WO2010071532A1

WO2010071532A1 - Acetylenic phenol-aldehyde resin

Info

Publication number: WO2010071532A1
Application number: PCT/SE2009/000103
Authority: WO
Inventors: Jan-Erik Rosenberg; David Persson; Rebecka Liedholm
Original assignee: Nexam Chemical Ab
Priority date: 2008-12-16
Filing date: 2009-02-25
Publication date: 2010-06-24

Abstract

Disclosed is an acetylenic phenol-aldehyde resin having at least one carbon-carbon triple bond. The resin is obtained by subjecting at least one phenolic compound (1), at least one acetylenic phenolic compound (2), having at least one carbon-carbon triple bond, at least one aldehyde (3) to basic or acidic co-condensation, or by subjecting at least one phenol-aldehyde resin, obtained by basic or acidic co-condensation of at least one phenolic compound (1) and at least one aldehyde, to further co-condensation with at least one acetylenic phenolic compound (2), having at least one carbon-carbon triple bond.

Description

ACETYLENIC PHENOL-ALDEHYDE RESIN

The present invention refers to a acetylenic phenol-aldehyde resin and a composition comprising said acetylenic phenol-aldehyde resin. Said phenol-aldehyde resin has at least one acetylenic carbon-carbon triple bond and is obtained by incorporation of at least one acetylenic phenolic compound, having at least one carbon-carbon triple bond, into a phenol-formaldehyde resin, hi further aspects the present invention refers to a composition comprising said acetylenic phenol-aldehyde resin and a moulded or coated article obtained from said acetylenic phenol-aldehyde resin or said composition.

Acetylenic above and hereafter refers to any chemical compound, including monomers, oligomers and polymers, and/or any chemical group, which compound or group has at least one carbon-carbon triple bond and phenol-aldehyde resin refers to any resin, including epoxidised species, obtained by acidic or basic co-condensation of at least one phenolic compound and at least one aldehyde. Phenolic compound is above and hereafter used as designation for any aromatic compound having one or more pendant phenolic hydroxyl group(s) and being capable of reacting with an aldehyde.

Phenol-aldehyde resins, such as phenol-formaldehyde resins, are well known resins produced by co-condensation of at least one phenolic compound, such as a phenol, a cresole, a hydroquinone, a catechol, a resorcinol and/or a bisphenol and at least one aldehyde, such as formaldehyde, acetaldehyde and/or furfural. Other reactants are known to be used in smaller amounts to provide specific properties, especially in coatings applications, such as rosin (abietic acid), dicyclopentadiene, unsaturated oils, such as tung oil and linseed oil, and polyvalent cations for crosslinking. Aniline has been incorporated into phenol-aldehyde resins but this has been generally discontinued because of the toxicity of aromatic amines. Phenol-aldehyde resins are formed by a step-growth polymerisation reaction which may be either acid or base catalysed.

The most commonly produced and used phenol-aldehyde resins are phenol-formaldehyde resins. Typically, base catalysed phenol-formaldehyde resins are made with a molar ratio of formaldehyde to phenolic compound of greater than one and are normally called resoles, while acid catalysed phenol-formaldehyde resins are made with a molar ratio of formaldehyde to phenolic compound of less than one and are called novolacs. Phenol can for instance react with formaldehyde at any of three possible sites and formaldehyde can react with one or two phenols. By adding for instance an acid catalyst, such as sulphuric acid or /?-toluenesulphonic acid, to a phenolic compound and slowly adding for instance formaldehyde, the formaldehyde will react with two phenols to form a methylene bridge yielding a dimer. The dimer will at higher concentrations generate trimers, tetramers and higher oligomers. The average molecule generated depends on the ratio of formaldehyde to phenolic compound.

In a conventional novolac process, typically molten phenol is placed in a reactor, followed by an amount of acid catalyst, such as sulphuric acid, a sulphonic acid and/or oxalic acid. A formaldehyde solution is slowly added at a temperature of about 90⁰C and at a formaldehyde to phenol molar ratio of for instance between 0.75:1 and 0.85:1. The heat of reaction is removed by refluxing the water combined with the formaldehyde or by using a small amount of a volatile solvent, such as toluene. Novolac resins are typically cured with 5-15% hexamethylene diamine as crosslinking agent.

In a typical resole process phenol and a formaldehyde solution are added to a reactor at a molar ratio of formaldehyde to phenol of typically 1.2-3.0:1. A basic catalyst, such as sodium hydroxide, barium hydroxide and/or hexamethylene diamine, is added and the pH is checked and if necessary adjusted. A reaction temperature of about 80-95⁰C is typically used with vacuum reflux. The advancement and cure of resole resins follow reaction steps similar to those used for resin preparation. Methylol groups condense with other methylols to give dibenzyl ethers and react at the ortho and para positions on the phenol to give diphenylmethylenes.

There are, despite the fact that phenol-aldehyde resins have good to excellent physical and chemical properties and for a long time have been widely used for coatings, fibres, moulded articles and so on, demands for improved and/or modified properties, such as increased operational temperatures and retained properties during and after exposure to for instance harsh conditions, such as increased resistance towards thermo-oxidative, thermal, oxidative and/or mechanical degradation.

It has now quite unexpectedly been found that acetylenic phenol-aldehyde resins can be obtained by incorporation of carbon-carbon triple bonds, for instance as endcapping group(s), as pendant group(s) along the molecular backbone and/or as group being part of the molecular backbone. Acetylenic phenol-aldehyde resins are nowhere reported or contemplated in the prior art literature. The carbon-carbon triple bond allows for instance acetylenic crosslinking, of the phenol-aldehyde resin according to the present invention, as alternative and/or additional crosslinking mechanism, thus implying improved and/or changed properties, such as changed E-module value, changed impact strength and improved resistance towards thermo-oxidative, thermal, oxidative and/or mechanical degradation.

The present invention accordingly refers to a novel acetylenic phenol-aldehyde resin. The phenol-aldehyde resin of the present invention is preferably obtained by acidic or basic co-condensation of at least one phenolic compound (1), at least one acetylenic phenolic compound (2) and at least one aldehyde (3) or by subjecting at least one phenol-aldehyde resin, obtained by acidic or basic co-condensation of at least one phenolic compound (1) and at least one aldehyde (3), to further acidic or basic co-condensation with at least one said acetylenic phenolic compound (2).

Phenolic compounds (1) used in the production of phenol-aldehyde resins typically include compounds of for instance general Formula I-Xπ below,

CO (H) m (IV)

(V) (VI)

wherein each substituent R independently is hydrogen or a linear or branched alkyl, alkenyl, amino, aminoalkyl, aminoalkenyl, alkylamino, alkenylamino, halo, haloalkyl, haloalkenyl, alkylhalo or alkenylhalo group. Said phenolic compounds (1) are accordingly among the preferred embodiments in the present invention.

Embodiments of said phenolic compound (1) include previously disclosed compounds of general Formula I-XII, such as at least one phenol, cresole, hydroquinone, catechole, resorcinol and/or bisphenol, such as a bisphenol A or F, and/or at least one linear or branched alkyl, alkenyl, amino, aminoalkyl, alkylamiiio, halo, haloalkyl or alkylhalo derivative thereof and can further be exemplified by />-t-butylphenol, jo-octylphenol, /»-nonylphenol, xylenol, o-, m- and /7-cresole, catechole, hydroquinone, resorcinol and /?-phenylphenol and/or bisphenols, such as bisphenol A and bisphenol F, including linear and branched alkyl, amino, aminoalkyl, alkylamino, halo, haloalkyl and alkylhalo derivatives thereof.

Embodiments of said acetylenic phenolic compound (2) include alkynyl and arylalkynyl phenols, alkynyl and arylalkynyl cresoles, alkynyl and arylalkynyl hydroquinones, alkynyl or arylalkynyl catechols, alkynyl or arylalkynyl resorcinols, alkynyl and arylalkynyl bisphenols, such as alkynyl and arylalkynyl bisphenol A or F, as well as acetylenic phenolic compounds (2) of Formula Xm and Formula XIV, Formula (XIII) Formula (XIV)

wherein the position in the aromatic ring of the acetylenic group and position of the hydroxyl group are variable and wherein each substituent R independently is hydrogen or hydroxyl or a linear or branched alkyl, amino, aminoalkyl, alkylamino, halo, haloalkyl or alkylhalo group and each substituent R independently is hydrogen or a linear or branched alkyl, aryl, arylalkyl or alkylaryl group.

Said aryl is above and hereinafter preferably phenyl or naphthyl, said alkyl likewise preferably linear or branched, aliphatic or cycloaliphatic Ci-Cs alkyl, such as methyl, ethyl, propyl or butyl, said alkenyl likewise preferably aliphatic or cycloaliphatic, linear or branched C₂-C₈ alkenyl, such as ethenyl, propenyl or butenyl, and said alkynyl likewise preferably aliphatic or cycloaliphatic, linear or branched C2-C₈ alkynyl, such as ethynyl, propynyl or butynyl.

Said acetylenic phenolic compound (2) is in its most preferred embodiments at least one ethynyl phenol, phenylethynyl phenol, naphthylethynyl phenol, ethynyl cresole, phenylethynyl cresole, naphthylethynyl cresole, ethynyl hydroquinone, phenylethynyl hydroquinone, naphthylethynyl hydroquinone, ethynyl catechole, phenylethynyl catechole, naphthylethynyl catechole, ethynyl resorcinole, phenylethynyl resorcinole, naphthylethynyl resorcinol, ethynyl bisphenol A, phenylethynyl bisphenol A, naphthylethynyl bisphenol A, ethynyl bisphenol F, phenylethynyl bisphenol F and/or naphthylethynyl bisphenol F and/or at least one linear or branched alkyl, aminoalkyl, alkylamino, halo, haloalkyl and/or alkylhalo derivative of a said acetylenic compound (2). Further suitable and preferred embodiments of said acetylenic phenolic compound (2) include phenolic compounds, such as N-(4-hydroxyphenyl)- -4-(arylalkynyl)phthalimides and N-(4-hydroxyphenyl)-4-(alkynyl)phthalimides, wherein aryl preferably is said phenyl or naphthyl and alkynyl is said C₂-C₈ alkynyl, such as ethynyl, propynyl and/or butynyl.

The most preferred aldehyde is formaldehyde, including paraformaldehyde and trioxane optionally in combination with one or more higher aldehydes, such as acetaldehyde, paraldehyde (paracetaldehyde), glyoxal and/or furfural. Higher aldehydes react with phenolic compounds in the same manner as formaldehyde, although typically at a lower rate. The acetylenic phenol-aldehyde resin according to the present invention is in its most preferred embodiments either an acetylenic novolac obtained by acidic co-condensation of at least one said phenolic compound (1), a said aldehyde (3), most preferably formaldehyde, and at least one said acetylenic phenolic compound (2) or is an acetylenic novolac obtained by subjecting at least one novolac, obtained by acidic co-condensation of a said aldehyde (3), most preferably formaldehyde, and at least one said phenolic compound (1), to further acidic co-condensation with at least one said acetylenic phenolic compound (2).

Said acetylenic phenolic compound (2) is in preferred embodiments of the present invention suitably present in said acetylenic phenol-aldehyde resin in an amount corresponding to at least 0.1, preferably corresponding to between 1 and 30 mole%, of the total molar amount of monomers used, that is said phenolic compound (1), said acetylenic phenolic compound (2) and said aldehyde (3) and/or any other compound used in production of the acetylic phenol-aldehyde resin of the present invention.

The purpose of the present invention is to modify the mechanical properties of phenol-aldehyde resins and compositions comprising phenol-aldehyde resins. Among these modifications of properties can be mentioned: higher softening temperature, higher E-modulus and improved ability to counteract creep strain.

It is understood that the acetylenic group of the acetylenic phenol-aldehyde resin of the present invention can be arranged as an endcapping, in-chain and/or pendent group. This will, of course in it self give different properties to the polymer after curing.

It is possible to further modify the mechanical properties by using methods known in the art together with the acetylenic phenol-aldehyde resin and/or the composition herein disclosed. The purpose of such modifications is typically to reinforce for strength, to fill for higher density, dimension stability and higher stiffness, adding of conductive materials for avoiding static charging and pigmentation for aesthetic properties.

It is known in the art to add different types of fibres as reinforcements. Fibres suitable for use together with the acetylenic phenol-aldehyde resin and/or the composition of the present invention can be exemplified by glass fibres, carbon fibres, steel fibres, aramide fibres, natural organic fibres, such as cellulose fibres, flax fibres, cotton fibres and silk. However, most organic and inorganic fibres that are able to withstand the process temperatures may prove useful. It is also possible to use fullerenes for reinforcing as well as for changing other mechanical properties. Fillers are typically used for increasing dimension stability even though a few other mechanical properties, such as density, rigidity and acoustic properties may be altered by means of fillers. Fillers may be organic like cellulose or inorganic, such as minerals like for instance mica, lime and talcum.

It is furthermore possible to add stabilisers to said acetylenic phenol-aldehyde resin and/or said composition, such as compounds stabilising towards exposure to ultraviolet light, heat or other exposure that may cause for instance polymer chain breakdown. One may in this context also mention the possibility to add different kinds of fire retarding agents to the polymer.

It is furthermore possible to modify the properties of the acetylenic phenol-aldehyde resin and/or the composition according to the present invention by means of a plasticisers, lubricants or impact modifiers yielding for instance a polymer with elastic properties having improved thermal stability. It is also possible to utilise the present invention together with polymer blends as well as copolymers.

The electrical properties of the acetylenic phenol-aldehyde resin and/or the composition of the present invention may also be modified within the scope of the invention. This may be achieved by adding for instance an insulation modifier. The most common modifier is carbon black which is used in smaller quantities to achieve antistatic properties. By adding more carbon black, the acetylenic phenol-aldehyde resin and/or the composition may exhibit receive from dissipating properties to conducting and shielding properties. There are besides carbon black also other known substances and compounds used for obtaining above or portions of thereof. Metal fibres, carbon fibres and metal powder are only a few examples of such materials. Some of these materials also serve the purpose of reinforcing and filling agents.

Said acetylenic phenol-aldehyde resin and/or said composition may also be expanded to change the density and thermal insulation property by adding a blowing, expanding or foaming agent. This may of course be used in combination with other additives.

It is in some applications also advantageous to modify the surface properties of the acetylenic phenol-aldehyde resin and/or the composition. One such way is by adding anti-microbial agents for which the purpose is obvious. Another way is by adding so called tackifiers increasing friction if and when needed.

In a further aspect, the present invention refers to a composition comprising at least one acetylenic phenol-aldehyde resin as disclosed above. The composition can in various embodiments further comprise at least one additional polymer, such as at least one additional phenol-aldehyde resin, alkyd resin, epoxy resin and/or at least one filler, reinforcement, pigment, plasticiser and/or any other additive known in the art. Preferred embodiments of said acetylenic phenol-aldehyde resin are as disclosed above. Said acetylenic phenol-aldehyde resin is suitably present in an amount of between 0.1 and 99.9, such as between 1 and 40 or between 1 and 25, % by weight of said composition.

hi yet a further aspect, the present invention refers to a moulded or coated three-dimensional article obtained by moulding at least one acetylenic phenol-aldehyde resin as disclosed above or at least one composition likewise disclosed above or by coating a three-dimensional object with at least one acetylenic phenol-aldehyde resin as disclosed above or at least one composition likewise disclosed above. The acetylenic phenol-aldehyde resin is suitably, upon and/or subsequent said moulding or coating, crosslinked by heat, provided externally or in situ generated, induced crosslinking reaction of its acetylenic group(s). Said crosslinking is suitably enhanced by the presence of an effective amount of at least one compound promoting crosslinking reactions of acetylenic polymers, such as a sulphur or an organic sulphur derivative as disclosed in for instance US patent no. 6,344,523 and/or a radical initiator.

Curing of the herein disclosed acetylenic phenol-aldehyde resin and/or the herein disclosed composition is advantageously initiated by providing the mould, the inlet or the hotrunner with a choking valve or check valve arrangement creating heat in the polymer through friction caused during the injection phase. The valve arrangement may be a solid arrangement whereas the generated heat is guided through the velocity of injection. There are numerous ways to guide the injection velocity.

The acetylenic phenol-aldehyde resin and the composition of the present invention can advantageously be used in coatings as alone resin or composition; as modifying resin/composition acting as for instance adhesion promoter, chemical crosslinker and/or hardening agent; and/or in combination with for instance alkyd resins, amino resins, epoxy resins and poly(vinyl butyral). Application areas of the acetylenic phenol-aldehyde resin and/or the composition of the present invention include, but are not limited thereto, coating of metal, ceramic, and plastic surfaces, such as equipment for heating and air conditioning, chemical processing, petroleum refining and water treatment as well as interior and exterior can and drum linings, metal primers and pipe coatings. Further application areas are find within electrical insulation varnishes; modifiers for baking alkyds, rosin and ester gum systems; clear and pigmented exterior paints and varnishes; aluminium maintenance paints; zinc-rich primers; and concrete paints.

The acetylenic phenol-aldehyde resin and the composition of the present invention can also advantageously be used for production of three-dimensional articles. The velocity can for instance be guided through PLC (Programmable Logic Controller) used for guiding the injection moulding parameters of most modern injection moulding machines. The operator will then have to perform a series of trials where he in small steps increase the injection speed until the threshold temperature in the valve arrangement is sufficient to initiate the curing process. The valve arrangement is advantageously made adjustable for the same purpose.

Another way is to guide the process actively by using a temperature sensor in the mould and/or in the valve arrangement. A pressure sensor advantageously arranged just before the valve arrangement, optionally with a second pressure sensor arranged after the valve arrangement, may serve the same purpose as it indicates the pressure drop and thereby the friction generated. The temperature and pressure sensor(s) may also be used in combination. The data generated from these sensor(s) are then used as process data for guiding the injection moulding cycle. This data may then be used for guiding the injection sequence through direct guiding or so-called statistical process guiding. Statistical process guiding is especially advantageous where there is a risk for measurement lag, data delay or process guiding resonance in the process.

It is also possible to design in such a way that choking portions in the mould itself will constitute a part of the article produced. It will in this way be possible to: a) manufacture articles that due to its size or through very quick curing of used polymers otherwise would be impossible to manufacture, and/or, b) manufacture articles wherein only certain portions are cured, while other portions have the properties of an uncured polymer.

It is furthermore possible to actively guide the orifice size of the check valve thus allowing the temperature profile to be guided through other means than only the injection speed. This can for example be achieved through means of an hydraulic actuator constantly adjusting the size of the opening through the check valve. This guiding can be performed through PLC data only or by the aid of measuring data in the mould and/or around the valve as described above.

The check valve may also be provided with guided heating and/or cooling, either as a replacement for mechanically adjusting the orifice size, or as a complement thereto. Also this can be guided through PLC data only or by the aid of measuring data in the mould and/or around the valve as described above.

The mould is advantageously provided with one or more temperature sensors for the purpose of detecting the exothermic heat caused by the curing process. It is suitable to arrange several such sensors along the flow path of the polymer in order to detect variations in the curing in different portions of the article produced. These measurements are suitably used for statistical process guiding. Similar principles as described above may be used in extrusion moulding. It will, however, be rather easy to achieve a favourable temperature profile for the curing where the polymer material is first plasticised, then heated further in the extrusion mould to initiate the curing while the later portions of the extrusion mould will cool the article enough to keep its shape. The continuos nature of the process is well suited for the curing of the acetylenic phenol-aldehyde resin and/or the composition herein disclosed. Further heating is advantageously achieved by heating a predetermined portion of the extrusion mould by means of an external heat source. This will allow the operator to guide the curing process not having to rely completely on the extrusion velocity for heat generation.

The herein disclosed acetylenic phenol-aldehyde resin and the herein disclosed composition are also well suited for use in a compression moulding process. A predetermined amount of polymeric material can here be preheated to a temperature somewhat under the curing temperature and placed in an open mould. The mould is then closed so that the polymeric material is distributed in the mould as is the normal procedure in compression moulding. The preheating, the mould temperature, the viscosity of the polymeric material and the compression pressure is adapted so that the friction and compression pressure will generate the heat needed to initiate the curing. It is also in a compression moulding process advantageous to provide the mould with one or more temperature and/or pressure sensors for the purpose of detecting the exothermic reaction during the curing.

The viscosity of the polymeric material during processing may be altered by means of rheology modifiers in order to obtain desired process parameters.

The temperature initiating curing is depending on the structure of the acetylenic portion of said acetylenic phenol-aldehyde resin and will have to be adapted to avoid material break down of the polymer chain on curing. There are several ways to modify the acetylenic portion as disclosed in the present application. There is also the possibility to modify the curing temperatures by utilising a catalyst or initiator as disclosed above. Said catalysts have proven to radically lower the curing initiation temperature. It is also possible to add coupling agents.

It is, according to one alternative embodiment of the invention possible to perform at least a portion of the curing after the moulding process. This can for example be performed through electron beam (EB) curing or ultraviolet (UV) curing. This will also call for the need of for instance one or more photoinitiators. hi most applications only a surface curing can be achieved through means of UV curing since the thermoplastic polymer is not transparent, however EB curing will be possible to utilise even for opaque polymers. It is also possible to continue an initiated curing at a lower temperature. The article produced is here after the moulding procedure placed in an oven for a period of time ranging from half an hour to a couple of days. This process is known as baking. In order to keep important portions of the article, such as the flange portion of an oil pan, within desired tolerances the article may be arranged on a jig during the curing process.

A surface curing can be performed through corona treatment or flash heating. It will through this process be possible to cure the surface of a produced article without softening the polymeric material.

The herein disclosed acetylenic phenol-aldehyde resin and composition are, due to the improved mechanical properties such as improved thermal stability and E-modulus allowing said acetylenic phenol-aldehyde resin and/or said composition to be used at higher temperatures then possible with prior art polymers, well suited for manufacturing of a great number of articles.

Suitable and typical application areas will be found within, but not limited to, civilian and military transportation vehicles, such as cars, trucks, busses, motorcycles, trains, ships and aircrafts as well as recreational vehicles wherein for instance demands for weight reduction is an increasing demand.

Automotive, aeronautic and aerospace components suitably produced from the acetylenic phenol-aldehyde resin and/or the composition of the present invention comprise, but are not limited to, for instance exterior body panels and glazing, such as back lights, door panels, fenders, panoramic roofs, roof modules, tailgates, heat shields, armours and spall linings. Further suitable articles include exterior components, such as vent grilles, door handles, front grilles, mirror systems, roof racks, running boards, spoilers, tank flaps, wheel housings and wheel covers as well as traditional after market products. It is also possible to produce larger components for trucks, busses, ships and aircrafts. Said acetylenic phenol-aldehyde resin and/or said composition may furthermore be used in lighting, such as fog lamp lenses, reflectors and housings; headlamp bezels, housings, lenses and reflectors; lamp support brackets; projector lamp reflectors and holders; rear combination lamp housings, reflectors and lenses. These can be base coated, primed for painting, direct metallised and/or moulded in colour. The acetylenic phenol-aldehyde resin and/or the composition of the present invention may also be used for other structural as well as interior components, such as composite headliners, energy absorption systems, front end modules, instrument panels, interior trimmings, load floors, pedestrian energy absorption systems and storage bins, as well as parts suitable for motorcycles, such as no-paint parts, tanks, fairing, chassis, frames, luggage containers and racks, as well as motorcycle rider safety items, such as helmets and all sorts of shields. The acetylenic phenol-aldehyde resin and the composition herein disclosed may also be used in power train parts, such as air intake, automotive gears, wire coatings, brackets, sealings, electronic and electronic housings, fuel system components, pulleys, sensors, throttle bodies, transmissions and transmission parts, and valve rocker covers as well as other components in vehicle engine bays wherein heat may render prior art polymers insufficient.

Further suitable application areas of the acetylenic phenol-aldehyde resin and/or the composition of the present invention include, but are not limited to, articles used in home entertainment, such as television apparatus and equipment, projectors and audio devices, as well as mobile entertainment and information carriers and communication devices. Further application areas include communication devices such as antennas, satellite dishes, articles and devices for recreation, entertainment and sport activities wherein for instance the weight to strength ratio is important, such as light weight components in extreme sport equipment including body protection, parts to mountain bikes, heat shields and the like. Further suitable applications include articles such as fishing rods and golf clubs.

A further industry having demands on higher mechanical strength, sometimes under elevated temperatures, is the packaging industry. The acetylenic phenol-aldehyde resin and/or the composition according to the present invention will solve a number of problems linked to medium to long term storage under for instance elevated temperatures. Furthermore, creep strain in polymers, which today is a problem calling for over-dimensioning of carrying structures made of polymeric materials, can be eliminated or reduced by use of the acetylenic phenol-aldehyde resin and/or the composition of the present invention.

It is also advantageous to utilise the acetylenic phenol-aldehyde resin and/or the composition herein disclosed in household, building and construction industry. Said acetylenic phenol-aldehyde resin and/or said composition can here be used for beams, girders, rails, panels, window frames and sub assemblies, roofing, flooring, doors and door frames, handles, knobs, cabinets, housings, kitchen appliances and central heating and energy recovery systems as well as for solar energy collectors and other parts of solar and wind energy and heating systems and equipment. Further application areas can be found among electrical components, equipment and installations, such as circuit breakers, films, flexible and rigid wire coatings, housings and discrete components.

The herein disclosed acetylenic phenol-aldehyde resin and/or composition are also suitably used in health care, including man and animal, and laboratory equipment such as cardiovascular and blood care equipment, oxygenators, filters, pumps, masks, sleep therapy equipment, drug delivery devices, inhales, syringes, injection devices, stopcocks and valves as well as orthopaedic equipment, external bone fixation, joint trials, mechanical instruments, surgical instruments, electrosurgical instruments, endomechanical instruments and access devices as well as sub components and spare parts to the above. Said acetylenic phenol-aldehyde resin and/or said composition can furthermore be used for supporting, diagnostic and monitoring equipment, such as hand instruments, equipment for imaging, ocular devices, dental devices, laboratory ware and vials as well as sterilisation trays.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilise the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. In the following Examples 1 and 2 refers to preparation of acetylenic phenol-formaldehyde novolacs according to embodiments of the present invention.

Example 1

60 parts by weight of 4-iodophenol, 800 parts by weight of phenol, 540 parts by weight of formaldehyde, 28 parts by weight of 4-phenylethynyl phenol, 4 part by weight of oxalic acid dihydrate and 200 parts by weight of water were charged in a reaction vessel equipped with a thermometer, a condenser and agitation. The mixture was over 20 minutes heated to 60°C and the temperature was subsequently over 75 minutes gradually increased to 90°C. The reaction mixture was held at 90°C for 175 minutes. Vacuum (50-300 mbar) was now applied for 45 minutes and the reaction mixture was finally cooled to room temperature to yield an acetylenic novolac resin having an average polymerisation degree exceeding 10, as determined by GPC analysis and a glass transition temperature (Tg) of 54⁰C as determined by DSC analysis. GC analysis evidenced that the acetylenic phenolic compound 4-phenylethynyl phenol was co-condensed into obtained novolac resin.

Example 2

1220 parts by weight of phenol, 270 parts by weight of N-(4-hydroxyphenyl)-4-(phenyl- ethynyl)phthalimide, 930 parts by weight of formaldehyde and 2500 parts by weight of methylethylketone were charged in a reaction vessel equipped with a thermometer, a condenser and agitation. The reactants were mixed and heated to 40°C and 1 part by weight of sulphuric acid was added. The reaction mixture was heated to reflux (about 76°C) and kept at reflux for 130 minutes. The solvent (methylethylketone) was gradually removed by atmospheric distillation until the temperature after 100 minutes reached 101°C. Vacuum was now applied and the mixture was heated for 155 minutes increasing the temperature from 101°C to 120°C. The reaction mixture was finally cooled to room temperature to yield a solid acetylenic novolac resin having an average having an average polymerisation degree exceeding 10, as determined by GPC analysis, and a glass transition temperature (Tg) of 26°C as determined by DSC analysis. LC analysis evidenced that the acetylenic phenolic compound N-(4-hydroxyphenyl)-4-(phenylethynyl)-phthalimide was co-condensed into obtained novolac resin.

Claims

Acetylenic phenol-aldehyde resin characteris ed in, that said acetylenic phenol-aldehyde resin has at least one crosslinkable acetylenic carbon-carbon triple bond and that said acetylenic phenol-aldehyde resin is obtained by subjecting at least one phenolic compound (1), at least one acetylenic phenolic compound (2), having at least one carbon-carbon triple bond, and at least one aldehyde (3) to acidic or basic co-condensation or by subjecting at least one phenol-aldehyde resin, obtained by basic or acidic co-condensation of at least one phenolic compound (1) and at least one aldehyde (3), to further co-condensation with at least one acetylenic phenolic compound (2), having at least one carbon-carbon triple bond.

Acetylenic phenol-aldehyde resin according to Claim 1 characterised in, that said acetylenic phenolic compound (2) is a compound of

Formula Xm and/or Formula XTV

Formula (XIII) Formula (XIV)

wherein position in the aromatic ring of acetylenic group and hydroxyl group are variable and wherein each R independently is hydrogen or hydroxyl or a linear or branched alkyl, amino, aminoalkyl, alkylamino, halo, haloalkyl or alkylhalo group and each R independently is hydrogen or a linear or branched alkyl, aryl, arylalkyl or alkylaryl group.

Acetylenic phenol-aldehyde resin according to Claim 1 characteri s ed in, that said acetylenic phenolic compound (2) is at least one alkynyl or arylalkynyl phenol, alkynyl or arylalkynyl cresole, alkynyl or arylalkynyl hydroquinone, alkynyl or arylalkynyl catechole, alkynyl or arylalkynyl resorcinol and/or alkynyl or arylalkynyl bisphenol and/or at least one linear or branched alkyl, amino, aminoalkyl, alkylamino, halo, haloalkyl and/or alkylhalo derivative of a said acetylenic phenolic compound (2).

Acetylenic phenol-aldehyde resin according to Claim 1 characteri sed in, that said acetylenic phenolic compound (2) is at least one N-(4-hydroxyphenyl)-4-(arylalkynyl)phthalimide and/or at least N-(4-hydroxyphenyl)-4- -(alkynyl)phthalimide.

5. Acetylenic phenol-aldehyde resin according to Claim 2, 3 or 4 characterised in, that said alkyl is linear or branched, aliphatic or cycloaliphatic

Ci-Cs alkyl, that said alkenyl is aliphatic or cycloaliphatic, linear or branched C2-C8 alkenyl and that said alkynyl is aliphatic or cycloaliphatic, linear or branched C₂-C₈ alkynyl.

6. Acetylenic phenol-aldehyde resin according to Claim 2, 3 or 4 characterised in, that said aryl is phenyl or naphthyl, that said alkyl is methyl, ethyl, propyl or butyl, that said alkenyl is ethenyl, propenyl or butenyl and that said alkynyl is ethynyl, propynyl or butynyl.

7. Acetylenic phenol-aldehyde resin according to Claim 1 characteris ed in, that said acetylenic phenolic compound (2) is at least one ethynyl phenol, phenylethynyl phenol, naphthylethynyl phenol, ethynyl cresole, phenylethynyl cresole, naphthylethynyl cresole, ethynyl hydroquinone, phenylethynyl hydroquinone, naphthylethynyl hydroquinone, ethynyl catechole, phenylethynyl catechole, naphthylethynyl catechole, ethynyl resorcinole, phenylethynyl resorcinole, naphthylethynyl resorcinol, ethynyl bisphenol A, phenylethynyl bisphenole A, naphthylethynyl bisphenol A, ethynyl bisphenol F, phenylethynyl bisphenol F and/or naphthylethynyl bisphenol F and/or at least one linear or branched alkyl, amino, aminoalkyl, alkylamino, halo, haloalkyl and/or alkylhalo derivative of a said acetylenic compound (2).

8. Acetylenic phenol-aldehyde resin according to any of the Claims 1-7 c h a r a c t e r i s e d i n, that said aldehyde (3) is formaldehyde, including paraformaldehyde and trioxane, acetaldehyde, paraldehyde, glyoxal and/or furfural.

9. Acetylenic phenol-aldehyde resin according to any of the Claims 1-8 characterised in, that said at least one aldehyde (3) is formaldehyde.

10. Acetylenic phenol-aldehyde resin according to any of the Claims 1-9 charac t eri s e d i n, that said phenolic compound (1) is at least one phenol, cresole, hydroquinone, catechole, resorcinol and/or bisphenol, such as a bisphenol A or F, and/or at least linear or branched alkyl, amino, aminoalkyl, alkylamino, halo, haloalkyl and/ alkylhalo derivative of a said phenolic compound (1).

11. Acetylenic phenol-aldehyde resin according to any of the Claims 1-10 characteri s e d in, that said acetylenic phenol-aldehyde resin is obtained by acidic co-condensation of at least one said phenolic compound (1), at least one said acetylenic phenolic compound (2) and at least one said aldehyde (3).

12. Acetylenic phenol-aldehyde resin according to any of the Claims 1-10 ch aract eri s ed in, that said acetylenic phenol-aldehyde resin is obtained by subjecting at least one phenol-aldehyde resin, obtained by acidic co-condensation of at least one said phenolic compound (1) and at least one said aldehyde (3), to further acidic co-condensation with at least one said acetylenic phenolic compound (2).

13. Acetylenic phenol-aldehyde resin according to any of the Claims 1-12 characterised in, that said acetylenic phenolic compound (2) is present in said acetylenic phenol-aldehyde resin in an amount corresponding to at least 0.1 mole% of total amount of monomers, oligomers and/or polymers used in production of said acetylenic phenol-aldehyde resin.

14. Acetylenic phenol-aldehyde resin according to any of the Claims 1-13 characterised in, that said acetylenic phenolic compound (2) is present in said acetylenic phenol-aldehyde resin in an amount corresponding between 1 and 30 mole% of total amount of monomers, oligomers and/or polymers used in production of said acetylenic phenol-aldehyde resin.

15. Acetylenic phenol-aldehyde resin according to any of the Claims 1-14 characteri s ed in, that said acetylenic phenol-aldehyde resin is an acetylenic phenol-formaldehyde novolac.

16. A composition c h ara c t eri s e d i n, that said composition comprises at least one acetylenic phenol-aldehyde resin according to any of the Claims 1-15.

17. A composition according to Claim 16 characteri sed in, that said composition comprises between 0.1 and 99.9 by weight of said acetylenic phenol-aldehyde resin.

18. A composition according to Claim 16 characterised in, that said composition comprises between 1% and 40% by weight of said acetylenic phenol-aldehyde resin.

19. A composition according to Claim 16 characterised in, that said composition comprises between 1% and 20% by weight of said acetylenic phenol-aldehyde resin.

20. A moulded three-dimensional article characterised in, that said article is obtained by moulding at least one acetylenic phenol-aldehyde resin according to any of the Claims 1-15 or at least one composition according to any of the Claims 16-19.

21. A coated three-dimensional article characterised in, that said article is obtained by coating a three-dimensional object with at least one acetylenic phenol-aldehyde resin according to any of the Claims 1-15 or at least one composition according to any of the Claims 16-19.