FR2564473A1 - COMPOSITIONS FOR RESOLUTION-BASED THERMOFORMING MOLDING AND MOLDED OBJECTS BASED THEREON - Google Patents

Abstract

COMPOSITION OF THERMOSETTING RESIN BASED ON RESOLE, CHARGE AND CONDENSATION CATALYSTS, AND POSSIBLY ONE (OR MORE) THICKENING AGENT (S), FIBERGLASS AND OTHER USUAL ADDITIVES. AT LEAST PART OF THE LOAD IS A HYDROPHILIC AGENT WHICH BECOMES ESSENTIALLY HYDROPHILIC ONLY AT A TEMPERATURE OVER 50C. THE COMPOSITIONS OF THERMOSETTING RESINS ARE PREFERREDLY USED IN THE FORM OF MOLDING COMPOUNDS SUCH AS, IN PARTICULAR, COMPOUNDS FOR BULK MOLDING (BMC), BALL (DOUGH MOULDING COMPOUND - DMC), OR IN BALL (DOUGH MOULDING COMPOUND - DMC), OR SHEET MOLDING COMPOUND - SMC).

Description

The present invention relates to composi-

  thermosetting resins, especially charge-based molding compounds and condensation catalysts, and optionally one or more thickeners), fiberglass and

other usual additives.

  Such resin compositions are known from, for example, what is described in

  U.S. Patent No. 4,075,155. nevertheless

  least, these known resin compositions create

  problems during thernodurcage due to the presence of water

feels in the resole.

  In a process for molding phenolic resin

  since fiberglass and acidic catalysts are

  vaporized together in a mold, in the descriptions

  of Belgian Patent No. 847449, the simultaneous use of a hydrophilic mineral material such as hemihydrate CaSO4 or B203. However, this idea is of no use for the ready-to-use molding compounds according to the present invention since a drying agent would modify the stability of the viscosity.

of the compound itself.

  The object of the present invention is to provide a thenmccurable composition based on resoles which do not have the disadvantages set out above and which

  are therefore usable as molding compounds.

  For this purpose, according to the invention, in a thermosetting composition based on resole, filler and condensation catalysts, and optionally one or more thickening agent (s), of glass fiber, and of other usual additives, at least a part of the

  charge being a hydrophilic agent which does not become essen-

  only hydrophilic at a temperature of 50 C.

  According to the invention, the thermosetting compositions

  "hardenable" are preferably used in the form of

  Bulk Molding Compounds -

  BMC), Dough Molding Compounds (DMC), and sheet molding compounds

(Sheet Molding Compounds - SMC).

  Such manufacturing techniques have been described for example in the communications made on the occasion of the "13th Offentliche Jahrestgung der Arbeitgemeinschaft Verstarkte Kunstoffen" from 5 to 7

October 1976.

  Thermosetting resin compositions

  sand, according to the invention, preferably contain at least 25% by weight, relative to the resole, of hydrophilic agent which does not become essentially hydrophilic

  at a temperature above 50 C.

  According to the invention, as a hydrophilic agent

  very suitable, anhydrous gypsum (CaSO 4, 0 H 2 O) is used.

  According to the invention, anhydrous gypsum will be used in proportions of at least 50% by weight relative to the resole. The additives in the molding compounds according to the invention comprise, for example, other fillers such as marl, quartz powder, Millicarb (load of the company Pliss Staufer AG), talc, etc .; thickeners such as MgO, epoxy resins, etc .; lubricating agents such as calcium stearate, ACMOS (internal lubricating agent from Tiejen & Co) and

other usual additives.

  Hydroxydes and / or

alkali metal carbonates.

  In the molding compounds according to the invention,

  For an application according to sheet molding techniques, the following proportions will preferably be applied: parts by weight of resole, 5-25 parts by weight of thickener, -200 parts by weight of anhydrous gypsum, 0-150 parts by weight of mass of binder other than anhydrous gypsum, 0-20 parts by weight of water, 10-175 parts by weight of fiberglass, 015 parts by weight of condensation catalyst, and

possibly other additives.

  In the resin compositions according to

  for an application according to the techniques of

  In bulk or in ball form, the following proportions will preferably be applied: parts by weight of resole, 0-20 parts by weight of thickener, -200 parts by weight of anhydrous gypsum, 0-150 parts by weight of binder other than anhydrous gypsum, 0-15 parts by weight of water, 025 parts by weight of fiberglass, 0-15 parts by weight of condensation catalyst,

  and possibly other additives.

  Other features and benefits of the

  The present invention will become apparent in the following examples:

solvents.

PREPARATION OF RESOLES

EXAMPLE 1

  5980 g of 90% phenol (the remainder being water) are introduced into a reactor equipped with an agitator, a thermometer, a condenser and a heating and cooling coil. The mixture is heated after adding 201 g of 50% NaOH. At about 80 C, we start

  the addition of 3819 g of paraformaldehyde. The temperature

  erage rises rapidly because of the exotic reaction

  thermal intervention; it is maintained at 95 ° C. by cooling. During cooling, the addition

  metformaldehyde is discontinued.

  After about 20 minutes, all the

  formaldehyde was added and the reaction was continued for 15 minutes at 95 ° C. Caprolactam was added to the resin (200 g) and condensation continued until the desired viscosity of the resin had been reached (8000 m. Not). The resin is cooled to room temperature. We obtain a resole I, which we will use

  in the molding compounds hereinafter.

EXAMPLE 2

  2990 g of 90% phenol and 5 g of 50% NaOH are introduced into a reactor similar to that described in Example 1. To the same amount as in Example 1, 1909.5 g will be added. paraformaldehyde,

  condensation is continued at 95 ° C. and the reaction

  continued as follows: Periods during which Viscosity Compatibility Continuous condensation in water * minutes 1170 m Pa.s 5.2 minutes 2062 m Pa.s 3.1 40 minutes 3375 m Pa.s 1.9 minutes 6150 m Pa.s 1 , 2 * Number of grams of water needed to cause a disorder

  standing in one gram of 20 C resin solution.

  Then, the temperature of the resin is lowered to 80 C, after which the condensation is

  continued until the resin reached a screw

cosity of 10000 m Pa.s.

  We obtain a resole II which will be used

  in the molding compounds according to the examples

after.

PREPARATION OF COMPOUNDS

SHEET MOLDING (SMC)

EXAMPLE 3

  2100 g of phenolic resin (Resole I of Example 1), 201 g of MgO (as thickener) 2100 g of anhydrous gypsum (product AB 20 from Bayer), 600 g of marl (as additional charge), 114 g of water, 96 g of calcium stearate (as internal lubricant), 50 g of 50% NaOH solution and 210 g of 50% K2CO3 solution are mixed into a compound.

homogeneous in a mixer.

  The compound is still more or less liquid

  and comparable to a cement mortar.

  On a SMC (Sheet Molding Compound) machine, a thin layer of compound is spread with a scalpel, on a polyethylene film that unfolds. Then, using a cutting device, wicks (roving) of glass, (30% by weight of fiberglass (calculated

  on the mass of the compound) are dispersed over.

  After that, a second layer of compound, also applied to a polyethylene film, which is applied on top. The "sandwich" of glass fiber compounds and resulting compound is then agglomerated by a number of rollers and pressure belts so that the glass fibers are impregnated with the resin. At the end of the machine, the slip, still wrapped in

  polyethylene films, is put in rolls.

  After the thickening of the compound, the polyethylene films can be removed from the sheet molding compound (SMC). At that moment, we got a

  sheet (or plate) flexible and non-adherent.

  Pieces of this sheet are stacked and placed in a hot mold in which they begin to flow under the effect of heat and pressure until the mold is completely filled and then cook to form the desired product. The molding conditions are: 160 C; pressure: kg / cm2; molding time: 3 minutes. The resulting objects are of good quality and show a

regular surface.

EXAMPLE 4

  2000 g of phenolic resin (Resole II of Example 2), 2600 g of anhydrous gypsum (product AB 20 from Bayer), 1100 g of Microdol (talc), 300 g of Eurepox (epoxy resin from Schering) 75 g of Euredur (curing agent from Schering), g of calcium stearate, 50 g of water and 2680 g of glass fibers are mixed as in Example 3 and then put into the form of flexible sheets. . Molding

  of this sheet-molding compound, under the same conditions

  tions than in Example 3 produces good objects

quality and good surface.

EXAMPLE 5

  2000 g of phenolic resin (Resole I of Example 1), 335 g of Europox (epoxy resin from Schering), 85 g of Euredur (curing agent from Schering), 1100 g of anhydrous gypsum, 1100 g of Millicarb (charge from PlUss Staufer AG), 85 g of calcium stearate, 20 g of water and 1925 g of glass fibers are mixed as in Example 3 and put into the form of

flexible sheet.

  Molding this sheet molding compound under the same conditions as in Example 3 gives

  objects of good quality and good surface.

EXAMPLE 6

  PREPARATION OF MASS GROWING COMPOUNDS (BMC)

  1100 g of phenolic resin (Resole II of Example 2, 1230 g of anhydrous gypsum (product AB 20 from Bayer), 325 g of quartz powder, 60 g of glass fiber with a length of ca. 5 cm, 35 g of calcium stearate, 220 g of 50% K 2 CO 3 solution, 70 g of 50% NaOH solution and 35 g of MgO (thickener) are mixed as in Example 3. The compound obtained can be molded according to the technique of mass molding and the results are good.

EXAMPLE 7

  PREPARATION OF BALLOLET MOLDING COMPOUNDS (DMC)

  1000 g of phenolic resin (Resole II of Example 2), 1320 g of anhydrite (product AB 20 from Bayer), 555 g of quartz powder, 30 g of calcium stearate, 65 g of NaOH solution at 50% and 55 g of fiberglass with a length of ca. 2.5 cm are mixed as in Example 3. The compound obtained can be molded into objects according to the molding technique

  in ball and the results are good.

Claims (7)

  1 - Composition of thermosetting resin, based on resole, filler and condensation catalysts, optionally one or more thickening agent (s), fiberglass and other usual additives, characterized by the at least a portion of the filler is a hydrophilic agent which becomes essentially hydrophilic only temperature above 50 C.   2 - thermosetting resin composition according to claim 1, characterized in that it   is in the form of a molding compound.   3 - thermosetting resin composition according to claim 2, characterized in that it is in the form of a compound for molding in bulk (Bulk Molding Compound), ball (Dough Molding Compound), or sheet (Sheet Molding Compound) ). 4 - Thermosetting resin composition,   according to one of claims 1 to 3, characterized   in that it contains at least 25% by weight, relative to the resole, of hydrophilic agent which is essentially hydrophilic only at a temperature greater than 50 C.   - Thermosetting resin composition,   according to one of claims 1 to 4, characterized   in that at least part of the load is anhydrous gypsum.   6 - thermosetting resin composition according to claim 5, characterized in that it comprises at least 50% by weight, relatively at the resole, anhydrous gypsum.   7 - Thermosetting resin composition,   according to one of claims 1 to 6, for an application   according to the sheet molding technique,   in that it consists of: parts by weight of resole -25 parts by weight of thickener 25-200 parts by mass of anhydrous gypsum 0-150 parts by mass of filler other than anhydrous gypsum 0-20 parts in mass of water -175 parts by weight of fiberglass   0-15 parts by weight of condensation catalyst   and possibly other additives.   8 - Thermosetting resin composition,   according to one of claims 1 to 6, for a   application according to the techniques of bulk molding or ball molding, characterized in that it consists of: parts by weight of resole 0-20 parts by weight of thickener -200 parts by mass of anhydrous gypsum 0150 parts by weight of filler other than anhydrous gypsum 0-15 parts by weight of water 0-25 parts by mass of fiberglass   0-15 parts by weight of condensation catalyst   tion, and possibly other heat additives formable.   9 - Molded object made from thermosetting materials obtained by hardening under pressure of compositions   thmicDcurable, according to one of claims 1 to 8.