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WO1999010293A1 - Produits lies et procedes de leur fabrication - Google Patents

Produits lies et procedes de leur fabrication Download PDF

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Publication number
WO1999010293A1
WO1999010293A1 PCT/GB1998/002474 GB9802474W WO9910293A1 WO 1999010293 A1 WO1999010293 A1 WO 1999010293A1 GB 9802474 W GB9802474 W GB 9802474W WO 9910293 A1 WO9910293 A1 WO 9910293A1
Authority
WO
WIPO (PCT)
Prior art keywords
cnsl
acid
weight
mixture
slate
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/GB1998/002474
Other languages
English (en)
Inventor
Dennis Jones
Jeremy Tomkinson
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.)
Bangor University
Original Assignee
Bangor University
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
Priority claimed from GBGB9717685.3A external-priority patent/GB9717685D0/en
Priority claimed from GBGB9717687.9A external-priority patent/GB9717687D0/en
Application filed by Bangor University filed Critical Bangor University
Priority to AU88691/98A priority Critical patent/AU8869198A/en
Publication of WO1999010293A1 publication Critical patent/WO1999010293A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02—Macromolecular compounds
    • C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • This invention relates to bonded products and processes for their manufacture.
  • the invention relates more particularly to bonded products (or composites) formed by compacting particulate material in the presence of a bonding agent based on cashew nut shell liquid (CNSL), and to processes of forming such composites using a reaction product of CNSL as a bonding agent.
  • CNSL cashew nut shell liquid
  • Typical composites formed by compacting particles in the presence of a bonding agent include such products as chemically resistant bricks, grinding wheels, slate composites, coal briquettes, and products made by compressing wood particles.
  • CNSL is extracted from the mesocarp of the cashew nut obtained from the cashew nut tree, Anacardium Occidentale Linn.
  • the extraction process includes a heating process which results in the chemical modification of one of the major components of the liquid.
  • the material obtained consists of a mixture of components containing a phenolic hydroxyl group and an unsaturated side chain.
  • CNSL thus produced is sometimes referred to as technical CNSL and can vary in composition as a result of many factors e.g. its country of origin. Brazil and India are the main producers.
  • UK-A-481960 (Harvel Corporation) describes the treatment of raw CNSL to thicken or give body thereto. This is done by polymerising raw CNSL with about 15 to 65 of its volume of concentrated sulphuric acid, e.g 100 parts by weight of raw CNSL and a solution of 5.4 parts of concentrated sulphuric acid in about 15 parts of water are emulsified and heated to about 300°F to 375°F for 30 to 45 minutes to produce a body which may vary in appearance from very heavy cold molasses to a ropy sticky mass. Longer reaction times of 8 to 15 hours are used to obtain material with rubberlike properties suitable for compounding with rubber.
  • concentrated sulphuric acid e.g 100 parts by weight of raw CNSL and a solution of 5.4 parts of concentrated sulphuric acid in about 15 parts of water are emulsified and heated to about 300°F to 375°F for 30 to 45 minutes to produce a body which may vary in appearance from very heavy cold molasses to a
  • US-A-2067919 in the name of the same applicants, states that the lower limit using sulphuric acid is one part by volume to 100 parts by volume of CNSL, and the upper limit is about 6 parts by volume of sulphuric acid to 100 parts by volume of CNSL.
  • UK-A-259959 discloses the treatment of raw CNSL to reduce the iodine number of the oil. This is done by oxidising the oil under acid conditions, e.g one example is given of reacting one part of raw CNSL with one part nitric acid and one part water.
  • oxidising agent such as manganese dioxide
  • the products are said to be gums which can be dissolved in solvents such as naptha, to make a coating which dries quickly.
  • U -A-536800 (Harvel Research Corporation) describes the conversion of CNSL to a dry hard and infusible state for use in frictional elements such as clutch facings. This material is produced by reacting paraformaldehyde or hexamethylene tetramine with polymerised CNSL.
  • the CNSL may be polymerised using sulphuric acid by the method described in UK-A-481960.
  • UK-A-742286 British Resin Products is directed to an improved method of polymerising CNSL by using a phenolic sulphonic acid devoid of ethylenic unsaturation, by which is meant a phenolic compound containing a sulphonic acid group attached to the aromatic nucleus which does not contain any ethlenically unsaturated hydrocarbon groups attached thereto. It is acknowledged that it has previously been proposed to polymerise CNSL by the action of heat using, as a polymerisation catalyst, either a strong mineral acid or hydrochloric acid, or an alkyl ester such as diethyl sulphate.
  • US-A-2754283 discloses the use of sulphonic acids to polymerise CNSL.
  • CNSL is mixed with the sulphonic acid so as to form a solution which is then heated until the viscosity has increased at least four-fold.
  • the product from this heating step can then be further reacted with an aldehyde so as to convert it into a substantially infusible resin.
  • aldehyde so as to convert it into a substantially infusible resin.
  • a dry moulding composition comprising a solid CNSL resin polymer, a chemically resistant filler, and an aldehyde or aldehyde yielding substance is disclosed in UK-A-664169 (British Resin Products).
  • the filler is carbon or graphite which may be mixed with one or more of silica flour, quartz, barytes, fused alumina, asbestos, brick dust, pumice, bentonite, kaolin and titanium dioxide. This method requires the prior reaction of CNSL to a polymerised form.
  • a process for forming a bonded product in which the particles to be bonded are mixed with CNSL and an acid to form a uniform mixture, and the mixture is then compacted under pressure in a mould.
  • a process for forming a bonded product in which the particles to be bonded are mixed with CNSL, water and an acid to form a uniform mixture, and the mixture is then compacted under pressure in a mould.
  • the method of the invention may be used to produce bonded products comprising 70 to 98%, preferably 80 to 98%, even more preferably 90 to 98% by weight of the bonded particulate material.
  • Particles which can be used to form the bonded products of the invention include those derived from carbonaceous materials such as coal or coke, mineral materials such as slate, and synthetic and natural materials used as abrasives.
  • the invention is also applicable to the manufacture of pressed products from wood particles.
  • CNSL reaction with an acid is related to the pKa value of the acid and to the concentration of double bonds relative to a fully saturated side chain.
  • CNSL can contain up to three double bonds in the side chain. It is believed these double bonds react with acids to generate reactive carbocationic intermediates which in turn react with further double bonds in adjacent molecules, further increasing the production of carbocatioiis. This propagation spreads quickly through the matrix giving a resilient cross linked polymer which acts as a bonding agent.
  • any acid may be used which achieves a satisfactory bonding.
  • acids with a pKa in the range +3 to -9 and of acids in this range we prefer to use sulphuric acid at a concentration of about 98% although any concentration can be used which causes the CNSL to polymerise with a exothermic reaction.
  • Other acids that can be used include other mineral acids e.g. phosphoric acid, with a pKa of +2, and organic crystalline acids, e.g. p-toluene sulphonic acid, with a pKa of -6.
  • organic crystalline acid such as p-toluene sulphonic acid, which can be added as a solid so that the acid only becomes effective under particular operating parameters.
  • the amount of acid (expressed as the acid as such) is preferably at least 0.2 parts by weight per part by weight of CNSL. Good results will be obtained with higher acid to CNSL ratios.
  • the amount of water present in the process of the invention does not exceed 30% by weight and is more preferably in the range 0% to 10% by weight.
  • the ratio of acid to CNSL, by weight is not less than 0.5 to 1 , preferably a ratio of acid to CNSL of 1 to 1; good results will be obtained up to a ratio of acid to CNSL of 2.5 to 1 by weight.
  • the water content of the whole mix, if present should be kept at less than 10%, as we find that as the water content increases above 10%, it is necessary to increase the quantity of acid present to compensate for the dilution of the acid. It will be seen that the quantity of acid used in forming composites to cause the CNSL to polymerise, is very much greater than that used in the prior art for the production of CNSL polymers using acids in so called catalytic amounts.
  • a compound having an active methylene group such as formaldehyde or a formaldehyde yielding substance
  • a compound having an active methylene group such as formaldehyde or a formaldehyde yielding substance
  • the addition of such materials is also believed to assist in avoiding any problems arising from variation in the composition of the technical CNSL from source to source.
  • the amount of the compound having an active methylene group is 5 to 40%, more preferably 15 to 20%, by weight of the CNSL.
  • formaldehyde or a formaldehyde yielding substance, such as paraformaldehyde or hexamethylenetetramine.
  • formaldehyde or a formaldehyde yielding substance, such as paraformaldehyde or hexamethylenetetramine.
  • sulphuric acid 97% concentration
  • formaldehyde is not added so as to form the primary bonds of the polymerised matrix, but so as to provide additional extra cross linking bonding, which assists in stabilising the matrix.
  • the quantity of bonding agent (polymerised CNSL) in the final product, and hence the amount of CNSL added relative to the total content of any particular product, is related to the void volume available between the particles when compaction has taken place, and also to the need to ensure adequate bonding.
  • bonding agent polymerised CNSL
  • stearates such as calcium stearate, give good release from the mould with the products of the present invention.
  • Satisfactory pressures for compacting the products of the invention fall in the range 500 to 1200 psi, and we have found for most products we can operate at a pressure of 1000 psi.
  • the reaction of CNSL with, for example, sulphuric acid is exothermic, and pressing at pressures of the order of a 1000 psi produces a strong composite within seconds.
  • acids other than sulphuric acid we prefer to operate at elevated temperatures.
  • the particulate material to be bonded may be coal and as such the invention may be applied to the production of coal briquettes.
  • Such briquettes as produced in accordance with the invention are of satisfactory strength, appearance and good burning characteristics.
  • Coal used for forming briquettes will usually have a particle size ranging from 0.01 mm to 15 mm. A typical distribution is:
  • the particle size distribution of the slate will vary according to the source but a typical distribution is:
  • the invention also includes composites formed by compacting particles together in the presence of a binder, in which the binder is a reaction product of CNSL with an acid, the reaction product being formed in situ during the production of the composite, and composites in which a compound with an active methylene group such as formaldehyde is present during the formation of the binder.
  • a binder in which the binder is a reaction product of CNSL with an acid, the reaction product being formed in situ during the production of the composite, and composites in which a compound with an active methylene group such as formaldehyde is present during the formation of the binder.
  • the invention also includes slate composites which have been prepared by compacting slate particles selected from slate grains and slate powder, or mixtures thereof, in the presence of a binder which is a reaction product of CNSL and an acid, the reaction product being formed in situ during the production of the composite.
  • the invention also includes slate composites which have been prepared by compacting slate particles selected from the group consisting of slate grains and slate powder, or mixtures thereof, and a binder precursor mixture at elevated temperature, the binder precursor mixture containing CNSL, an organic crystalline acid, a material containing an active methylene group, and water.
  • Our invention also includes a bonded wood particle board which has been prepared by pressing a mixture of particulate wood and a binder precursor mixture at an elevated temperature, the binder precursor mixture containing CNSL, an organic crystalline acid, a material containing an active methylene group and water.
  • the material containing an active methylene group can be formaldehyde, and when formaldehyde is used it is preferably added as hexamethylene tetramine.
  • aromatic sulphonic acids are organic crystalline acids which remain substantially undissolved for a period of days in CNSL, until the temperature is raised to greater than 120°C.
  • a readily available aromatic sulphonic acid which has been found satisfactory for manufacturing both wood and slate composites is p-toluene sulphonic acid.
  • test briquettes were made on a laboratory scale in a Kenwood Major Batch Blender and the pressing carried out in a single daylight press with a single ram. None of the test briquettes produced from mixtures with the compositions given in Table 1 failed a drop test .
  • the drop test is a drop of 1.5 metres onto a brick flooring surface, and the briquettes fail if they fall apart on impact. Testing is carried out within one minute of the briquette being removed from the press. It was found that if the quantity of CNSL fell below 5 parts there was an increased risk of the test briquette disintegrating despite attempts to modify the formulation and pressing conditions.
  • the slate was used as slate powder or slate granules, or a mixture thereof.
  • the acid in all cases was 97.5% sulphuric acid.
  • Formaldehyde may be added as paraformaldehyde, and the stearate release agent is calcium stearate.
  • a slate tile was made by compressing, for ten minutes at 180 degrees centigrade, a mixture containing ;
  • the binder mixture was made by placing 133.2 g of technical CNSL in a vessel, to which was added 26.6 g of p-toluene sulphonic acid, followed by 13.6 g of paraformaldehyde and then 27 g of water. The materials were thoroughly mixed without any heating or vigorous stirring, but so as to ensure the components were thoroughly mixed together. Once mixing was completed the binder mixture was mixed with the slate dust and grain in a Z-blade mixer, and sufficient mix transferred to the press to form a tile. The tile had a satisfactory strength properties and a good surface appearance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)

Abstract

La présente invention a trait aux produits liés et aux procédés de leur fabrication, et plus particulièrement aux produits liés ou composites formés par le compactage d'une substance particulaire en présence d'un agent liant fabriqué in situ, produit réactif à base d'huile de cajou. L'invention concerne également les procédés de formage de ce type de composites en utilisant un produit réactif à base d'huile de cajou comme agent de liaison.
PCT/GB1998/002474 1997-08-22 1998-08-24 Produits lies et procedes de leur fabrication Ceased WO1999010293A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU88691/98A AU8869198A (en) 1997-08-22 1998-08-24 Bonded products and processes for their manufacture

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB9717685.3 1997-08-22
GB9717687.9 1997-08-22
GBGB9717685.3A GB9717685D0 (en) 1997-08-22 1997-08-22 Bonded products and processes for their manufacture
GBGB9717687.9A GB9717687D0 (en) 1997-08-22 1997-08-22 Bonded products and processes for their manufacture

Publications (1)

Publication Number Publication Date
WO1999010293A1 true WO1999010293A1 (fr) 1999-03-04

Family

ID=26312101

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1998/002474 Ceased WO1999010293A1 (fr) 1997-08-22 1998-08-24 Produits lies et procedes de leur fabrication

Country Status (2)

Country Link
AU (1) AU8869198A (fr)
WO (1) WO1999010293A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2578670B1 (fr) * 2010-06-03 2019-09-25 Idemitsu Kosan Co., Ltd. Baume de cajou ayant une stabilité améliorée
US20240209178A1 (en) * 2021-05-14 2024-06-27 Procarbon Bio Ab Charcoal products made with phenolic resin binder and methods for making thereof

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB259959A (fr)
GB283803A (en) * 1926-10-11 1928-01-11 Mortimer Thomas Harvey Improvements in or relating to reaction products of cashew nut shell oil
US2067919A (en) 1935-06-20 1937-01-19 Harvel Corp Compositions of matter, and methods and steps of making and using the same
GB481960A (en) 1936-06-19 1938-03-21 Harvel Corp Improvements in or relating to the polymerization of cashew nut shell liquid
GB536800A (en) 1939-03-10 1941-05-28 Harvel Res Corp Improvements in or relating to the manufacture of frictional elements
GB664169A (en) 1948-01-27 1952-01-02 British Resin Prod Ltd Improvements in or relating to purified cashew nut shell liquid and derivatives thereof
GB742286A (en) 1952-11-06 1955-12-21 British Resin Prod Ltd Process for the production of polymers of anacardic material
US2754283A (en) 1952-11-06 1956-07-10 Harvel Corp Polymerization of anacardic materials using sulfonic acid catalysts
EP0015761A2 (fr) * 1979-03-09 1980-09-17 Anthony Jack Hawkes Polymère, sa préparation et son application à la production de matériaux agglomérés
JPS57123279A (en) * 1980-12-18 1982-07-31 Hitachi Chem Co Ltd Friction modifier
BR8804522A (pt) * 1988-09-02 1989-01-03 Cheila Goncalves Mothe Composicao de resina fenolica com elevada estabilidade termica

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB259959A (fr)
GB283803A (en) * 1926-10-11 1928-01-11 Mortimer Thomas Harvey Improvements in or relating to reaction products of cashew nut shell oil
US2067919A (en) 1935-06-20 1937-01-19 Harvel Corp Compositions of matter, and methods and steps of making and using the same
GB481960A (en) 1936-06-19 1938-03-21 Harvel Corp Improvements in or relating to the polymerization of cashew nut shell liquid
GB536800A (en) 1939-03-10 1941-05-28 Harvel Res Corp Improvements in or relating to the manufacture of frictional elements
GB664169A (en) 1948-01-27 1952-01-02 British Resin Prod Ltd Improvements in or relating to purified cashew nut shell liquid and derivatives thereof
GB742286A (en) 1952-11-06 1955-12-21 British Resin Prod Ltd Process for the production of polymers of anacardic material
US2754283A (en) 1952-11-06 1956-07-10 Harvel Corp Polymerization of anacardic materials using sulfonic acid catalysts
EP0015761A2 (fr) * 1979-03-09 1980-09-17 Anthony Jack Hawkes Polymère, sa préparation et son application à la production de matériaux agglomérés
JPS57123279A (en) * 1980-12-18 1982-07-31 Hitachi Chem Co Ltd Friction modifier
BR8804522A (pt) * 1988-09-02 1989-01-03 Cheila Goncalves Mothe Composicao de resina fenolica com elevada estabilidade termica

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 110, no. 26, 26 June 1989, Columbus, Ohio, US; abstract no. 232702, XP002088931 *
PATENT ABSTRACTS OF JAPAN vol. 006, no. 219 (C - 132) 2 November 1982 (1982-11-02) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2578670B1 (fr) * 2010-06-03 2019-09-25 Idemitsu Kosan Co., Ltd. Baume de cajou ayant une stabilité améliorée
US20240209178A1 (en) * 2021-05-14 2024-06-27 Procarbon Bio Ab Charcoal products made with phenolic resin binder and methods for making thereof

Also Published As

Publication number Publication date
AU8869198A (en) 1999-03-16

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