CA2132796A1 - Process for the continuous preparation of flowable, foamable and curable phenolresol resin mixtures - Google Patents
Process for the continuous preparation of flowable, foamable and curable phenolresol resin mixturesInfo
- Publication number
- CA2132796A1 CA2132796A1 CA002132796A CA2132796A CA2132796A1 CA 2132796 A1 CA2132796 A1 CA 2132796A1 CA 002132796 A CA002132796 A CA 002132796A CA 2132796 A CA2132796 A CA 2132796A CA 2132796 A1 CA2132796 A1 CA 2132796A1
- Authority
- CA
- Canada
- Prior art keywords
- foamable
- twin
- curable
- resin mixtures
- 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.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 title claims abstract description 19
- 239000011347 resin Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000008569 process Effects 0.000 title claims abstract description 14
- 230000009969 flowable effect Effects 0.000 title abstract description 4
- 238000002360 preparation method Methods 0.000 title description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000007493 shaping process Methods 0.000 claims abstract description 3
- 238000010924 continuous production Methods 0.000 claims description 2
- 238000005187 foaming Methods 0.000 abstract description 4
- 239000006260 foam Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000306 component Substances 0.000 description 10
- 229920003987 resole Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- CVLHGLWXLDOELD-UHFFFAOYSA-N 4-(Propan-2-yl)benzenesulfonic acid Chemical compound CC(C)C1=CC=C(S(O)(=O)=O)C=C1 CVLHGLWXLDOELD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- IULJSGIJJZZUMF-UHFFFAOYSA-N 2-hydroxybenzenesulfonic acid Chemical compound OC1=CC=CC=C1S(O)(=O)=O IULJSGIJJZZUMF-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000002844 continuous effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002937 thermal insulation foam Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2061/00—Use of condensation polymers of aldehydes or ketones or derivatives thereof, as moulding material
- B29K2061/04—Phenoplasts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2301/00—Use of unspecified macromolecular compounds as reinforcement
- B29K2301/10—Thermosetting resins
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Molding Of Porous Articles (AREA)
- Moulding By Coating Moulds (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
Abstract A process for the production of shaped articles from curable and foamable phenolresol resin mixtures is disclosed.
According to the process, components of the resin are mixed using a twin-screw extruder, the exit of which is preferably constructed as a slot die. Shaping of the foamed body during foaming and curing is preferably carried out on a twin-belt press. Resin mixtures prepared according to the process of the invention are homogenous and readily flowable. The process is simple, continuous and free of many disadvantages of known processes serving the same purpose.
According to the process, components of the resin are mixed using a twin-screw extruder, the exit of which is preferably constructed as a slot die. Shaping of the foamed body during foaming and curing is preferably carried out on a twin-belt press. Resin mixtures prepared according to the process of the invention are homogenous and readily flowable. The process is simple, continuous and free of many disadvantages of known processes serving the same purpose.
Description
. 2132796 H~LS ARTIEWG~SELLSCHAFT
- PATENTABTEILUWG - - 1 - O.Z. 4788 Process for the continuous preparation of flowable, - foamable and curable phenolresol re8in mlxture~
.
The invention relates to the preparation of curable ~nd foamable phenolresol resin mixtures by means of a twin-screw extruder.
The processing of phenolres~l resins to insulation foam~
is known. In general, the following components are mixed with one another in this procedure:
Basic components:
Phenolresol : -Polycondensation product of phanol - and formaldehyde using alkaline catalysts. Viscosity range: 2000 to 120,000 mPa.s (20C).
Cell regulators : Surface-active compound for estab-lishing a certain closed-cell struc-ture.
Blowing agent : Low-boiling hydrocarbons, H-FCHC, H-FHC or compounds which split off gas under the action of acids.
Curing agent : Inorganic or organic acids and mix-tures thereof or solid acids or acid anhydrides.
Additives:
Fillers : Pulverulent or fibrous substances, for example barium sulphate or glass fibres.
Modifying agents : Fireproofing agents in solid or liquid form, plasticizers, coloured pigments for coloration, accelera~
tors.
Foamable phenolresol resin mixtures cannot be preparedcontinuously or can be prepared continuously only if particular mea~ures are taken and at be~t if solid components such as filllers, modifying agents or solid curing agents are absent.
.` ` 213279~
- PATENTABTEILUWG - - 1 - O.Z. 4788 Process for the continuous preparation of flowable, - foamable and curable phenolresol re8in mlxture~
.
The invention relates to the preparation of curable ~nd foamable phenolresol resin mixtures by means of a twin-screw extruder.
The processing of phenolres~l resins to insulation foam~
is known. In general, the following components are mixed with one another in this procedure:
Basic components:
Phenolresol : -Polycondensation product of phanol - and formaldehyde using alkaline catalysts. Viscosity range: 2000 to 120,000 mPa.s (20C).
Cell regulators : Surface-active compound for estab-lishing a certain closed-cell struc-ture.
Blowing agent : Low-boiling hydrocarbons, H-FCHC, H-FHC or compounds which split off gas under the action of acids.
Curing agent : Inorganic or organic acids and mix-tures thereof or solid acids or acid anhydrides.
Additives:
Fillers : Pulverulent or fibrous substances, for example barium sulphate or glass fibres.
Modifying agents : Fireproofing agents in solid or liquid form, plasticizers, coloured pigments for coloration, accelera~
tors.
Foamable phenolresol resin mixtures cannot be preparedcontinuously or can be prepared continuously only if particular mea~ures are taken and at be~t if solid components such as filllers, modifying agents or solid curing agents are absent.
.` ` 213279~
- 2 - O.Z. 4788 The components are homogenized continuously by mean~ of a permanently installedl high-speed mixing element (for - example turbine stirrer, 800 to 1500 rpm) in mixing chambers with a flooded mixing ~pace (tank3 of given volume). The components are conveyed into the mixing chamber via metering pump8 with relatively low pre3sures, and mixing is in prin~iple carried out under normal pressure. In the case of phenolre ol resin foams, there is the disadvantage that heat is introduced into the system by the high-speed mixing and leads to an increase in temperature of the emerging, foamable mixture, so that in the extreme case, evaporation of the blowing agent and thus preliminary foaming already occurs before entry into the belt channel and destroys the structure of the foam.
This effect can be counteracted only in the short term by cooling the raw material components and the metering and mixing units.
~ : .
High-pressure mixing chambers are suitable for the preparation of polyurethane foams. Their mixing action is based on the fact that the components are fed under high pressures via ~ets into a small mixing chamber (volume of ~;
2 to 10 cm3), a homogeneous foamable and curable mixture emerging from the chamber. However, the use of such high-pressure mixers has not proved suitable for the continuous preparation of foamable resol resin mixtures because of high losses of blowing agent and a non-uniform pore structure of the resol foams.
If the foam mix~ure comprises ~olid substances, however, both mixing systems are unsuitable. There are two ways of mixing a solid into a liquid system:
use of a premixer for preparation of a homogeneous resin/
solid mixture, feeding to the end mixer, where the remaining liquid components are metered in, or making of a paste of the solid compc)nents with liquid compounds and in this way conveying of the substances via metering pumps into mixing apparatuses with downstr~am mould units. In addition to this additional working operation, ,~. .
. .
This effect can be counteracted only in the short term by cooling the raw material components and the metering and mixing units.
~ : .
High-pressure mixing chambers are suitable for the preparation of polyurethane foams. Their mixing action is based on the fact that the components are fed under high pressures via ~ets into a small mixing chamber (volume of ~;
2 to 10 cm3), a homogeneous foamable and curable mixture emerging from the chamber. However, the use of such high-pressure mixers has not proved suitable for the continuous preparation of foamable resol resin mixtures because of high losses of blowing agent and a non-uniform pore structure of the resol foams.
If the foam mix~ure comprises ~olid substances, however, both mixing systems are unsuitable. There are two ways of mixing a solid into a liquid system:
use of a premixer for preparation of a homogeneous resin/
solid mixture, feeding to the end mixer, where the remaining liquid components are metered in, or making of a paste of the solid compc)nents with liquid compounds and in this way conveying of the substances via metering pumps into mixing apparatuses with downstr~am mould units. In addition to this additional working operation, ,~. .
. .
- 3 - O.Z. 4788 the process is limited to those cases where the solids do not react with the agent with which the paste i8 formed.
It is thus the ob~ect of the invention to develop a pro-cess which is capable of preparing a foamable and curable mixture continuou~ly without the disad~antages de~cribed above.
The invention relates to a process for the continuous production of shaped articles from foamable and curable resol resin mixtures, characterized in that mixing of the resin batch is carried out with a twin-screw extruder.
Resin mixtures prepared in thi~ way are surprisingly of a homogeneous consistency and readily flowable.
The exit of the twin-screw extruder can be constructed as a slot die, which can be heated if appropriate. Shaping of the foamed body during foaming and curing i8 prefer-ably carried out on a twin-belt press.
It has been found that the continuous preparation of a homogeneous foamable and curable mixture from the com-ponents described above, although it was not possible to perform this hitherto, can be carried out by means of a twin-screw extruder.
The following advantages arise~
Both mixtures for the preparation of closed-cell foams -comprising no fillers - and those for the preparation of open-cell foams - comprising fillers - can be produced on the same machine without an additional working operation.
The filler content can be up to 300 ~ by weight, based on resin. It i9 not possible to prepare a foamable mixture which comprises this high filler content by means of the conventional mixing techniques because of the viscosities of above 150,000 mPa.s (20C) which then arise.
200 to 400 revolutions of the extruder scxews per minute are sufficient to procesE low-viscosity substances, such as blowing agents, with high-viscosity substances, such as resin and solids, to give a homogeneous mixture in one ~'~ .r~
~; ~ ` ' A
i - 4 - 2344~-528 operation.
No bubbles containing air, which could ha~e an ~dverso effect on the cell structure of the foams, are stirred in by the low-~peed mixing at 200 to 400 rpm.
No noticeable introduction of heat with the consequence of premature foaming is ob~erved.
The twin-screw extruder is self-cleaning, so that the use of solvents, such as alcohols or acetone, for cleaning purposes is unnecessary.
Examples The following components listed in Table 1 were fed continuously via pumps to a twin-screw extruder (Continuo*
model from Werner & Pfleiderer) for the preparation of -flowable, foamable and curable phenolresol resin mixtures. The emerging mixture was introduced into a con~
tinuously operating twin-belt press which had the follow-ing data:
s~
Length of the twin-belt press : 20 m Distance between the upper and lower belt : 50 mm 0 Width of the twin belt : 1.2 m Temperature of the twin-belt press : 50 to 60C
The mixture was foamed and cured between the lower and upper belt of the sheet press. The fresh density of the foamed resol sheets emerging from the belt press was determined. The other properties listed were determined after conditioning of the sheets.
The resol foams in Example 1 are a foam having a closed-cell structure of more than 90% and good insulating properties, and in Examples 2 and 3 they are low combustibility foams with the classification B-l or A-2 according to DIN 4102.
* Trade-mark . ~;
_ 5 _ 23~43-.5~8 In the table, the term~ have the following meaning~:
DYNAPOR Re~ol 1153 * Vi~co~ity 3500 mPa/~ (20C~
DYNAPOR Resol 9700/8314 ~ Visco~ity 9000 mPa~s (20C) DYNAPOR*curing agent 7153 Novolak + phenolsulphonic acid + H2SO4 -DYNAPOR*curing agent 7156 Cumenesulphonic acid/toluenesul-phonic acid/H2SO4 60/14/8/H20 DYNAPOR*curing agent VW 420 Cumenesulphonic acid + poly-glycol.
10 ~ Foamed re~in ~. ~
~ ` ' * Trade-mark ~ ;
' ' ~::
~; . 6 2344~-528 Table 1 . ._ ... .
¦ Example No: 1 2 3 :
¦ 1. Foamable reaction ¦ rn twe :
~ ..
J ¦ 1.1 DYNAPOR Resol 1153kglminute . 7.7 3.8 ~:~
DYNAPOR Resol 970018314kg/minute 7.7 1.2 Pentane kg/minute 0.08 0.07 0.04 -~
1.3 Soud kglminute l Boric acid 1.54 10 ¦ Aluminium hydroxide 3.8 I
1.4 Curing agent DYNAPOR*7153 kglminute 0.9 ::
Curing agent DYNAPOR 7156 0.9 Curing aBenl DYNAPOR VW 420 1.1 :
. _ 2. Technical data ~ t :i~ :~
2.1 Resin temperature C 17 17 17 _ :: ~ :2.2 Mixture lemperature C 18 19 19 aher emergence ~ :-2.3 Belt speed m/minute 2.5 4 2 .~: ~-.:
3- PF foam properti~s .. ::
2 0 3.1 Structure fine-pore fine-pore fine-pore . .............. ..
3.2 Production density kg/m' 53 92 3.3 Closed-cell structure ~o 92 20 5 .. _ :.
3.4 Thermal conductivityW/r~lC 0.021 0.03 0.033 - :~:::
.
3.5 Burning properties according Class B2 B1 A2 to DIN 4102/1 * Trade-mark -
It is thus the ob~ect of the invention to develop a pro-cess which is capable of preparing a foamable and curable mixture continuou~ly without the disad~antages de~cribed above.
The invention relates to a process for the continuous production of shaped articles from foamable and curable resol resin mixtures, characterized in that mixing of the resin batch is carried out with a twin-screw extruder.
Resin mixtures prepared in thi~ way are surprisingly of a homogeneous consistency and readily flowable.
The exit of the twin-screw extruder can be constructed as a slot die, which can be heated if appropriate. Shaping of the foamed body during foaming and curing i8 prefer-ably carried out on a twin-belt press.
It has been found that the continuous preparation of a homogeneous foamable and curable mixture from the com-ponents described above, although it was not possible to perform this hitherto, can be carried out by means of a twin-screw extruder.
The following advantages arise~
Both mixtures for the preparation of closed-cell foams -comprising no fillers - and those for the preparation of open-cell foams - comprising fillers - can be produced on the same machine without an additional working operation.
The filler content can be up to 300 ~ by weight, based on resin. It i9 not possible to prepare a foamable mixture which comprises this high filler content by means of the conventional mixing techniques because of the viscosities of above 150,000 mPa.s (20C) which then arise.
200 to 400 revolutions of the extruder scxews per minute are sufficient to procesE low-viscosity substances, such as blowing agents, with high-viscosity substances, such as resin and solids, to give a homogeneous mixture in one ~'~ .r~
~; ~ ` ' A
i - 4 - 2344~-528 operation.
No bubbles containing air, which could ha~e an ~dverso effect on the cell structure of the foams, are stirred in by the low-~peed mixing at 200 to 400 rpm.
No noticeable introduction of heat with the consequence of premature foaming is ob~erved.
The twin-screw extruder is self-cleaning, so that the use of solvents, such as alcohols or acetone, for cleaning purposes is unnecessary.
Examples The following components listed in Table 1 were fed continuously via pumps to a twin-screw extruder (Continuo*
model from Werner & Pfleiderer) for the preparation of -flowable, foamable and curable phenolresol resin mixtures. The emerging mixture was introduced into a con~
tinuously operating twin-belt press which had the follow-ing data:
s~
Length of the twin-belt press : 20 m Distance between the upper and lower belt : 50 mm 0 Width of the twin belt : 1.2 m Temperature of the twin-belt press : 50 to 60C
The mixture was foamed and cured between the lower and upper belt of the sheet press. The fresh density of the foamed resol sheets emerging from the belt press was determined. The other properties listed were determined after conditioning of the sheets.
The resol foams in Example 1 are a foam having a closed-cell structure of more than 90% and good insulating properties, and in Examples 2 and 3 they are low combustibility foams with the classification B-l or A-2 according to DIN 4102.
* Trade-mark . ~;
_ 5 _ 23~43-.5~8 In the table, the term~ have the following meaning~:
DYNAPOR Re~ol 1153 * Vi~co~ity 3500 mPa/~ (20C~
DYNAPOR Resol 9700/8314 ~ Visco~ity 9000 mPa~s (20C) DYNAPOR*curing agent 7153 Novolak + phenolsulphonic acid + H2SO4 -DYNAPOR*curing agent 7156 Cumenesulphonic acid/toluenesul-phonic acid/H2SO4 60/14/8/H20 DYNAPOR*curing agent VW 420 Cumenesulphonic acid + poly-glycol.
10 ~ Foamed re~in ~. ~
~ ` ' * Trade-mark ~ ;
' ' ~::
~; . 6 2344~-528 Table 1 . ._ ... .
¦ Example No: 1 2 3 :
¦ 1. Foamable reaction ¦ rn twe :
~ ..
J ¦ 1.1 DYNAPOR Resol 1153kglminute . 7.7 3.8 ~:~
DYNAPOR Resol 970018314kg/minute 7.7 1.2 Pentane kg/minute 0.08 0.07 0.04 -~
1.3 Soud kglminute l Boric acid 1.54 10 ¦ Aluminium hydroxide 3.8 I
1.4 Curing agent DYNAPOR*7153 kglminute 0.9 ::
Curing agent DYNAPOR 7156 0.9 Curing aBenl DYNAPOR VW 420 1.1 :
. _ 2. Technical data ~ t :i~ :~
2.1 Resin temperature C 17 17 17 _ :: ~ :2.2 Mixture lemperature C 18 19 19 aher emergence ~ :-2.3 Belt speed m/minute 2.5 4 2 .~: ~-.:
3- PF foam properti~s .. ::
2 0 3.1 Structure fine-pore fine-pore fine-pore . .............. ..
3.2 Production density kg/m' 53 92 3.3 Closed-cell structure ~o 92 20 5 .. _ :.
3.4 Thermal conductivityW/r~lC 0.021 0.03 0.033 - :~:::
.
3.5 Burning properties according Class B2 B1 A2 to DIN 4102/1 * Trade-mark -
Claims (3)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A continuous process for the production of shaped articles from curable and foamable phenolresol resin mixtures, which process comprises the step of mixing components of the resin using a twin-screw extruder.
2. A process according to claim 1, which process further comprises the step of shaping of the articles in a twin-belt press.
3. A process according to claim 1, wherein the exit of the twin-screw extruder is constructed as a slot die.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4332698A DE4332698A1 (en) | 1993-09-25 | 1993-09-25 | Process for the continuous production of flowable, foamable and curable phenolic resole resin mixtures |
| DEP4332698.6 | 1993-09-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2132796A1 true CA2132796A1 (en) | 1995-03-26 |
Family
ID=6498628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002132796A Abandoned CA2132796A1 (en) | 1993-09-25 | 1994-09-23 | Process for the continuous preparation of flowable, foamable and curable phenolresol resin mixtures |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0645229B1 (en) |
| JP (1) | JP3842306B2 (en) |
| KR (1) | KR100322320B1 (en) |
| CA (1) | CA2132796A1 (en) |
| DE (2) | DE4332698A1 (en) |
| ES (1) | ES2109571T3 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0108167A1 (en) * | 1982-11-01 | 1984-05-16 | ISOMO, naamloze vennotschap | Process for the continuous manufacture of phenolic foam layers and installation applying said process |
| GB8404860D0 (en) * | 1984-02-24 | 1984-03-28 | Bp Chem Int Ltd | Preparation of phenolic foam |
| JP2500277B2 (en) * | 1990-11-27 | 1996-05-29 | 三井東圧化学株式会社 | Extrusion molding method and apparatus for phenol resin pipe |
-
1993
- 1993-09-25 DE DE4332698A patent/DE4332698A1/en not_active Withdrawn
-
1994
- 1994-08-27 ES ES94113417T patent/ES2109571T3/en not_active Expired - Lifetime
- 1994-08-27 EP EP94113417A patent/EP0645229B1/en not_active Expired - Lifetime
- 1994-08-27 DE DE59404571T patent/DE59404571D1/en not_active Expired - Fee Related
- 1994-09-21 JP JP22690994A patent/JP3842306B2/en not_active Expired - Fee Related
- 1994-09-23 CA CA002132796A patent/CA2132796A1/en not_active Abandoned
- 1994-09-24 KR KR1019940024046A patent/KR100322320B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE4332698A1 (en) | 1995-03-30 |
| EP0645229A1 (en) | 1995-03-29 |
| KR950008588A (en) | 1995-04-19 |
| JPH07148820A (en) | 1995-06-13 |
| KR100322320B1 (en) | 2002-05-13 |
| ES2109571T3 (en) | 1998-01-16 |
| JP3842306B2 (en) | 2006-11-08 |
| DE59404571D1 (en) | 1997-12-18 |
| EP0645229B1 (en) | 1997-11-12 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |