GB2158834A - Thermosetting moulding compounds on the basis of resole - Google Patents

Thermosetting moulding compounds on the basis of resole Download PDF

Info

Publication number
GB2158834A
GB2158834A GB08512177A GB8512177A GB2158834A GB 2158834 A GB2158834 A GB 2158834A GB 08512177 A GB08512177 A GB 08512177A GB 8512177 A GB8512177 A GB 8512177A GB 2158834 A GB2158834 A GB 2158834A
Authority
GB
United Kingdom
Prior art keywords
weight
parts
resole
thermosetting resin
filler
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.)
Granted
Application number
GB08512177A
Other versions
GB2158834B (en
GB8512177D0 (en
Inventor
Hans Pieter Braber
Arie Tinkelenberg
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.)
Covestro Resins BV
Original Assignee
DSM Resins BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DSM Resins BV filed Critical DSM Resins BV
Publication of GB8512177D0 publication Critical patent/GB8512177D0/en
Publication of GB2158834A publication Critical patent/GB2158834A/en
Application granted granted Critical
Publication of GB2158834B publication Critical patent/GB2158834B/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

Thermosetting resin composition on the basis of resole, filler and condensation catalysts possibly with thickener(s), glass fibre and other usual additives. At least a portion of the filler is a water-binding agent which does not become essentially water-binding until above a temperature of 50 DEG C. The thermosetting resin compositions are preferably used as moulding compounds, such as, in particular 'Bulk moulding compounds' (BMC), 'Dough moulding compounds' (DMC) or 'Sheet moulding compounds' (SMC). The water-binding agent is suitably gypsum anhydrite.

Description

SPECIFICATION Thermosetting moulding compounds on the basis of resole The invention relates to thermosetting resin compositions, in particular moulding compounds, on the basis of resole, filler and condensation catalysts, possibly with thickener(s), glass fiber and other usual additives.
Such resin compositions are known from, for example, US Patent Specification No.
4,075,1 55. However, these known resin compositions give rise to problems during thermosetting on account of the water present in the resole.
In a process for moulding phenolic resin, glass fibre and acid catalysts jointly sprayed into a mould, the Belgian Patent Specification No. 847449 proposes the simultaneous use of a hydrophylic inorganic material, such as CaSO4 hemihydrate or B203. However, this idea is of no use for ready-for-use moulding compounds as meant in the present application, since a waterwithdrawing agent would affect the viscosity stability of the compound itself.
The object of the invention is to provide a thermosetting composition on the basis of resoles which does not have the above-mentioned disadvantages and is therefore suitable for use as a moulding compound.
To this end, according to the invention, in a thermosetting composition on the basis of resole, filler and condensation catalysts and possibly thicknener(s), glass fibre and other usual additives at least a portion of the filler is a water-binding agent which does not become essentially (i.e.
substantially) water-binding until above a temperature of 50"C.
According to the invention, such thermosetting compositions are preferably used as moulding compounds, such as, in particularl, 'Bulk Moulding Compounds' (BMC), 'Dough Moulding Compounds' (DMC) or 'Sheet Moulding Compounds' (SMC).
Such processing techniques have been described in, for example, the lectures read during the '1 3e Offentliche Jahrestagung der Arbeitsgemeinschaft Verstärkte Kungststoffen', October 5-7, 1976.
The thermosetting resin compositions according to the invention preferably contain at least 25 per cent by weight, relative to the resole, of the water-binding agent which is not essentially water-binding until above 50"C.
A very suitable water-binding agent to be used according to the invention is gypsum anhydrite (CaSO4. 0 H2O). According to the invention, gypsum anhydrite is preferably used in a ratio of at least 50 per cent by weight relative to the resole.
Additives in moulding compounds according to the invention include, for example, further fillers such as marl, powdered quartz, Millicarb (filler of the firm Pliiss Staufer AG), talc etc.; thickeners such as MgO, epoxy resins etc.; mould release agents such as calcium stearate, ACT OPS (mould release agent of the firm of Tietjen s Co) and further usual additives. As condensation catalyst, alkalimetal hydroxides and/or carbonates can very suitably be used.
For moulding compounds according to the invention for application according to the sheet moulding technique the following component ratios are preferably applied: 100 parts by weight of resole; 5-25 parts by weight of thickener; 25-200 parts by weight of gypsum anhydrite; 0-150 parts by weight of filler other than gypsum anhydrite; 0-20 parts by weight of water; 10-175 parts by weight of glass fibers; 0-15 parts by weight of condensation catalyst; and, possibly, other usual additives.
For compositions according to the invention for application according to the bulk moulding technique or the dough moulding technique, the following component ratios are preferably applied: 100 parts by weight of resole; 0-20 parts by weight of thickener; 25-200 parts by weight of gypsum anhydrite; 0-150 parts by weight of filler other than gypsum anhydrite; 0-15 parts by weight of water; 0-25 parts by weight of glass fibres; 0-15 parts by weight of condensation catalyst; and, possibly, further usual additives.
The invention is explained in more detail by the following examples but is not restricted thereto.
Preparation of resoles.
Example 1 5980 grams of 90% (phenol (the rest being water) are introduced into a reactor provided with a stirrer, a thermometer, a condensor and a heating and cooling coil. After addition of 201 grams of 50% NaOH the mixture is heated.
At about 80'C, dosage of 3819 grams of paraform is started. The temperature quickly rises on account of the exothermic reaction that occurs, and is kept at 95% by cooling. During cooling, paraform dosage is interrupted.
After about 20 minutes all paraform has been added and the reaction is continued for 1 5 minutes at 95"C. To the resin 200 grams of caprolactam are added, after which the condensation is continued until the desired resin viscosity has been reached (8000 m.Pa.s). The resin is cooled to room temperature. A Resole I is obtained, which is used in moulding compounds according to the examples below.
Example 2 2990 grams of 90% phenol and 1 00.5 grams of 50% NaOH are introduced into a reactor like the one in Example 1. 1909.5 grams of paraform are dosed in the same manner as in Example 1. After paraform dosage, the condensation is continued at 95"C, the reaction proceeding as follows: period for which condensation viscosity water-compatibility is continued 20 minutes 1170 mPa.s 5.2 30 minutes 2062 mPa.s 3.1 40 minutes 3375 mPa.s 1.9 50 minutes 6150 mPa.s 1.2 number of grams of water needed to cause permanent turbidity in 1 gram of resin solution at 20"C.
Next, the temperature of the resin is lowered to 80"C, after which condensation is continued until the resin has reached a viscosity of 10,000 mPa.s. A resole II is obtained, which is used in moulding compounds according to the examples below.
Preparation of sheet moulding compounds Example 3 2100 grams of phenolic resin (Resole I of Example 1), 210 grams of MgO (as thickener), 2100 grams of gypsum anhydrite (product AB 20 of the firm of Bayer), 600 grams of marl (as additional filler), 114 grams of water, 96 grams of calcium stearate (as mould release agent), 50 grams of 50% NaOH solution and 210 grams of 50% K2CO3 solution, are mixed to a homogeneous compound in a mixer.
The compounds is still more or less liquid; comparable with a cement mortar.
On an SMC machine a thin layer of compound is spread with a doctor blade on a proceeding polyethylene film. Subsequently, using a cutting device glass roving (30% (wt) glass fibre calculated on the weight of the compound) is strewn on it, after which a second layer of compound, also applied to a polyethylene film, is applied on top. The resulting 'sandwich' of compound glass fibre and compound is further compacted with a number of pressure rolls and a pressure belt so that the glass fibres are moistened by the resin. At the end of the machine sheet-still packed in the polyethylene films-is rolled up.
After the thickening of the compound the polyethylene films can be pulled from the SMC. At this moment a non-sticky flexible sheet (plate) has been obtained.
Parts of this sheet are piled up and put in a hot mould in which they first flow out under heat and pressure until the mould is completely filled and subsequently cure to form the desired product. Moulding conditions are at 160"C; pressure 100 kg/cm2, moulding period 3 minutes.
The resulting objects are of good quality and show a smooth surface.
Example 4 2000 g of phenolic resin (resole II of Example 2), 2600 g of gypsum anhydrite (product AB of the firm of Bayer), 1100 g of Microdol (talc), 300 g of Eurepox (epoxy resin of the firm of Schering), 75 g of Euredur (setting agent of the firm of Schering), 1 30 g of calcium stearate, 50 g of water and 2680 g of glass fibres are mixed as in Example 3 and processed to flexible sheeting.
Moulding of this sheet moulding compound under the same conditions as in Example 3 yields of objects with a good quality and surface.
Example 5 2000 g of phenolic resin (resole I of Example 1), 335 g of Eurepox (epoxy resin of the firm of Schering), 85 g of Euredur (setting agent from Schering), 1100 g of gypsum anhydrite, 1100 g of Millicarb (filler of the firm of Plüss Staufer AG), 85 g of calcium stearate, 20 g of water and 1 925 g of glass fibres are mixed as in Example 3 and processed to flexible sheet.
Moulding of this sheet moulding compound under the same conditions as in Example 3 yields objects with a good quality and surface.
Example 6 Preparation of bulk moulding compounds.
1100 9 of phenolic resin (resole II of Example 2), 1230 g of gypsum anhydrite (product AB 20 of the firm of Bayer), 325 g of powdered quartz, 60 g of glass fibres with a length of ca.
2.5 cm, 35 g of calcium stearate, 220 g of 50% K2CO3 solution, 70 g of 50% NaOH solution and 35 g of MgO (thickener) are mixed as in Example 3. The compound obtained can be moulded according to the bulk moulding technique with good results.
Example 7 Preparation of dough moulding compounds.
1000 g of phenolic resin (resole II of Example 2), 1 320 g of gypsum anhydrite (product AB 20 of the firm of Bayer), 555 g powdered quartz, 30 g of calcium stearate, 65 g of 50% NaOH solution and 55 g of glass fibres with a length of ca. 2.5 cm are mixed as in Example 3. The compound obtained can be moulded to objects according to the dough moulding technique with good results.

Claims (10)

1. Thermosetting resin composition on the basis of resole, filler and condensation catalysts, possibly with thickener(s), glass fibre and other usual additives, characterized in that at least a portion of the filler is a water-binding agent which does not become substantially water-binding until above a temperature of 50"C.
2. Thermosetting resin composition according to Claim 1, characterized in that it is in the form of a moulding compound.
3. Thermosetting resin composition according to Claim 2, characterized in that it is in the form of a BMC (bulk moulding compound), a DMC (dough moulding compound) or an SMC (sheet moulding compound).
4. Thermosetting resin composition according to any one of the Claims 1-3, characterized in that it contains at least 25 wt %. relative to the resole, of a filler that does not become essentially waterbinding until above 50on.
5. Thermosetting resin composition according to any one of the Claims 1-4, characterized in that at least a portion of the filler is gypsum anhydrite.
6. Thermosetting resin composition according to Claim 5, characterized in that it comprises at least 50 wt %, relative to the resole, of gypsum anhydrite.
7. Thermosetting resin composition according to any one of the Claims 1-6, for application as a sheet moulding compound, characterized in that it is composed of 100 parts by weight of resole; 5-25 parts by weight of thickener; 25-200 parts by weight of gypsum anhydrite; 0-150 parts by weight of filler other than gypsum anhydrite; 0-20 parts by weight of water; 10-175 parts by weight of glass fibres; 0-15 parts by weight of condensation catalyst; and, possibly, other usual additives.
8. Thermosetting resin composition according to any one of the Claims 1 through 6, for application as bulk or dough moulding compound, characterized in that it is composed of 100 parts by weight of resole; 0-20 parts by weight of thickener; 25-200 parts by weight of gypsum anhydrite; 0-150 parts by weight of filler other than gypsum anhydrite; 0-15 parts by weight of water; 0-25 parts by weight of glass fibres; 0-15 parts by weight of condensation catalyst; and, possibly, other usual additives.
9. Moulded object from thermosetting material obtained by the setting, under pressure, of a thermosetting composition according to any one of the Claims 1-8.
10. Process substantially as described and/or explained by the examples.
GB08512177A 1984-05-16 1985-05-14 Thermosetting moulding compounds on the basis of resole Expired GB2158834B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL8401570A NL8401570A (en) 1984-05-16 1984-05-16 THERMO-CURING PRESS COMPOUNDS BASED ON PHENOLIC RESOL RESIN.

Publications (3)

Publication Number Publication Date
GB8512177D0 GB8512177D0 (en) 1985-06-19
GB2158834A true GB2158834A (en) 1985-11-20
GB2158834B GB2158834B (en) 1987-05-28

Family

ID=19843960

Family Applications (1)

Application Number Title Priority Date Filing Date
GB08512177A Expired GB2158834B (en) 1984-05-16 1985-05-14 Thermosetting moulding compounds on the basis of resole

Country Status (8)

Country Link
BE (1) BE902426A (en)
DE (1) DE3516004A1 (en)
ES (1) ES8703502A1 (en)
FR (1) FR2564473B1 (en)
GB (1) GB2158834B (en)
IT (1) IT1181652B (en)
NL (1) NL8401570A (en)
PT (1) PT80462B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1167428A1 (en) * 2000-06-30 2002-01-02 Dainippon Ink And Chemicals, Inc. Resol-type phenol resin composition and method for curing the same

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1037368A (en) * 1965-06-16 1966-07-27 Timesaver Products Company Process for the production of non-foamed, urethane-type polymers
GB1522995A (en) * 1974-11-18 1978-08-31 Owens Corning Fiberglass Corp Moulding compound
GB1548959A (en) * 1975-11-12 1979-07-18 Comptoir Plastiques Method of manufacturing reinforced phenol resin aricles and products thus abtained
GB2038348A (en) * 1978-12-12 1980-07-23 Desai Polymer Dev Phenolic materials

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1419648A (en) * 1972-06-09 1975-12-31 Exxon Research Engineering Co Manufacture of phenolic foam boards
DE2262484A1 (en) * 1972-12-20 1974-06-27 Siemens Ag Moulding of electrical components - from material with high filler content contg. material with strong adsorption in gases and steam
FR2331587A1 (en) * 1975-11-12 1977-06-10 Comptoir Plastiques Glass reinforced phenolic resin mouldings prodn. - by spraying resin, catalyst, glass fibres and anhydrous inorganic cpd. onto mould
US4075155A (en) * 1976-01-08 1978-02-21 Owens-Corning Fiberglas Corporation Molding compounds
FR2414403A1 (en) * 1978-01-16 1979-08-10 Stratiforme PANEL BASED ON PHENOLIC RESIN AND ITS MANUFACTURING PROCESS
US4235762A (en) * 1979-01-23 1980-11-25 The Dow Chemical Company Stabilized phenolic resins

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1037368A (en) * 1965-06-16 1966-07-27 Timesaver Products Company Process for the production of non-foamed, urethane-type polymers
GB1522995A (en) * 1974-11-18 1978-08-31 Owens Corning Fiberglass Corp Moulding compound
GB1548959A (en) * 1975-11-12 1979-07-18 Comptoir Plastiques Method of manufacturing reinforced phenol resin aricles and products thus abtained
GB2038348A (en) * 1978-12-12 1980-07-23 Desai Polymer Dev Phenolic materials

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1167428A1 (en) * 2000-06-30 2002-01-02 Dainippon Ink And Chemicals, Inc. Resol-type phenol resin composition and method for curing the same
US7041724B2 (en) 2000-06-30 2006-05-09 Dainippon Ink And Chemicals, Inc. Resol-type phenol resin composition and method for curing the same
KR100783685B1 (en) * 2000-06-30 2007-12-07 다이니혼 잉키 가가쿠 고교 가부시키가이샤 Resol-type phenol resin composition and process for curing the same

Also Published As

Publication number Publication date
ES543122A0 (en) 1987-02-16
NL8401570A (en) 1985-12-16
IT1181652B (en) 1987-09-30
GB2158834B (en) 1987-05-28
DE3516004A1 (en) 1985-11-21
BE902426A (en) 1985-11-14
FR2564473A1 (en) 1985-11-22
IT8548040A0 (en) 1985-05-03
FR2564473B1 (en) 1989-01-20
PT80462A (en) 1985-06-01
GB8512177D0 (en) 1985-06-19
PT80462B (en) 1986-12-12
ES8703502A1 (en) 1987-02-16

Similar Documents

Publication Publication Date Title
CA2321994A1 (en) Process for preparing polyarylethers
US6133403A (en) Reactive diluents for acid curable phenolic compositions
US4075155A (en) Molding compounds
US3839251A (en) Phenolic resin and process for making same
US2966473A (en) Molding composition containing urea formaldehyde resin, gypsum, and glass fiber
GB2158834A (en) Thermosetting moulding compounds on the basis of resole
EP0466754B1 (en) Insulating product of mineral fibre wool, intended in particular for heat insulation of pipes, and method for making this product
EP0343433B1 (en) Phenolic moulding compositions
EP0447232B1 (en) Composition and method for forming a tile body
EP0180257A1 (en) Thermosetting resin composition based on resole resin
US4105623A (en) Method of making molding compounds and materials made thereby
EP0869980B1 (en) Reactive diluents for acid curable phenolic compositions
US4210562A (en) Cellulose-containing phenolic resin-based binder
US3903041A (en) Composition board and process
US2683133A (en) Acetone formaldehyde resin
JPH0158144B2 (en)
US1771033A (en) Furfural resin composition and process of making same
US5308642A (en) Process for the production of stiffening materials containing hydraulic binders, in particular plaster bandages
US2861977A (en) Preparation of intercondensation product of monohydric phenol-furfural resin and formaldehyde, and utilization thereof in the production of plywood
EP0122894A1 (en) Process for preparing polyurethanes with the use of a polyhydroxyalkylphosphine oxide as curative
US5352509A (en) Insulating product of mineral fibre wool, intended in particular for heat insulation of pipes and method for preparing this product
US4070331A (en) Method of making molding compounds and products produced thereby
SU747862A1 (en) Composition for producing porous plastic material
US5162403A (en) Phenolic resin preforms and method of manufacturing them
US2652373A (en) Composition of matter with plastic bonding and method of making from cresol-formaldehyde, comminuted wood, and sodium silicate

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee