereas the static mixer is no device to carry out the reaction for resin making; the solution is pumped through heat exchanger.
  • the first mixing can also be maintained by a batch mixer.
  • JP2005075939 mentions a manufacture approach of novolak, where the formaldehyde and phenol is mixed with a phosphoric acid solution in a continuous mixing device. Although there is no indication that this mixing device is used for the reaction, it is mentioned that both, mixing devices with mechanical moving parts and mixing devices without mechanical moving parts can be used. The latter type may include in-line mixers with 180 degree rotation, which have a reduced mixing performance as the in-line mixers mentioned in this invention. Additionally, the condensation reaction takes several hours, which is too long for such a producing method.
  • JP5986618 shows a semi-continuous approach, where acid, phenol and formaldehyde are premixed in a batch vessel and then continuously pumped through a column which is filled with mixing device of the type as they are known from distillation and rectification.
  • mixing device of the type as they are known from distillation and rectification.
  • JP20050075939 also in-line mixing devices with 180 degree rotation are described, which are not aim of this invention.
  • the disadvantage of this application is the insufficient mixing effect.
  • a mechanically mixed tube is introduced by WO03037955, whereas the reaction educts are added into a multistage stirring structure to be reacted; in the second step unreacted material is removed.
  • Multistage stirring mechanical devices are not comparable with the present invention.
  • US4413113 teaches a continuous feeding of phenol and paraformaldehyde, which is put into a mixing vessel by a conveyor screw. The mixing is discontinuous and the slurry is made up with water to a solution which is - after addition of catalyst - pumped into a liquid heated coil with circulation means.
  • GB1323301 shows a very similar approach, with the difference that all ingredients are added at the same time. These approaches are not comparable to the approach in this invention.
  • the process according to the invention can produce a hydroxy-aryl- formaldehyde solution in a continuous process without the need to use expensive equipment for processing highly viscous melts, like extruders as mentioned in WO9908856 or WO2004092239. Although it may be desired for certain applications to use an additional concentration step, the process according to the invention can provide a low solid containing liquid as well as a highly concentrated solution. Due to the well defined reaction time a well defined molecular weight distribution is obtained.
  • EP1785438 describes a continuous production for phenolic novolac resins which premixes the phenol, formaldehyde and acid catalyst and then the mixture is pumped through a tube reactor into the product vessel.
  • the tube reactor has - among other possibilities like reduction of diameter and thus flow speed enhancement or variations of the length of the heating zone - also the possibility to be equipped with in-line mixers.
  • the disadvantage of the system compared to the invention is the u-shaped tube, which support the occurrence of undesired wall effects and gel particles. Also this system is only suitable for Novolak, while the present invention can be used also for resoles.
  • a process for the continuous production of an aqueous hydroxy-aryl formaldehyde resin solution comprising the steps of a. preparing a reaction mixture of a hydroxy-aryl compound and an aqueous formaldehyde, b. adding a catalyst, c. reacting the reaction mixture in the presence of the catalyst, characterised in that, in step c) the reaction takes place in a continuous plug flow of the reaction mixture, followed by d. an optional step of adding an amount of amino compound after reaction, e. an optional step of removing water to reach a higher solid content.
  • the catalyst can be mixed into the reaction mixture in different ways known in the art.
  • the catalyst can be continuously added to a pre-mixture of the hydroxy-aryl compound and the aqueous formaldehyde or the catalyst can be added to the hydroxy-aryl compound followed by continuous addition of the aqueous formaldehyde.
  • the reaction mixture is prepared by mixing the hydroxy-aryl compound, preferably phenol, substituted hydroxy-aryl compounds, dihydroxy arenes, resorcinol, as a 63 - 100 wt% solution (wt % relative to the total solution weight) and the formaldehyde as a concentrated formaldehyde aqueous solution to a total solid content of 30 - 75 wt% (dry weight relative to the total weight of the reaction mixture), where after the catalyst is continuously added and finely dispersed into the reaction mixture through one or more, preferably multiple, addition points.
  • the hydroxy-aryl compound preferably phenol, substituted hydroxy-aryl compounds, dihydroxy arenes, resorcinol
  • the reaction mixture is prepared by pre-mixing the hydroxy-aryl compound, preferably a phenol, substituted hydroxy-aryl compounds, dihydroxyarenes, resorcinol, as a 63 - 100 wt. % solution (wt% relative to the total solution weight) with the catalyst, where after the formaldehyde is continuously added as a concentrated formaldehyde aqueous solution to a total solid content of 30 - 75 wt% (dry weight relative to the total weight of the reaction mixture) and finely dispersed into the reaction mixture through multiple addition points.
  • the hydroxy-aryl compound preferably a phenol, substituted hydroxy-aryl compounds, dihydroxyarenes, resorcinol
  • step c) the reaction takes place in the formed reaction mixture in a continuous plug flow of the reaction mixture, an optional step d) adding an amount of amino compound, preferably urea or melamine, or an aldehyde, e.g. furfural after and an optional step e) for removing water to reach a higher solid content.
  • amino compound preferably urea or melamine, or an aldehyde, e.g. furfural after and an optional step e) for removing water to reach a higher solid content.
  • the hydroxy-aryl compound is added as a concentrated aqueous solution, liquid or as a solid.
  • concentration preferably is as high as possible, preferably at least 63 wt%, more preferably at least 80 wt%, even more preferably at least 85 wt% or even at least 90 wt% and most preferably at least 95% of its saturation value.
  • the phenol will be dosed as a liquid and not as solution (MP Phenol about 4O 0 C)
  • aldehydes as a class, preferably those having from 1 to about 10 carbon atoms in aliphatic or cycloaliphatic or aromatic or mixed form, to produce the condensation-type resins useful in the invention.
  • aldehydes include, for example, formaldehyde, glyoxal, glutaraldehyde, acetaldehyde, propionaldehyde, crotonaldehyde, benzaldehyde, furfuraldehyde, and the like.
  • Formaldehyde is presently preferred.
  • the formaldehyde is added as a concentrated formaldehyde aqueous solution
  • concentration implies having a formaldehyde concentration of at least 40, preferably at least 45, more preferably at least 50 and most preferably at least 55 wt% in water (wt% relative to the total weight of the formaldehyde solution).
  • the total amount of hydroxy-aryl formaldehyde reactants in the reaction mixture is between 30 and 75 wt%, preferably between 45 and 70 wt%, more preferably between 50 and 65 wt% (dry solids weight relative to the total weight of the reaction mixture).
  • the relative amount of formaldehyde and hydroxy-aryl compounds may vary between broad ranges.
  • the molar ratio hydroxy-aryl compound to formaldehyde P/F can range between 0.1 and 10.0, preferably between 0.2 and 2.5, and most preferably between 0.33 and 1.6, for resoles preferably between 0.33 and 1 and for novolaks preferably between 1.0.and 1.6.
  • the process can be used where the reaction conditions are not so critical, for example for preparing hydroxy-aryl formaldehyde solutions paper impregnations usually having an P/F molar ratio below 2, for example between 1.2 and 1.8. However, the process according to the invention is designed for and is preferably used in more critical conditions.
  • the catalyst in the reaction can be a basic or an acid catalyst for all hydroxy-aryl formaldehyde resins. However, for Novolak resins an acid catalyst is preferred and for resole formaldehyde resin a basic catalyst is preferred. It is essential for the control of the reaction that in step b) the catalyst is continuously added and finely dispersed into the reaction mixture through one or more addition points. It is highly preferred to have multiple addition points to achieve a quick homogeneous dispersion of the catalyst. However, although less preferred, acceptable results can also be obtained using a single addition point in combination with appropriate mixing means, preferably a prepended static or dynamic mixing device, optionally in combination with a lower temperature. In many cases good results can be obtained by using undiluted acids like oxalic acid or undiluted bases like amines, sodium hydroxides are preferably used at concentrations of 50%. Preferred ways of adding the catalyst are described below.
  • a Novolak reaction mixture is preferably reacted in the reaction step in the presence of an acid catalyst, preferably a protic acid, preferably a strong acid such as Paratoluenesulfonic acid or oxalic acid.
  • an acid catalyst preferably a protic acid, preferably a strong acid such as Paratoluenesulfonic acid or oxalic acid.
  • a Resole reaction mixture is preferably reacted in a reaction step in the presence of a basic catalyst, for example sodium hydroxide or amines.
  • the reaction step c) takes place in a continuous plug flow of the reaction mixture.
  • the specified method of catalyst addition creates a very homogeneous reaction mixture which, under the continuous plug flow conditions with a well defined residence time, low backflow coefficient and narrow residence time distribution, can be reacted in a continuous process to a highly concentrated resin solution without substantial risk of a runaway reaction.
  • the continuous plug flow reaction conditions can be characterized by a Bodenstein number.
  • the Bodenstein number is a dimensionless characteristic number describing the relationship between the moles convectively supplied to the moles supplied by diffusion.
  • the length of the reactor is defined as the length between the start and the stop of the reaction, typically between point of the addition of the catalyst and of the addition of the catalyst stopper.
  • the Bodenstein number in the process according to the invention is at least 10, typically between 20 and 50. Preferably, the number is as high as possible, preferably at least 15, more preferably at least 20, even more preferably at least 30, more preferably at least 50.
  • the reaction mixture is continuously mixed during the reaction by in-line mixing elements in laminar or quasi-laminar plug flow.
  • the reaction mixture can be mixed by turbulent plug flow. It is known in the art how to determine the Bo number for a specified process. This involves calculating theoretical velocity distribution curves for different Bo numbers for a given reactor, then measuring the velocity profiles, normalizing and fitting of the determined profiles on the calculated theoretical profiles to find the Bodenstein number.
  • a reaction mixture is prepared (in step a) by reacting the formaldehyde with the hydroxy-aryl compound in the presence of an acid or a base catalyst to produce a solution of methylolated hydroxy-aryl compound in case of insulation resins or to react the educts to higher substituted polymers/oligomers.
  • the methylolation step is preferably done at a temperature chosen above a sedimentation temperature where sedimentation of the reactants may occur, at least 30, more preferably at least 40 and most preferably at least 50 0 C.
  • the temperature is chosen below the reaction temperature to avoid excessive polymerization, above 3O 0 C, and below 150°C, preferably for Resols between 5O 0 C and 100 0 C, and most preferably between 60 and 90 0 C and preferably for Novolaks between 70 0 C and 130°C, and most preferably between 80 and 110 0 C.
  • the pH in the methylolation step in case of Novolak is preferably adjusted between 1.0 and 14.0, in case of Novolak between 1.0 and 7.0 and in case of Resole between 7.0 and 14.0.
  • the pressure can rise above atmospheric pressures and the temperatures can be well above the boiling temperature of water, i.e. above 100 0 C.
  • the pressure during the condensation step is preferably above atmospheric pressure because the formaldehyde is more reactive at high temperature and high pressure conditions.
  • the pressure is preferably at least 1.1 , more preferably at least 1.5, even more preferably at least 2, even more preferably at least 3 and most preferably at least 5 bar.
  • the pressure is typically in a range between 1 and 20 bars, more preferably between 1 and 15 bars and most preferably between 1 and 10 bars.
  • a further advantage of the high temperature during the condensation reaction is that the viscosity of the product stream is low. At low viscosity the catalyst stopper can be mixed in more quickly and more homogeneously, so a sharper cut off of the condensation reaction can be obtained resulting in better product homogeneity, a smaller molecular weight distribution and lower risk of gelation.
  • the viscosity of the reaction mixture at the start of the reaction step is between 1 and 100 mPas.
  • the term viscosity implies viscosity determined according to DIN EN ISO 3219 at room temperature (20.0 +/- 0.2°C) and at a shear rate of 200/s.
  • the viscosity of a sample was measured according to DIN EN ISO 3219 with a rotary viscosimeter (PAAR PHYSICA MCR 51 ).
  • the system contains two static symmetric coaxial plates between which a bubble free liquid sample is applied of which viscosity has to be measured. One of the plates rotates with a defined angle velocity (rotor), while the other is static (stator). One plate is connected to a system which is able to measure the rotary moment at the point of overcoming the friction resistance of the plates with the liquid.
  • the shear rate is 200/s.
  • the reaction is exothermal the generated heat must be transported out of reaction mixture. This is preferably done by cooling the reactor, for example using a cooling liquid circulating in a double wall around the reactor tube.
  • a cooling liquid circulating in a double wall around the reactor tube.
  • the static mixing elements in the process according to the invention provide such efficient mixing and temperature homogeneity during the reaction.
  • the set- temperature during the reaction may be substantially isothermal because this provides an easier control of the reaction temperature conditions.
  • the reaction step may comprise two or more, preferably 2 to 10, preferably 2 to 6, more preferably 2 to 4 consecutive substantially isothermal sub-steps at different set temperatures.
  • the reaction is stopped by cooling of the reaction mixture and/or by adding and mixing an additional compound (e.g. urea) or a catalyst stopper (neutralisation).
  • the reaction mixture is cooled before, during and/or after said addition.
  • the reaction mixture directly obtained after the reaction step has a very high solids content of 40 to 75 wt.%, preferably 45 to 75 wt.%, more preferably 50 to 75 wt.% at most preferably 55 to 75 wt.% without an additional concentration step.
  • urea is the most preferred post addition compound in view of its highest reactivity.
  • Melamine can also be used, but is less reactive and less preferred.
  • hydroxy-functional aromatic compounds preferably phenol can be added and preferably reacted at temperatures above 100 0 C to achieve full conversion of the hydroxyfunctional aromatic compound, in reaction with the resin solution.
  • the amino compound in the post addition step d) can be added as a highly concentrated solution in water. However, it is preferred to add water as little as possible.
  • the additional amino compound, preferably urea is preferably added as plastified composition to avoid too much addition of water.
  • the plastification of the amino compound urea can take place by kneading the compound at elevated temperature where the compound is plastic, preferably close to the melting point, preferably in a single- or double screw extruder or a planet-extruder. The advantage thereof is that the decomposition of the compound is prevented. Optionally, a small amount of water is added to prevent too high temperatures and decomposition.
  • the addition is preferably done continuously from the fore mentioned plastification extruder, but may also be done by continuous addition from a batch.
  • the resin can further be extended by addition, preferably after step (d), of 1 to 15, preferably 1 - 12, more preferably 1 - 10 wt% (relative to the total weight of the resin solution) of extension components, preferably chosen from the group of rape seed flour, proteins, wheat flour. This is mostly done to reduce the cost of the resin solution.
  • plug flow conditions and intense mixing can also be achieved without mixing elements if the reaction takes place in a tube reactor with turbulent plug flow, most preferably at a Reynolds number above 2300 Good results may be achieved in thee process according to the invention Reynolds number above 1500, more preferably above 1700, even more preferably above 2000.
  • the Bodenstein number is at least 10, typically between 20 and 50.
  • the number is as high as possible, preferably at least 15, more preferably at least 20, even more preferably at least 30, more preferably at least 50.
  • the in-line mixing element can in principle be any object that changes the flow direction of the reaction mixture in the tube and causes mixing.
  • the in-line mixing elements can be glass beads, metal balls, spikes or baffles statically positioned inside the tube.
  • the static mixer device preferably consists of a number of consecutive static mixer elements positioned in the tube (in-line) comprising one or more baffles at an angle relative to the flow direction forcing changes in the flow direction.
  • the baffles in each subsequent mixer element have an orientation different from the orientation in the previous and/or following mixer element.
  • the orientation of the baffles in each consecutive mixer element is offset by 90°.
  • the baffles can be alternating spiral parts with each spiral part offset by 90°.
  • the mixing elements comprise two sets of two or more, preferably to 2 - 10, baffles wherein the baffles of each set are positioned essentially plan-parallel to each other, but at an angle, preferably 90°, with the baffles of the other set and wherein each baffle of one set is positioned alternately next to a baffle of the other set in a crosswise arrangement to divide the flowing reaction mixture into separate streams flowing in different directions within the mixer element, and wherein the baffles in each subsequent mixer element are offset at an angle, preferably 90°, relative to the previous mixer element.
  • Suitable static mixers are for example mikromakro ⁇ mixers from company Fluitec.
  • the static mixer preferably has a double wall for temperature control with a cooling fluid.
  • static mixers are used for mixing or blending and optionally reacting two or more fluid streams.
  • the reaction does not involve mixing of two or more fluid streams.
  • the static mixers are used for creating homogeneous reaction conditions throughout the reaction mixture to maintain a good heat transition to the tube walls and achieve homogenous temperature distribution to avoid local temperature rises due to the exothermic reaction.
  • the mixing elements maintain a high shear force avoiding wall effects whilst maintaining a plug flow at laminar flow conditions.
  • a catalyst is continuously added to the flowing reaction mixture and finely dispersed into the reaction mixture through one or more addition points.
  • the catalyst can be added in different ways, for example by one or more, preferably multiple separate supplies (for example tubes or hoses) each connected to the tube of the static mixer.
  • the catalyst is continuously added in a prepended continuous mixing device comprising a tube with mixing elements wherein the tube has one or more, preferably multiple addition points for finely dispersing the catalyst into the reaction mixture
  • the static mixing device of step b) more preferably is double walled comprising an inner tube and an outer casing wherein the inner tube comprises at least 4, preferably at least 6 static mixing elements which tube is perforated, preferably only at the position of the first or first two mixing elements, and wherein the outer casing provides a closed space over at least the perforated part of the inner tube and has an inlet opening for adding catalyst in said closed space to finely disperse droplets of the catalyst through the perforations into the inner tube.
  • the static mixing device can be one or more perforated tubes, which can be inserted into one or several static mixing elements, preferably into the center.
  • the number of addition points is preferably high, the diameter of the perforations is small and the perforations preferably are arranged substantially equidistant on the surface of the tube.
  • the tube comprises 4 - 40 perforations having a diameter between 0.1 and 1 mm, preferably between 0.1 and 0.5 mm.
  • the number of perforations and the diameter thereof are chosen in view of the amount of catalyst that needs to be added. Almost ideal mixing is achieved when the reaction mixture in the static mixer passes 8 mixing elements. However, acceptable mixing may also be achieved with 4 or 6 mixing elements.
  • the invention also relates more generally to the use of the above described static mixing device in a process for the continuous preparation of a resin solution, preferably a formaldehyde resin solution, most preferably a hydroxy-aryl compound resin solution described herein, for continuously dispersing a catalyst through said addition point(s) into a reaction mixture flowing through the tube.
  • a resin solution preferably a formaldehyde resin solution, most preferably a hydroxy-aryl compound resin solution described herein
  • the invention also relates to a continuous plug flow reactor and to the use thereof in a process for the preparation of hydroxy-aryl formaldehyde resins, comprising a static mixer comprising a thermostated, preferably double walled, tube having an inner diameter of between 2 and 10 cm, preferably between 2 and 7 cm, more preferably between 2 and 5 cm and comprising at least 20, preferably at least 40, more preferably at least 60 and most preferably at least 80 in-line mixing elements providing a high mixing efficiency, preferably characterised by a Bodenstein number of at least 20, preferably at least 40, more preferably at least 60 and most preferably at least 80.
  • the invention further relates to an hydroxy-aryl formaldehyde resin solution obtainable by the process according to the invention described above, having a viscosity for Resols between 5 and
  • the invention is illustrated with the drawing in Figure 1 describing a continuous plug flow reactor for the manufacture of a resin solution, comprising a catalyst addition section (1 ), a continuous plug flow reactor section (2) comprising four connected static mixers, a catalyst stopper inlet section (3), a catalyst stopper or additional compound mixing and cooling section (4) and a resin solution outlet section (5). All sections (1 ) to (5) are provided with static mixing elements and are connected to operate as one continuous tube reactor, wherein the reaction mixture is continuously makes from the beginning (6) to the end (7) of the reactor.
  • the catalyst addition section (1 ) comprises an outer tube (8) providing a closed space for feeding catalyst through the perforations (13) into the inner tube.
  • the continuous plug flow reactor section (2) in this example comprises four static mixers.
  • the static mixers are double walled for cooling and are provided with temperature and/or pressure measuring means (c) and control means (9) to monitor and control the temperature and/or pressure conditions.
  • the four static mixers are connected and controlled in a single cooling loop to keep substantial isothermal conditions over the full length of the reactor.
  • the catalyst stopper and additional compound inlet section (3) comprises a sample withdrawing means (12) for measurement, in particular of the pH and the viscosity and means (10) for addition of a catalyst stopper/additional compound.
  • a steady state operation mode is set by adjusting the amount of catalyst added (8) to get the desired viscosity of the resin solution at (12).
  • the catalyst stopper/additional compound is mixed into the reaction mixture in section (4) and cooled by cooling water (11).
  • the obtained end-product i.e. the product obtained directly condensation or, as the case may be, after post addition of additional amino compound, are characterised in that they have a very small Mw polydispersity ⁇ ⁇ Mn compared to conventional batch produced resin solutions (wherein Mw is the weight average molecular weight, and Mn is the number average molecular weight as determined by gel permeation chromatography (GPC)).
  • Mw is the weight average molecular weight
  • Mn is the number average molecular weight as determined by gel permeation chromatography (GPC)
  • GPC gel permeation chromatography
  • Q for that portion of the resin in the Mw range 900 and 3000 gr/mole is below 1.15, more preferably below 1.12, even more preferably below 1.10 and most preferably even below 1.08.
  • the PF resin solution according to the invention is advantageously used as binder resin in particle boards, for example wood fiber boards or as paper impregnation resin.
  • the invention therefore also relates to particle board comprising particles and a binder resin, or resin impregnated paper wherein the binder resin is the PF resin according to the invention.
  • the resin has distinct advantages in the manufacture and end-quality of the particle boards because of the molecular characteristics and high reactivity of the resin.
  • a further advantage of the present invention is that the particle board made with the PF resin solution according to the invention have, at comparable composition and production conditions, lower formaldehyde emission (measured by EN 120) compared to traditional batch prepared particle boards.
  • Formaldehyde Emissions typically are below 6, preferably below 5.5, more preferably below 5, even more preferably below 4.5 and most preferably below 4 mg / 100 g.
  • the particle board product comprising PF resin according to the invention cures faster compared to boards made by traditional batch resins.
  • the production time of a particle board according to the invention (expressed in sec/mm; time required to fully cure per mm thickness of the board) is preferably at least 5% lower, more preferably at least 10%, even more preferably at least 20% and most preferably at least 30% lower (based on production rate of 8 sec/mm and average board pressing temperature of 220 0 C in a particle board press).
  • a shorter press time also implies less energy consumption and higher production capacity.
  • the reactivity of the PF resin can be measured by determining the B-Time.
  • the hot plate of the B-time-oven After the hot plate of the B-time-oven is tempered to 13O 0 C, 420 ⁇ l of the sample (or 0,5g) will be placed in a hollow of the hot plate (the equipment is described in DIN 16916-02-C1 ). At the moment when the whole sample amount is placed on the plate a stop watch will be started. The sample will be stirred circularly from the rim to the centre with a glass rod. The diameter of the glass rod is 5mm, at the top 2mm. If the B-time is longer than three minutes the sample will be stirred continuously for one minute and then in intervals of one minute for 10 seconds. When the sample becomes viscous, the stirring should be done continuously The endpoint will be indicated by lifting the glass rod. When the sample should snap up rubber-like the end point is reached and the time measure is stopped.

Landscapes

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

Abstract

La présente invention concerne un procédé de production en continue d'une solution de résine aqueuse de formaldéhyde hydroxyaryle. Le procédé comprend : a. la préparation d'un mélange réactionnel d'un composé hydroxyaryle et d'un formaldéhyde aqueux, b. l'ajout d'un catalyseur, c. la réaction du mélange réactionnel en présence du catalyseur, d. une étape facultative d'ajout d'une quantité de composé aminé après réaction, e. une étape facultative d'élimination de l'eau afin de à une teneur en substances solides plus importante. À l'étape c, la réaction s'effectue dans un écoulement en piston continu du mélange réactionnel.
PCT/EP2010/058750 2009-06-22 2010-06-21 Procédé de production en continue d'une solution de résine aqueuse de formaldéhyde hydroxyaryle Ceased WO2010149632A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0910638.6 2009-06-22
GBGB0910638.6A GB0910638D0 (en) 2009-06-22 2009-06-22 Continuous phenolic resin making process

Publications (1)

Publication Number Publication Date
WO2010149632A1 true WO2010149632A1 (fr) 2010-12-29

Family

ID=40972474

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/058750 Ceased WO2010149632A1 (fr) 2009-06-22 2010-06-21 Procédé de production en continue d'une solution de résine aqueuse de formaldéhyde hydroxyaryle

Country Status (2)

Country Link
GB (1) GB0910638D0 (fr)
WO (1) WO2010149632A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180326393A1 (en) * 2015-11-11 2018-11-15 Fluitec Invest Ag Device for Carrying Out a Chemical Reaction by a Continuous Method
US10450400B1 (en) 2014-01-15 2019-10-22 Arclin Usa, Llc Extruded resorcinol-formaldehyde, phenol-formaldehyde and phenol-resorcinol-formaldehyde gel resins
CN110885651A (zh) * 2019-10-30 2020-03-17 福建雪龙竹木工贸有限公司 一种防腐型复合氨基树脂的制备方法

Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1660403A (en) 1924-02-20 1928-02-28 Bakelite Corp Process for the continuous preparation of phenolic resins
GB680245A (en) 1949-03-14 1952-10-01 Philips Nv Improvements in continuous processes for producing novolaks
GB783537A (en) 1953-09-01 1957-09-25 Allied Chem & Dye Corp Phenol-aldehyde resinification
GB1233785A (fr) * 1967-09-22 1971-05-26
US3657188A (en) 1970-03-02 1972-04-18 Butler Manufacturing Co Continuous production of resoles
GB1323301A (en) 1969-07-03 1973-07-11 Saint Gobain Continuous production of water-soluble phenol formaldehyde resins
US3816376A (en) 1971-03-02 1974-06-11 Basf Ag Continuous manufacture of amino resin solutions
DE2454675A1 (de) * 1974-11-19 1976-05-20 Dynamit Nobel Ag Verfahren zur gewinnung von novolak aus phenol- und formaldehyd-haltigem abwasser
JPS51130498A (en) * 1975-05-10 1976-11-12 Nissei Kagaku Kogyo Kk Process of manufacturing phenol formaldehyoeresin
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
US4413113A (en) 1981-04-03 1983-11-01 Formica Limited Continuous production of phenol-formaldehyde resin and laminates produced therefrom
JPS5986618A (ja) 1982-11-09 1984-05-18 Hitachi Chem Co Ltd フエノ−ル樹脂の製造方法
WO1999008856A1 (fr) 1997-08-18 1999-02-25 Basf Aktiengesellschaft Procede continu de production d'aminoplastes et/ou de phenoplastes
WO2003037955A1 (fr) 2001-11-02 2003-05-08 Nippon Petrochemicals Co., Ltd. Procede de production de resines phenolique et epoxyde
JP2003212945A (ja) * 2002-01-18 2003-07-30 Sumitomo Bakelite Co Ltd ノボラック型フェノール樹脂の製造方法
WO2004092239A1 (fr) 2003-04-16 2004-10-28 Ami Agrolinz Melamine International Gmbh Procede de synthese d'une resine liquide de melamine en continu
JP2005075939A (ja) 2003-09-01 2005-03-24 Sumitomo Bakelite Co Ltd ノボラック型フェノール樹脂の製造方法
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
WO2009065771A1 (fr) * 2007-11-22 2009-05-28 Dsm Ip Assets B.V. Procédé de fabrication d'une résine de condensation

Patent Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1660403A (en) 1924-02-20 1928-02-28 Bakelite Corp Process for the continuous preparation of phenolic resins
GB680245A (en) 1949-03-14 1952-10-01 Philips Nv Improvements in continuous processes for producing novolaks
GB783537A (en) 1953-09-01 1957-09-25 Allied Chem & Dye Corp Phenol-aldehyde resinification
GB1233785A (fr) * 1967-09-22 1971-05-26
GB1323301A (en) 1969-07-03 1973-07-11 Saint Gobain Continuous production of water-soluble phenol formaldehyde resins
US3657188A (en) 1970-03-02 1972-04-18 Butler Manufacturing Co Continuous production of resoles
US3816376A (en) 1971-03-02 1974-06-11 Basf Ag Continuous manufacture of amino resin solutions
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
DE2454675A1 (de) * 1974-11-19 1976-05-20 Dynamit Nobel Ag Verfahren zur gewinnung von novolak aus phenol- und formaldehyd-haltigem abwasser
JPS51130498A (en) * 1975-05-10 1976-11-12 Nissei Kagaku Kogyo Kk Process of manufacturing phenol formaldehyoeresin
US4413113A (en) 1981-04-03 1983-11-01 Formica Limited Continuous production of phenol-formaldehyde resin and laminates produced therefrom
JPS5986618A (ja) 1982-11-09 1984-05-18 Hitachi Chem Co Ltd フエノ−ル樹脂の製造方法
WO1999008856A1 (fr) 1997-08-18 1999-02-25 Basf Aktiengesellschaft Procede continu de production d'aminoplastes et/ou de phenoplastes
WO2003037955A1 (fr) 2001-11-02 2003-05-08 Nippon Petrochemicals Co., Ltd. Procede de production de resines phenolique et epoxyde
JP2003212945A (ja) * 2002-01-18 2003-07-30 Sumitomo Bakelite Co Ltd ノボラック型フェノール樹脂の製造方法
WO2004092239A1 (fr) 2003-04-16 2004-10-28 Ami Agrolinz Melamine International Gmbh Procede de synthese d'une resine liquide de melamine en continu
JP2005075939A (ja) 2003-09-01 2005-03-24 Sumitomo Bakelite Co Ltd ノボラック型フェノール樹脂の製造方法
EP1785438A1 (fr) 2004-08-19 2007-05-16 Asahi Organic Chemicals Industry Co., Ltd. Procede de fabrication de resine phenolique de type novolak
US20070112168A1 (en) * 2004-08-19 2007-05-17 Asahi Organic Chemicals Industry Co., Ltd. Process for producing phenolic novolak resin
WO2008128908A1 (fr) * 2007-04-20 2008-10-30 Dsm Ip Assets B.V. Processus de préparation d'une résine de condensation
WO2009065771A1 (fr) * 2007-11-22 2009-05-28 Dsm Ip Assets B.V. Procédé de fabrication d'une résine de condensation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10450400B1 (en) 2014-01-15 2019-10-22 Arclin Usa, Llc Extruded resorcinol-formaldehyde, phenol-formaldehyde and phenol-resorcinol-formaldehyde gel resins
US20180326393A1 (en) * 2015-11-11 2018-11-15 Fluitec Invest Ag Device for Carrying Out a Chemical Reaction by a Continuous Method
US10933398B2 (en) * 2015-11-11 2021-03-02 Fluitec Invest Ag Device for carrying out a chemical reaction by a continuous method
CN110885651A (zh) * 2019-10-30 2020-03-17 福建雪龙竹木工贸有限公司 一种防腐型复合氨基树脂的制备方法

Also Published As

Publication number Publication date
GB0910638D0 (en) 2009-08-05

Similar Documents

Publication Publication Date Title
EP2231735B1 (fr) Procédé de fabrication en continu de solutions aqueuses hautement efficaces de résine d'aminoformaldéhyde
US20090163694A1 (en) Process for the continuous production of high efficient aqueous amino formaldehyde resin solutions
JP3905559B2 (ja) 独特の組成を有するシアネートエステル樹脂の改良された製造方法
WO2010149632A1 (fr) Procédé de production en continue d'une solution de résine aqueuse de formaldéhyde hydroxyaryle
US20110014487A1 (en) Process for the continuous production of high efficient aqueous amino formaldehyde resin solutions
JPH0365826B2 (fr)
US4656239A (en) Process for the preparation of phenol formaldehyde resole resins
CN108440730A (zh) 一种铸造用高质量酚醛树脂的精制纯化方法
US5750597A (en) Thermosetting resin compositions
WO2009065771A1 (fr) Procédé de fabrication d'une résine de condensation
CN100519609C (zh) 生产酚醛清漆树脂的方法
US3558560A (en) Composition consisting of novolac resins and aromatic polycarboxylic compounds
JPS6241604B2 (fr)
JP5252130B2 (ja) ノボラック型フェノール樹脂の製造方法
US10450400B1 (en) Extruded resorcinol-formaldehyde, phenol-formaldehyde and phenol-resorcinol-formaldehyde gel resins
WO2008128908A1 (fr) Processus de préparation d'une résine de condensation
JP2003342443A (ja) ブレーキ用フェノール樹脂組成物およびその製造方法
CN119955041A (zh) 一种酚醛树脂的生产方法及生产装置
Pullichola et al. Synthesis of water soluble phenolic resins
JPH10204139A (ja) ノボラック型フェノール樹脂の製造方法
JPH0559256A (ja) 酸硬化剤組成物及び合成樹脂組成物
JP2004277624A (ja) ナフトール樹脂の製造方法
JPS6212933B2 (fr)
JPS6226666B2 (fr)
CN107262009A (zh) 一种新型反应器及其在生产聚芳醚中的应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10725765

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10725765

Country of ref document: EP

Kind code of ref document: A1