WO2017096423A1 - Procédé de formation de mousse phénolique - Google Patents

Procédé de formation de mousse phénolique Download PDF

Info

Publication number
WO2017096423A1
WO2017096423A1 PCT/AU2016/051199 AU2016051199W WO2017096423A1 WO 2017096423 A1 WO2017096423 A1 WO 2017096423A1 AU 2016051199 W AU2016051199 W AU 2016051199W WO 2017096423 A1 WO2017096423 A1 WO 2017096423A1
Authority
WO
WIPO (PCT)
Prior art keywords
foam
phenolic foam
phenolic
bodies
precursor
Prior art date
Application number
PCT/AU2016/051199
Other languages
English (en)
Inventor
Tong Lin
Zhiguang Xu
Yan Zhao
Original Assignee
Deakin 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 AU2015905060A external-priority patent/AU2015905060A0/en
Application filed by Deakin University filed Critical Deakin University
Publication of WO2017096423A1 publication Critical patent/WO2017096423A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/56—After-treatment of articles, e.g. for altering the shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/22—After-treatment of expandable particles; Forming foamed products
    • C08J9/228—Forming foamed products
    • C08J9/236—Forming foamed products using binding agents
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/56—After-treatment of articles, e.g. for altering the shape
    • B29C44/5681—Covering the foamed object with, e.g. a lining
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2463/00—Use of EP, i.e. epoxy resins or derivatives thereof as filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2511/00—Use of natural products or their composites, not provided for in groups B29K2401/00 - B29K2509/00, as filler
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0063—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/776—Walls, e.g. building panels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/026—Crosslinking before of after foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with monohydric phenols
    • C08J2361/10—Phenol-formaldehyde condensates
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B1/78—Heat insulating elements
    • E04B1/80—Heat insulating elements slab-shaped
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/74—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls
    • E04B1/76—Heat, sound or noise insulation, absorption, or reflection; Other building methods affording favourable thermal or acoustical conditions, e.g. accumulating of heat within walls specifically with respect to heat only
    • E04B2001/7691—Heat reflecting layers or coatings

Definitions

  • the present invention generally relates to a method of forming phenolic foam.
  • the invention is particularly applicable for forming novolac resin based foams, particularly novolac resin based composite foams for building and/or insulation applications and it will be convenient to hereinafter disclose the invention in relation to that exemplary application.
  • the invention is not limited to that application and could be used to form other types of phenolic foam products.
  • Mineral fibre includes glass wool and stone wool.
  • Polymer foams include expanded polystyrene, extruded polystyrene, polyurethane foam, and phenolic foam. Expanded polystyrene and extruded polystyrene materials currently dominate the polymeric foam segment of the thermal insulating material market.
  • polyurethane and polystyrene foams have a restricted use at high temperature because they generate harmful smoke when burning.
  • Glass wool has a restricted to the supply of boron raw material primary mined in the United States and Turkey.
  • the use of glass wool and stone wool also has health concerns with constituent short mineral fibres often causing breathing problems and allergic reaction.
  • Phenolic foam is an excellent high-temperature insulating material. Phenolic foam is known to have excellent fire-resistance and thermal-insulation ability. It has advantages in high thermal insulating efficiency, fire-resistant, negligible smoke emission, and does not melt and therefore not drip when burnt. Due to these excellent properties, phenolic foam has attracted great attention, especially in high temperature insulating market. Phenolic foam can replace polyurethane foam, polystyrene foam and mineral wool in the field where high temperature susceptibility, thermal insulation or fire-resistant is required. Moreover, the cost of phenolic foam is cheaper than polyurethane foam, sometimes only about two-thirds the cost of an equivalent amount of polyurethane foam.
  • Phenolic resins are polymers synthetized by the reaction of formaldehyde with phenol derivatives. Based on the molar ratio of phenol to formaldehyde and the pH value during the reaction, phenolic resin can be classified into two main types, resole and novolac. The resin is made by reaction of phenol with extra formaldehyde at alkaline condition often results in resole resin. The resin from formaldehyde with extra phenol at acidic condition gives novolac resin.
  • the typical chemical structures of resole and novolac are set out below:
  • Resole resin is a thermoset with high chemical activity, and it cured using acidic catalyst. Resole is formaldehyde rich due to the extra formaldehyde content than phenol. It has to be used immediately after produced due to the short shelf life at room temperature, making it unsuitable for long distance transport.
  • resole-based phenolic foam is prepared by uniformly mixing aqueous resole resin with blowing agent, surfactant, additive and acid catalyst. The reaction between acid catalyst and resole resin is highly exothermic, vapourising the constituent water and the blowing agent expanding the resin into foam during curing.
  • the acid catalyst used for foaming phenolic resin usually includes sulfonic acid, hydrochloric acid, sulfoacid and substituted acid.
  • Hydrocarbon chemicals for example butane, pentane, hexane, heptane, cyclopentane, isobutane and isopentane are often used as blowing agent.
  • ethanol or acetone solvent could be used to adjust the viscosity of phenolic resin.
  • the acid catalyst, solvent and extra formaldehyde trapped in the foam can slowly release from the foam, leading to corrosion, health hazards and pollution to the environment.
  • novolac is a thermoplastic resin prepared with a low formaldehyde to phenol molar ratio, typically less than one.
  • Novolac resin can be cured by formaldehyde, paraformaldehyde, formaldehyde polymers (for example dioxolane, trioxane), or hexamethylenetetramine (HMTA).
  • HMTA hexamethylenetetramine
  • Novolac resin can also be cured by a resole resin.
  • the use of novolac resin therefore has advantages over resole resin because an acid catalyst is not involved in the curing process. Accordingly, novolac resin does not release corrosive acid after curing.
  • a first aspect of the present invention provides a method of forming a phenolic foam comprising:
  • At least one precursor body comprising a mixture of at least one novolac resin, at least one crosslinking foaming agent, and at least one curing agent; foaming the precursor body mixture by heating the mixture to at least the melting temperature of the novolac resin, to produce a foamed precursor body;
  • the first aspect of the present invention provides a new method to prepare novolac-based phenolic foam.
  • the composite phenolic foam is prepared using a dry foaming method of novolac phenolic resin as opposed to using an acid catalyst and an organic solvent to dissolve and generate the foam.
  • the foam product of the present invention does not release solvent or acid during use.
  • the preparation method is therefore simple, environmentally friendly, and can be cost effective.
  • novolac-based phenolic resin is used as foam precursor without using organic solvent as foaming agent for foaming;
  • the first aspect of the present invention can also provide a two-step process in which involves small phenolic foam pieces according to the first aspect of the present invention are formed first followed by bonding the foam pieces into desired shapes is employed to prepare the final products.
  • the at least one precursor body comprises a plurality of precursor bodies, thereby producing a plurality of phenolic foam bodies and the process further includes the step of:
  • the consolidated phenolic foam product is prepared using this two-step method from by assembling, agglomerating and/or consolidating together a plurality small foam pieces prepared using a dry foaming method of Novolac phenolic resin into a larger consolidated foam body.
  • the dry foaming method differs to prior novolac foaming methods as it does not use an organic solvent to dissolve and generate the foam or use an acid catalyst. Accordingly, the product does not have corrosion or solvent releases issues in use.
  • dry foaming normally has issues with foaming uniformity.
  • the two- step method addresses this issue by controlling uniformity (for example through limited foaming volume) within a plurality of small foam pieces, which are then adhered together to form a consolidated body.
  • the agglomerated or consolidated construction of the consolidated foam body can provide an improvement in mechanical strength compared to a unitary foamed foam body because each small foam piece forming the consolidated body has an outer shell, typically a hard shell, which is introduced into the consolidated body.
  • the assemblage of the foam pieces together can also create pores, in some cases large pores in the final foam block, reducing the bulk density.
  • the technique also allows foam product of different shapes to be prepared, improving the processing flexibility.
  • the consolidated foam body is formed in a selected configuration, preferably by assembling and consolidating the plurality of phenolic foam bodies within a mould.
  • Phenol formaldehyde resins are synthetic polymers obtained by the reaction of phenol or substituted phenol with formaldehyde.
  • a novolac resin is a reaction product of a phenol compound and an aldehyde prepared with a low formaldehyde to phenol molar ratio, typically less than one.
  • the phenol compound is selected from at least one of phenol, resorcinol, bisphenol, cresols, alkyl phenols, phenol ethers, tannins or lignins
  • the aldehyde is selected from at least one of formaldehyde, propionaldehyde, acetaldehyde, benzaldehydes, cyclohexanedicarboxaldehydes, furfural, aryl aldehyde, or heterocyclic aldehyde.
  • the novolac resin can have any suitable molecular weight. In some embodiments, the novolac resin preferably has a molecular weight from 200 to 20000, more preferably from 300 to 15000, yet more preferably from 500 to 10000.
  • the curing agent in the present invention is preferably a curing agent suitable for a dry curing process.
  • Various curing techniques can be used, including thermally activated curing, UV activated curing, radiation activated curing or the like.
  • the curing agent is a thermally activated curing agent.
  • heating the precursor body mixture to at least the melting temperature of the novolac resin also cures the foamed precursor body.
  • the steps of foaming and curing the precursor body therefore preferably comprises heating the at least one precursor body to a temperature which foams and cures the at least one precursor body, thereby forming at least one phenolic foam body.
  • the first aspect of the present invention can relate to a method of forming a phenolic foam comprising:
  • At least one precursor body comprising a mixture of at least one novolac resin, at least one crosslinking foaming agent, and at least one curing agent;
  • the curing agent is selected from at least one of dioxolane, trioxane, paraformaldehyde, hexamethylenetetramine (HMTA), melamine, polyamines, or a resole resin.
  • the curing agent is preferably selected to cure the formed foam at a temperature of at least 100 ° C, preferably at least 120 ° C, more preferably between 120 °C to 200 °C.
  • the amount of curing agent in the precursor body is preferably from 4% to 30% by weight of novolac resin, more preferably from 5% to 25% by weight of novolac resin, yet more preferably from 10 to 20 % by weight of novolac resin.
  • the crosslinking foaming agent in the present invention is preferably a crosslinking foaming agent suitable for a dry curing process.
  • the crosslinking foaming agent comprises a polyphenol foaming agent, preferably a polyphenol containing multiple phenol groups.
  • the crosslinking foaming agent is selected from at least one of tannins, ellagitannin or theaflavin-3-gallate.
  • the amount of crosslinking foaming agent in the precursor body is preferably from 5% to 40% by weight of novolac resin.
  • the at least one precursor body further comprises at least one filler material.
  • the addition of the filler into the foam can be used to reduce the cost of the overall composite.
  • the filler material can comprise any suitable material or mixture of two or more materials.
  • the filler material comprises at least one micro- or nano-sized material or mixtures thereof.
  • the filler material is preferably sized from 5 nm to 10 pm, more preferably from 10 nm to 5 pm.
  • the filler material comprises a nano size filler or "nanofiller".
  • a nanofiller can assist in reducing adhesion of the foam on the module and associated cleaning, and thereby facilitate the method/ process.
  • the addition of nanofiller also increases the compressive strength of the phenolic foam of the present invention (for example from 0.7 MPa to 1 .5 MPa).
  • the filler material comprises organic and inorganic nanowires, nanoparticles, nanoplatelet or a combination thereof.
  • filler material can include at least one of: a) inorganic particles preferably selected from at least one of silica particles (Si0 2 ), ferriferous oxide particles (Fe 3 0 4 ), titanium dioxide particles (Ti0 2 ), carbon particles, calcium carbonate particles (CaC0 3 ), of aluminium oxide b) organic/inorganic nano- or micro-sized wires, preferably selected from at least one attapulgite, palygorskite, cellulose wires, metal wires or metal oxide wires;
  • nanoplatelets preferably selected from at least one clay, layered double hydroxide (LDH), graphite, graphene, graphene oxide, boron nitride (BN), carbon nitride (C 3 N 4 ), ormica layers;
  • LDH layered double hydroxide
  • BN boron nitride
  • C 3 N 4 carbon nitride
  • organic powder preferably selected from at least one PTFE powder, recycled powders from plastics, wood, bones or fibres;
  • organic/inorganic compounds preferably selected from at least one urea, sodium carbonate (Na 2 C0 3 ), sodium bicarbonate (NaHC0 3 ), ammonium bicarbonate (NH 4 HC0 3 ), of ammonium carbonate ((NH 4 ) 2 C0 3 ).
  • the filler material comprises nanofibres prepared from electrospinning.
  • the filler material comprises attapulgite, kaolin clay, silica particles, graphene oxide, or polymer particles.
  • the filler material comprises attapulgite or palygorskite.
  • Palygorskite is a fibrous magnesium aluminium silicate.
  • Attapulgite is a variety of Palygorskite. Both are a mineral clay with a compound structure known as being a hydrated magnesium aluminium silicate typically having the formula (Mg,AI) 2 Si 4 O 10 (OH)-4(H 2 O).
  • the amount of filler material added to the foam precursor body can vary depending on the final application, the desired properties of the foam body and in some cases other factors.
  • the amount of filler material in the precursor body is from 0 to 40 wt %, preferably from 0 to 30 wt%, more preferably from 0 to 20 wt% by weight of novolac resin.
  • the amount of filler material in the precursor body is from 5 to 40 wt %, preferably from 10 to 40 wt%, more preferably from 5 to 30 wt%, yet more preferably from 10 to 30 wt%.
  • the amount of filler material in the precursor body is from 5 to 20 wt %, preferably from 10 to 25 wt%, more preferably from 5 to 35 wt%, yet more preferably from 20 to 40 wt%.
  • the mixture of components forming the precursor body can be accomplished by a variety of methods and apparatus.
  • the step of forming precursor bodies comprises uniformly mixing the mixture thereof and forming the precursor bodies into a selected configuration.
  • the filler is mixed with novolac powder and foaming agent using a blender or miller, and then with the curing agent.
  • the selected configuration can be formed using a variety of shaping techniques.
  • the consolidated foam body is formed in a selected configuration using a mould.
  • the foam bodies can be consolidated into a rectangular block, brick, sheet, slab, billet or the like.
  • the plurality of phenolic foam bodies are introduced into a mould, and moulded therein.
  • the mixture of the precursor body is pressure formed into a selected configuration.
  • a pressure of between 0.5 tons to 9 tons is preferably applied to the mixture of the precursor body in the pressure forming process.
  • the exact pressure applied may vary depending on the specific pressure forming process or apparatus used. This allows the precursor body to be formed in any suitable configuration.
  • the precursor body has at least one of a square, rectangle, cylindrical, pill, or donut-shaped configuration.
  • Suitable pressure forming apparatus include presses, punches, extruders, rollers, moulding presses, dies, injection moulders, vacuum formers or the like.
  • the mixture of the precursor body is pressed into pill, tablet, or donut-shape, using a press machine (for example a tablet press or punch) or similar in a tablet forming process similar to making pharmaceutical tablets.
  • the precursor composite could be pressed into pills or tablets with the diameter of 9 mm and thickness of 3 mm. The tablets are made under the load pressure of 3 tons using a press machine and the shape of the pills is confirmed by a mould.
  • the mixture of the precursor body is extruded into a small rod or tube, and then cut into short pieces. In some embodiments, the mixture of the precursor body is rolled into a thin sheet, and then cut or otherwise comminuted into suitably sized pieces.
  • the at least one precursor body is preferably formed having an average particle size of from 0.5 mm to 500 mm, preferably from 1 mm to 200 mm, more preferably from 1 mm to 100 mm.
  • the phenolic foam bodies can be formed in any suitable configuration.
  • the phenolic foam bodies have at least one of a square, rectangle, cylindrical, pill, or donut-shape configuration
  • a dry foaming method is used to prepare phenolic foam from novolac resin.
  • this process does not use an organic solvent or acid catalyst during the preparation process.
  • a cross-linkable foaming agent and a curing agent preferably a heat sensitive curing agent is used to prepare foam.
  • the precursor bodies are heated.
  • the novolac resin melts inducing decomposition of the foaming agent, causing a volume expansion which foams the composition.
  • the temperature also initiates the curing agent, curing the foamed body.
  • the temperature the precursor body is heated for foaming and curing depends on the specific requirements of the foaming agent and the curing agent.
  • the foaming/ heating step comprises heating the precursor bodies to a temperature from 100 to 300°C, preferably from 120 to 260 °C, more preferably 140 °C to 230 °C.
  • the foaming step can be carried out in any suitable heating device, for example an oven, furnace or the like. As noted above, in some embodiments heating to the above temperature results in both foaming and curing occurring.
  • the consolidated foam body is preferably formed in a selected configuration.
  • the step of assembly of the plurality of phenolic foam bodies comprises:
  • the amount of adhesive used must be sufficient to adhere the foam pieces together to form the consolidated foam body.
  • the ratio of adhesive to foam pieces is from 1 % to 20%, preferably from 1 to 15%, more preferably from 5 to 15% by weight of phenolic foam bodies.
  • a certain amount of adhesive preferably coats the surface of the phenolic foam bodies.
  • the adhesive is coated on the surface of the phenolic foam bodies with a thickness of 0.01 mm to 2 mm, preferably from 0.01 to 1 .5 mm, more preferably from 0.05 to 1 .5 mm, yet more preferably from 0.1 to 1.0 mm.
  • the adhesive can comprise any suitable and compatible adhesive composition.
  • the adhesive comprises a thermosetting resin based adhesive, preferably an epoxy based adhesive, a phenolic resin based adhesive, a fire-retardant silicone adhesive, or a heat resistant silicone.
  • the adhesive comprises the same or chemically similar phenolic resin as used in the phenolic foam bodies.
  • the adhesive can be applied to the phenolic foam bodies using a number of techniques.
  • the adhesive is coated on the surface of the phenolic foam bodies using spraying, brushing, or blending.
  • a variety of curing techniques can be used to cure the adhesive, including heating, hot-press, UV- irradiation or the like.
  • the method of the present invention further comprises the step of: applying a protective material or coating on or over the consolidated foam body.
  • the protective material can comprise any suitable cover, fabric or the like.
  • the protective material comprises aluminium foil, sulphate paper such as Kraft, fabric, metal sheet, plaster board, polymer sheet, polymer films such as polyimide film, polyphenylene sulphide film, or polyvinyl chloride) film.
  • the protective material can be applied in any suitable manner. For example, it can be wrapped around the consolidated foam body after formation. In some embodiments, the protective material is applied during the casting step of the consolidated foam.
  • the consolidated foam body can be formed with a range of properties.
  • the consolidated foam body has a density of from 0.03 g/cm 3 to 0.25 g/cm 3
  • the consolidated foam body has a compressive strength ranges from 0.2 MPa to 3.5 MPa.
  • the novolac resin can comprise pure or unmodified novolac resins and/or modified novolac resins.
  • novolac resin can be modified by either physical or chemical method, for example mechanical mixing and copolymerization with a monomer other than phenolic.
  • Modified novolac resins include polyamide-modified phenolic resin, dicyandiamide-modified phenolic resin, epoxy-modified phenolic resins, polyvinyl acetal-modified phenolic resin, silicone-modified phenolic resin, boron-modified phenolic resin, xylene-modified phenolic resin, aryl alkyl ether- phenol based phenolic resin and the likes.
  • a second aspect of the present invention provides a method of forming a composite phenolic foam comprising:
  • precursor bodies comprising a mixture of novolac resin, a crosslinking foaming agent, curing agent and a filler material
  • This second aspect of the present invention provides a two-step method of forming a composite foam body in which a composite precursor mixture (i.e. containing both phenol resin and a filler) is formed from by assembling, agglomerating and/or consolidating together a plurality small foam pieces prepared using a dry foaming method of novolac phenolic resin.
  • a composite precursor mixture i.e. containing both phenol resin and a filler
  • the dry foaming method differs to prior novolac foaming methods as it does not use an organic solvent to dissolve and generate the foam or use an acid catalyst. Accordingly, the product does not have corrosion or solvent releases issues in use.
  • dry foaming normally has issues with foaming uniformity.
  • the two-step method address this issue by controlling uniformity (through limited foaming volume) within a plurality of small foam pieces, which are then adhered together to form a consolidated body.
  • a filler material particularly a nanofiller material imparts advantageous mechanical properties to the composite foam.
  • a third aspect of the present invention provides a method of forming a composite phenolic foam comprising:
  • the phenolic foam bodies in this third aspect of the present invention can comprise either a resole based phenolic foam or a novolac based phenolic foam or a mixture thereof.
  • the phenolic foam bodies comprise novolac based phenolic foam formed by the method or process of the first aspect of the present invention.
  • phenolic foams can also be used in the aspect of the present invention, for example both pure and modified novolac resins, pure and modified resole based phenolic foam, thermoplastic phenolic resins, such taught in CN 102504155A (Modified thermoplastic phenolic resin and preparation method) or CN102875752 B (Lignin modified thermoplastic phenolic resin and preparation method) the contents of which should be understood to be incorporated into this specification by these references.
  • This third aspect of the present invention provides a two-step method of forming a composite foam body in which a plurality small foam pieces are formed into a larger consolidated foam body by assembling, agglomerating and/or consolidating the smaller foam pieces together.
  • the agglomerated or consolidated construction of the consolidated foam body provides an improvement in mechanical strength compared to a unitary foamed foam body because each small foam piece forming the consolidated body has an outer shell, typically a hard shell, which is introduced into the consolidated body.
  • the assemblage of the foam pieces together also creates large pores in the final foam block, reducing the bulk density.
  • a fourth aspect of the present invention provides a phenolic foam formed from a method according to the first, second or third aspects of the present invention.
  • a fifth aspect of the present invention provides a phenolic foam comprising a novolac resin foam comprising a mixture of novolac resin, a crosslinking foaming agent, and curing agent.
  • a sixth aspect of the present invention provides a phenolic foam comprising a plurality of consolidated and adhered phenolic foam bodies comprising a novolac resin foam comprising a mixture of novolac resin, a crosslinking foaming agent, curing agent and a filler material.
  • the foam of the fourth, fifth and sixth aspects of the present invention and produced by the process of first, second and third aspects of the present invention comprises a low cost, environmentally-friendly, fire-resistant, thermal- insulating, sound shielding foam materials with relatively higher mechanical strength for decoration and construction use.
  • the phenolic foam of the present invention can be used in the following non-limiting applications:
  • Figure 1 provides a schematic illustration of one-step procedure for making phenolic foam according to one embodiment of the present invention.
  • Figure 2 provides a schematic Illustration of a two-step procedure for making phenolic foam according to one embodiment of the present invention.
  • Figure 3 illustrates TGA results of phenolic foam (PF), phenolic foam containing 20% attapulgite (ATP) in air and nitrogen atmosphere.
  • Figure 4 provides compression strength curves of phenolic foam (PF) and phenolic foam with 20 wt% attapulgite (ATP).
  • the present invention relates to a phenolic foam that is made from novolac thermoplastic resin, cross-linkable foaming agent, curing agent and an optional filler material.
  • Embodiments of the present invention also relate to a method of preparing this phenolic foam through a two-step process including producing small foam pieces followed by assembling them into desired shapes.
  • the present invention provides a dry foaming method of forming a phenolic foam by forming at least one precursor body comprising a mixture of at least one novolac resin, at least one crosslinking foaming agent, at least one curing agent and optional filler material; and then foaming and curing that precursor body to form at least one phenolic foam body.
  • foaming and curing is preferably accomplished through heating the precursor body to a temperature that foams and cures the at least one precursor body, so to form a highly porous foam during heating.
  • the resulting phenolic foam is made of a mixture of novolac- based phenolic resin with curing agent, cross-linkable foaming agent, and optional filler material.
  • a novel dry-method is therefore used for making the novolac-based phenolic foam.
  • the foaming process does not use an organic solvent as foaming agent or to dissolve the novolac resin.
  • the elimination of organic solvents reduces the cost and also ensures environmentally-friendly production.
  • the first aspect of the present invention can also provide a two-step process in which a plurality of phenolic foam bodies are formed using the dry foaming method and then these phenolic foam bodies are assembled, agglomerated or otherwise consolidated together into a consolidated foam body.
  • the mixture of novolac phenolic resin, curing agent, cross-linkable foaming agent and filler is shaped into small precursor pieces, followed by foaming and curing to convert them into small phenolic foam pieces.
  • the small phenolic foam pieces are adhered together to form final products with desired shapes.
  • the two-step processing technique has great flexibility in preparing phenolic foams with various shapes compared to forming the phenolic foam as a unitary body. Bonding small foam pieces in the second step can further reduce the density of the final foam products, and simultaneously improve the foam strength.
  • the resulting phenolic composite foam is made of a mixture of novolac- based phenolic resin with curing agent, cross-linkable foaming agent and optional filler material.
  • the mixture is shaped into small bodies or pieces, and then heated to form foam pieces.
  • the as-prepared foam pieces can then be assembled together to form any shapes desired.
  • the foam does not contain acid catalyst and organic solvent, thus eliminating the release of corrosive acid and organic vapour during use.
  • the phenolic foam is thermal-insulating, fire- resistant, and has high sound-shielding property. The compression strength of this phenolic foam is superior to the commercial phenolic foams.
  • the phenolic foam of the present invention can be formulated to be fire-resistant, thermos-insulating and sound shielding.
  • the phenolic foam of the present invention can also be light weight and have acceptable mechanical strength for a large number of processing, building, construction and insulation uses.
  • the novolac resin used in the present invention is preferably prepared by the reaction of phenol compound and aldehyde under conditions of an acidic catalyst with extra molar of phenolic compound to aldehyde (molar ratio of phenol compound to aldehyde is more than one).
  • the phenolic compound can be phenol, resorcinol, bisphenol, cresols, alkyl phenols, phenol ethers, tannins and lignins.
  • the aldehyde can be formaldehyde, propionaldehyde, acetaldehyde, benzaldehydes, cyclohexanedicarboxaldehydes, furfural, aryl aldehyde, heterocyclic aldehyde.
  • the novolac resin molecular weight preferably ranges from 200 to 8000.
  • the novolac resin can comprise pure or unmodified novolac resins and/or modified novolac resins.
  • novolac resin can be modified by either physical or chemical method, for example mechanical mixing and copolymerization with a monomer other than phenolic.
  • Modified novolac resins include polyamide-modified phenolic resin, dicyandiamide-modified phenolic resin, epoxy-modified phenolic resins, polyvinyl acetal-modified phenolic resin, silicone-modified phenolic resin, boron-modified phenolic resin, xylene-modified phenolic resin, aryl alkyl ether- phenol based phenolic resin and the likes.
  • the curing agent in the present invention is preferably a curing agent suitable for a dry curing process.
  • Various curing techniques can be used, including thermally activated curing, UV activated curing, radiation activated curing or the like.
  • the curing agent is a thermally activated curing agent.
  • heating the precursor body mixture to at least the melting temperature of the novolac resin also cures the foamed precursor body.
  • the curing agent used in the present invention can be dioxolane, trioxane, paraformaldehyde, and hexamethylenetetramine (HMTA).
  • HMTA hexamethylenetetramine
  • novolac resin can also be cured by a resole resin.
  • the most common novolac resin curing agent is hexamethylenetetramine, which is a water soluble, heterocyclic organic compound with a cage-like structure resembling adamantane.
  • hexamethylenetetramine will react directly with phenolic resin and phenol without producing appreciable amounts of free formaldehyde at curing temperature, and then form cross-linked phenolic thermosetting.
  • the amount of curing agent is in the range of 5% to 55% by weight of novolac resin, preferably from 5% to 25% by weight of novolac resin.
  • polyphenol materials are preferably used as cross-linkable foaming agent.
  • the polyphenol can react with phenol resin and increase the mechanical strength of the foam.
  • Suitable polyphenol crosslinkers preferably comprise polyphenols that contain multiple phenol groups in the molecule.
  • Typical polyphenols include tannins, ellagitannin and theaflavin-3- gallate.
  • the polyphenols can be of natural source (for example plant-derived), and are found to exist largely in gallnuts, magnolia, fruits, vegetables, cereals, and beverages. For instance, tannic acid, a typical tannin, is up to 56% in gallnut. At present, the annual output of gallnuts is about 5,000 tons to 10,000 tons in China.
  • Polyphenol is mainly natural materials, and can also be synthesized, semi-synthesized and organic chemicals.
  • the weight percentage of polyphenols to novolac resin is preferably controlled in the range of 5 to 40 wt%.
  • the phenolic foam can optionally include one or more filler materials.
  • the weight percent of the filler material is preferably from 0 to 40 wt% based on the novolac-based phenolic resin.
  • filler material can be a single material or the mixture of different filler materials.
  • the addition of the filler can reduce, and in some cases significantly reduce foam manufacturing cost due to the cheaper price of the filler relative to novolac phenolic resin.
  • Adding filler can also improves the mechanical properties of phenolic foam.
  • Filler material can improve the processing and property of the final foam products. For example, it stops the adhesion of the foam onto the mould and increases mechanical strength depending on the type of filler material used.
  • the filler material used in the foam mixture is preferably micro- or nano-sized materials or their mixtures, including organic and inorganic nanowires, nanoparticles, nanoplatelet or their combination.
  • the filler materials preferably have an average particle size in the range of 10 nm to 5 pm.
  • the filler material can be micro- or nano-sized materials or their mixtures.
  • examples include inorganic clays, e.g. fibrous clays such as sepiolite and palygorskite (also known as attapulgite), layered clays such as montmorillonite and layered double hydroxides can be used as filler material.
  • functional groups for example hydroxide groups on clay surface, which can react with both phenolic resin and the foaming agent, polyphenol.
  • the filler material can be inorganic particles such as silica particles (Si0 2 ), ferriferous oxide particles (Fe 3 0 4 ), titanium dioxide particles (Ti0 2 ), carbon particles, calcium carbonate particles (CaC0 3 ), and aluminium oxide (AI2O3).
  • the filler material can be organic/inorganic nano- or micro-sized wires such as attapulgite, palygorskite, cellulose wires, metal wires and metal oxide wires; or nanoplatelets such as clay, layered double hydroxide (LDH), graphene, graphene oxide, boron nitride (BN), carbon nitride (C 3 N 4 ), mica layers;
  • organic/inorganic nano- or micro-sized wires such as attapulgite, palygorskite, cellulose wires, metal wires and metal oxide wires
  • nanoplatelets such as clay, layered double hydroxide (LDH), graphene, graphene oxide, boron nitride (BN), carbon nitride (C 3 N 4 ), mica layers;
  • the filler material can be organic powder such as PTFE powder, recycled powders from plastics/polymers, wood, bones and fibres, and nanofibres prepared from various technique (for example electrospinning) can be used as a filler.
  • organic powder such as PTFE powder, recycled powders from plastics/polymers, wood, bones and fibres, and nanofibres prepared from various technique (for example electrospinning) can be used as a filler.
  • the filler material can be organic filler materials including polymer particles, nanofibers and powders prepared from nature materials (for example plants such as cotton, wool, wood, and marine organism), epoxy resin powders, phenolic resin powders, wasted/recycled rubber powders.
  • organic filler materials including polymer particles, nanofibers and powders prepared from nature materials (for example plants such as cotton, wool, wood, and marine organism), epoxy resin powders, phenolic resin powders, wasted/recycled rubber powders.
  • the filler materials may also include chemicals which can react with phenolic resin or/and polyphenols.
  • reactive chemicals that can be included in the filler material are inorganic and organic chemicals, such as urea, sodium carbonate (Na 2 C0 3 ), sodium bicarbonate (NaHCOs), ammonium bicarbonate (NH 4 HC0 3 ), or ammonium carbonate ((NH 4 ) 2 C0 3 ).
  • FIG. 1 illustrates a typical process in which a phenolic foam can be made by directly curing the phenolic foam precursor in a mould using a process according to a first embodiment of the present invention.
  • a novolac-based phenolic resin, curing agent, cross-linkable foaming agent, and optional filler materials are uniformly mixed, and then poured into a mould.
  • the mould is heated, for example in an oven, to initiate foaming and cure the produced foam.
  • the novolac resin melts inducing decomposition of the foaming agent.
  • a highly porous foam forms as a result of volume expansion. Concurrently, the temperature also initiates the curing agent to cure the novolac resin into a highly cross-linked structure.
  • the foaming and curing temperature is therefore at least the melting point of the novolac-based phenolic resin, and is preferably selected in the range of 120 to 200 °C, and more preferably from 140 °C to 190 °C.
  • that filler material can be blended with novolac powder and foaming agent using a blender or miller, and then with polyphenol.
  • Figure 2 illustrates an embodiment of the two step process of the present invention.
  • the composite foam can also be prepared by:
  • Foaming Step Forming small bodies of phenolic foam.
  • any suitable phenolic foam bodies could be produced, for example a resole based foam bodies or novolac based foam bodies, for example both pure and modified novolac resins, pure and modified resole based phenolic foam, thermoplastic phenolic resins, such taught in CN 102504155A (Modified thermoplastic phenolic resin and preparation method) or CN102875752 B (Lignin modified thermoplastic phenolic resin and preparation method) the contents of which should be understood to be incorporated into this specification by these references.
  • thermoplastic phenolic resins such taught in CN 102504155A (Modified thermoplastic phenolic resin and preparation method) or CN102875752 B (Lignin modified thermoplastic phenolic resin and preparation method) the contents of which should be understood to be incorporated into this specification by these references.
  • the foaming step involves mixing together, preferably uniformly mixing together dry novolac-base phenolic resin powder, curing agent, foaming agent and an optional filler material, and then shaped into small precursor bodies, for example tablets (see below).
  • the small precursor bodies are then placed heated, for example in an oven.
  • the novolac resin melts inducing decomposition of the foaming agent.
  • a highly porous foam forms as a result of volume expansion.
  • the temperature also initiates the curing agent to cure the novolac resin into a highly cross-linked structure.
  • the foaming and curing temperature is therefore at least the melting point of the novolac-based phenolic resin, and is typically set in the range of 120 to 200 °C.
  • the preferred foaming and curing temperature range is 140 °C to 190 °C.
  • each phenolic foam precursor body or bit forms a corresponding foam body or piece.
  • a multitude of foam pieces can be produced on a mass scale when the pressing and foaming processes are operated in continuous manner.
  • the precursor bits expand during foaming and curing, typically having an expansion rate of from 3 times to 15 times.
  • the expansion rate depends on many factors, such as the composition, the types of filler materials, filler content, curing temperature, and shape of precursor bits.
  • the foam piece can be of any shape, either regular or irregular. Regular shapes of foam units are like square, rectangle, cylindrical, pill, donut-shape etc.
  • the precursor bodies can be formed into different shapes using a number of moulding or shaping processes. When moulds with different shapes and sizes are used, the precursor composite can be processed into different shapes and sizes.
  • a pressure forming process is used such as extrusion, pressuring moulding, punching, rolling or the like.
  • the mixture of novolac resin with other ingredients is pressed into pill, tablet, or donut-shape, using a press machine similar to the process of making drug tablets.
  • the mixture can be extruded into a small rod or tube, and then cut into short pieces.
  • the load pressure is can be 0.5 tons to 9 tons to form the precursor bodies.
  • the size of each precursor body depends on the pressure forming process. However, each precursor is preferable formed with a particle size from
  • the precursor composite can be pressed into pills with the diameter of 9 mm and thickness of 3 mm.
  • the pills are made under the load pressure of 3 tons using a press machine.
  • the shape of the pills is dictated by the configuration of the mould used.
  • the foam bodies/ pieces are assembled into a desired consolidate shape and/or configuration suitable for a desired product.
  • the foam bodies can be consolidated into a rectangular block, brick, sheet, slab, billet or the like.
  • FIG. 2 illustrates a schematic process of assembling the formed phenolic foam bodies or pieces into a desired shape.
  • foam pieces are blended with an adhesive.
  • the blended mixture is then cast into a mould and then held at a curing temperature, for example room temperature, for a set length of time (for example 48 hours) to allow the adhesive to cure.
  • a consolidated foam body with the desired shape is formed.
  • the adhesive is applied to the surface of the phenolic foam pieces and it binds the phenolic foam bodies into larger size with desired shape.
  • the adhesive can be applied by any suitable process, including dipping, spraying, brushing, or other coating techniques. Various adhesives can be used.
  • the adhesive is applied just on the surface of the foam pieces so that it does not fill into the pores but can bond the foam pieces into a unit block.
  • the adhesive can be applied onto the surface of phenolic foam pieces through spraying, brushing, or blending.
  • Preferably, only a thin coating is applied on the surface of foam bodies.
  • the surface of the foam bodies can be coated with 0.01 mm to 0.15 mm thick adhesive in some embodiments.
  • the ratio of adhesive to foam pieces is from 1 % to 15 % by weight of foam bodies. The ratio depends on the types of adhesive, coating method, foam shape, porosity, pore size and dimension. [092]
  • the condition for bonding foam pieces is dependent on the adhesive agent.
  • the adhesive used to bond the phenolic foam bodies can be thermosetting resin based adhesive, such as epoxy based adhesive, phenolic resin based adhesive, fire-retardant silicone adhesive, or heat resistant silicone.
  • curing can be accomplished using high temperature, hot-press, UV-irradiation or the like.
  • a suitable adhesive is flame retardant adhesive Araldite 1570 A/B supplied by Huntsman Corporation. This particular adhesive comprises a resin and a hardener that is blended for use.
  • a protective material or shell can be applied on the consolidated foam body.
  • the protective materials can include aluminium foil, sulphate paper such as Kraft, fabric, metal sheet, plaster board, polymer sheet, polymer films such as polyimide film, polyphenylene sulphide film, or polyvinyl chloride) film.
  • the protective material can be applied during the shaping process of the foam, for example covering an inner surface of the mould with the protective material prior to adhesive curing.
  • the shell adheres on the phenolic foam assembly after removal from the mould.
  • the protective shell can be mounted onto the surface of the foam assembly after removal from the mould.
  • the shape of the consolidated foam body can be achieved from a moulding or casting process, and/or from mechanical methods such as cutting after the consolidated foam body is formed.
  • the present invention provides a way of bonding the phenolic foam bodies with other materials such as fire-resistant or/and thermal insulating blocks, concrete foam pieces, starch foam units or polymer-based foam units.
  • the phenolic foam bodies can be adhered to these materials during the assembling, agglomeration and/or consolidation step. In this way, a multifunction composite foam product or arrangement could result.
  • Example 1 A phenolic foam without filler
  • the Kraft paper was well adhered around the foam body.
  • the foam together with the Kraft paper was easy to remove from the mould.
  • the resulting phenolic foam block had a dimension of 450 mmx300 mmx60 mm (length ⁇ width ⁇ thickness).
  • the phenolic foam block was cut into small pieces to test the properties.
  • the phenolic foam was cut into small block with the dimension of 100 mmx100 mmx60 mm, and weight using a balance. The density can be calculated from the weight and volume.
  • the density of the phenolic foam was found to be approximately 0.056 g/cm 3
  • the compression strength was tested using Instron 5967 under compression model. The compression strength was found to be about 0.328 MPa.
  • the thermal conductivity was tested using thermal constants analyser TPS 2500S under the temperature 25 °C. The thermal conductivity was found to be about 0.025 W/(m K).
  • Example 2 A phenolic foam without a filler made using two-step process technique.
  • the phenolic foam block was cut into small pieces to test the properties.
  • For density the phenolic foam was cut into small block with the dimension of 100 mmx100 mmx60 mm, and weight using a balance. The density can be calculated from the weight and volume.
  • the compression strength was tested using Instron 5967 under compression model. The density of the phenolic foam was approximately 0.070 g/cm 3 , and compression strength was about 0.652 MPa.
  • the thermal conductivity of the phenolic foam was about 0.0314 W/(m K).
  • Example 3 A phenolic foam containing filler made by the two-step technique.
  • the phenolic foam block was cut into small pieces to test the properties.
  • the phenolic foam was cut into small block with the dimension of 100 mmx100 mmx60 mm, and weight using a balance. The density can be calculated from the weight and volume.
  • the density of the phenolic foam was approximately 0.076 g/cm 3 .
  • the compression strength was about 1 .554 MPa.
  • the thermal conductivity was tested using thermal constants analyser TPS 2500S under the temperature 25 °C. The thermal conductivity was about 0.0349 W/(m K).
  • Example 4 A phenolic foam with filler made by one-step technique.
  • Novolac resin a kind of two stage phenol-formaldehyde polymer supplied by Plenco Company, USA, was grounded into fine powder.
  • 100 g novolac resin, 15 g hexamethylenetetramine, 20 g attapulgite and 20 g tannic acid were milled together.
  • the milled mixture was poured into a mould.
  • the inner mould wall was covered with an aluminium foil.
  • the mould was put into an oven at 165 °C, and the phenolic foam precursor compounds were cured for 20 minutes.
  • the aluminium foil was well adhered onto the foam.
  • the final phenolic foam was removed from the mould, together with aluminium foil.
  • a phenolic foam block (length 800 mm, width 400 mm and thickness 70 mm) was prepared.
  • the phenolic foam block was cut into small pieces to test the properties.
  • the phenolic foam was cut into small block with the dimension of 100 mmx100 mmx60 mm, and weight using a balance. The density can be calculated from the weight and volume.
  • the density of the obtained phenolic foam was approximately 0.095 g/cm 3 .
  • the compression strength was about 0.789 MPa.
  • the thermal conductivity was tested using thermal constants analyser TPS 2500S under the temperature 25 °C. The thermal conductivity was about 0.0297 W/(m K).
  • Example 5 A phenolic foam with filler prepared by the two-step method.
  • the final phenolic foam was removed together with aluminium foil from the mould.
  • the small foam pieces were bonded into a foam disk (diameter 800 mm and thickness 100 mm) and properties measured.
  • the phenolic foam was cut into small block with the dimension of 100 mmx100 mmx60 mm, and weight using a balance. The density can be calculated from the weight and volume.
  • the density of the phenolic foam was approximately 0.070 g/cm 3
  • the compression strength was about 1 .219 MPa.
  • the thermal conductivity was tested using thermal constants analyser TPS 2500S under the temperature 25 °C. The thermal conductivity was about 0.0378 W/(m K).
  • Example 6 A phenolic foam with filler prepared using one-step method.
  • Novolac phenolic resin powder prepared in the lab based on the pastille two stage phenol-formaldehyde polymer resin supplied by Plenco Company, USA was pre-blended with hexamethylenetetramine (HMTA), 15% weight percent of novolac resin. 1 15 g pre-blended novolac- HMTA was blended with 13 g tannic acid and 5 g attapulgite using a blender. Then, the mixture was poured into a mould. The whole inner wall of the mould was covered by a polyimide film. The mould was then put into an oven at the temperature 175 °C for 20 minutes to prepare phenolic foam. The polyimide film was well adhered onto the foam. The final phenolic foam was removed from the mould together with polyimide film.
  • HMTA hexamethylenetetramine
  • the phenolic foam block was cut into small pieces to test the properties.
  • the phenolic foam was cut into small block with the dimension of 100 mmx100 mmx60 mm, and weight using a balance. The density can be calculated from the weight and volume.
  • the density of the phenolic foam was approximately 0.058 g/cm 3 .
  • the compression strength was about 0.395 MPa.
  • the thermal conductivity was tested using thermal constants analyser TPS 2500S under the temperature 25 °C. The thermal conductivity was about 0.0298 W/(m K).
  • Example 7 A phenolic foam prepared from modified novolac thermoplastic phenolic resin using one-step method.
  • Modified novolac thermoplastic phenolic resin prepared by mixing novolac resin and silicone resin in the lab. 100 g modified novolac thermoplastic phenolic resin was blended with 13 g hexamethylenetetramine (HMTA), 10 g tannic acid and 8 g attapulgite using a blender. Then, the mixture was poured into a mould. The whole inner wall of the mould was covered by aluminium foil. The mould was then put into an oven at the temperature 170 °C for 20 minutes to prepare phenolic foam. The aluminium foil was well adhered onto the foam. The final phenolic foam was removed from the mould.
  • HMTA hexamethylenetetramine
  • the phenolic foam block was cut into small pieces to test the properties.
  • phenolic foam was cut into small block with the dimension of 100 mmx100 mmx60 mm, and weight using a balance. The density can be calculated from the weight and volume.
  • the density of the phenolic foam was approximately 0.068 g/cm 3
  • the compression strength was about 0.380 MPa.
  • the thermal conductivity was tested using thermal constants analyser TPS 2500S under the temperature 25 °C. The thermal conductivity was about 0.0310 W/(m K).
  • Example 8 Novolac resin powder with 15% HMTA, 20% tannic acid and 20% attapulgite
  • One particular embodiment of the present invention comprises a foam body formed from a mixture of novolac resin powder prepared in the lab based on the pastille two stage phenol-formaldehyde polymer resin supplied by Plenco Company, USA with 15% HMTA, 20% tannic acid and 20% attapulgite (all based on weight of novolac resin).
  • a foam block was prepared using the two step method described above.
  • phenolic resin without attapulgite was also prepared.
  • the mixture of phenolic foam precursor compounds was poured into a mould whose inner walls covered with aluminium foil, and then cured at 165 °C for 20 minutes.
  • the cured phenolic foam was removed from the mould and cut into small blocks with desired size to test the properties of phenolic foam.
  • the use of filler, attapulgite can stop the powder of phenolic foam precursor sticking on the blender in the mixing process.
  • the presence of attapulgite improved the thermal stability of the phenolic foam in air environment. As shown in Figure 3, the attapulgite-containing sample can increase the thermal decomposition temperature by 10 °C to 25 °C.
  • Attapulgite also improved the compression strength of the phenolic foam.
  • the stress-strain curves were shown in Figure 4.
  • the compression strength was about 0.328 MPa.
  • the compression strength increases to 0.767 MPa.

Abstract

La présente invention concerne un nouveau procédé de préparation d'une mousse phénolique à base de novolac comprenant : la formation d'au moins un corps précurseur comprenant un mélange d'au moins une résine novolaque, d'au moins un agent moussant de réticulation, et d'au moins un agent de durcissement ; le moussage du mélange de corps précurseur par chauffage du mélange jusqu'à au moins la température de fusion de la résine novolaque, pour produire un corps précurseur expansé ; et le durcissement du corps précurseur expansé, formant ainsi au moins un corps en mousse phénolique.
PCT/AU2016/051199 2015-12-07 2016-12-07 Procédé de formation de mousse phénolique WO2017096423A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AU2015905060 2015-12-07
AU2015905060A AU2015905060A0 (en) 2015-12-07 Method of forming Phenolic Foam

Publications (1)

Publication Number Publication Date
WO2017096423A1 true WO2017096423A1 (fr) 2017-06-15

Family

ID=59012493

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU2016/051199 WO2017096423A1 (fr) 2015-12-07 2016-12-07 Procédé de formation de mousse phénolique

Country Status (1)

Country Link
WO (1) WO2017096423A1 (fr)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107162309A (zh) * 2017-07-04 2017-09-15 浙江海洋大学 一种基于温敏性磁纳米材料的乳化石油废水处理装置
CN108276615A (zh) * 2017-12-29 2018-07-13 华中科技大学 一种高导热层状石墨烯复合材料及制备方法
CN108624195A (zh) * 2018-06-07 2018-10-09 西南石油大学 一种g-C3N4-G/水性环氧复合涂料的制备方法
CN108744959A (zh) * 2018-06-05 2018-11-06 广西中医药大学 一种除甲醛石墨烯碳包的制备方法及应用
CN108772083A (zh) * 2018-08-17 2018-11-09 佛山朝鸿新材料科技有限公司 一种氧化石墨烯-类水滑石复合薄膜的制备方法
CN108842168A (zh) * 2018-06-29 2018-11-20 太原理工大学 一种两步电化学法制备g-C3N4/MMO复合薄膜光电极
CN110305467A (zh) * 2019-07-12 2019-10-08 常州大学 一种石墨烯协效阻燃抑烟材料及其制备方法
CN110305443A (zh) * 2019-06-03 2019-10-08 泰能环保科技（浙江）有限公司 一种石墨烯复合导热材料及其制备方法
CN110437500A (zh) * 2019-08-15 2019-11-12 浙江宇翔生物科技有限公司 一种提高橡胶刚度的橡胶加工助剂及其生产工艺
CN110918051A (zh) * 2018-09-20 2020-03-27 中国科学院上海硅酸盐研究所 一种可用于污水处理的强吸附型石墨烯基复合材料
CN111716619A (zh) * 2020-06-03 2020-09-29 南通市众惠模具有限公司 一种高清理效率的发泡模具加工方法
CN111944193A (zh) * 2020-07-23 2020-11-17 马鞍山市金韩防水保温工程有限责任公司 一种轻质耐用建筑保温板及其制备方法
CN112409757A (zh) * 2020-10-21 2021-02-26 江苏科化新材料科技有限公司 一种高功率模块封装用高导热环氧塑封料及其制备方法
CN112724447A (zh) * 2020-12-14 2021-04-30 苏州圣杰特种树脂有限公司 一种墙面保温酚醛树脂发泡材料及其制备方法
CN117283743A (zh) * 2023-11-23 2023-12-26 绵阳华远同创科技有限公司 一种树脂生产成型加工流程预测控制系统及方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3511789A (en) * 1966-04-21 1970-05-12 Owens Corning Fiberglass Corp Polymerizable materials of improved stability and foams produced therefrom
JPS595038A (ja) * 1982-07-02 1984-01-11 Toyo Rubber Chem Ind Co Ltd フエノ−ル発泡成形体の製造方法
SU448745A1 (ru) * 1970-06-08 1984-10-30 Предприятие П/Я Г-4059 Способ получени пенопластов на основе жидких фенолформальдегидных смол новолачного типа
WO2004063259A1 (fr) * 2003-01-16 2004-07-29 Abdeslam Kasseh Nanocomposites organo-argile/novolak auto-expansibles et procedes connexes
US7605189B1 (en) * 2006-05-22 2009-10-20 Brotz Gregory R Process for producing a phenolic foam

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3511789A (en) * 1966-04-21 1970-05-12 Owens Corning Fiberglass Corp Polymerizable materials of improved stability and foams produced therefrom
SU448745A1 (ru) * 1970-06-08 1984-10-30 Предприятие П/Я Г-4059 Способ получени пенопластов на основе жидких фенолформальдегидных смол новолачного типа
JPS595038A (ja) * 1982-07-02 1984-01-11 Toyo Rubber Chem Ind Co Ltd フエノ−ル発泡成形体の製造方法
WO2004063259A1 (fr) * 2003-01-16 2004-07-29 Abdeslam Kasseh Nanocomposites organo-argile/novolak auto-expansibles et procedes connexes
US7605189B1 (en) * 2006-05-22 2009-10-20 Brotz Gregory R Process for producing a phenolic foam

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; AN 1985- *

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107162309A (zh) * 2017-07-04 2017-09-15 浙江海洋大学 一种基于温敏性磁纳米材料的乳化石油废水处理装置
CN108276615A (zh) * 2017-12-29 2018-07-13 华中科技大学 一种高导热层状石墨烯复合材料及制备方法
CN108744959A (zh) * 2018-06-05 2018-11-06 广西中医药大学 一种除甲醛石墨烯碳包的制备方法及应用
CN108624195A (zh) * 2018-06-07 2018-10-09 西南石油大学 一种g-C3N4-G/水性环氧复合涂料的制备方法
CN108842168B (zh) * 2018-06-29 2020-06-02 太原理工大学 一种两步电化学法制备g-C3N4/MMO复合薄膜光电极
CN108842168A (zh) * 2018-06-29 2018-11-20 太原理工大学 一种两步电化学法制备g-C3N4/MMO复合薄膜光电极
CN108772083A (zh) * 2018-08-17 2018-11-09 佛山朝鸿新材料科技有限公司 一种氧化石墨烯-类水滑石复合薄膜的制备方法
CN108772083B (zh) * 2018-08-17 2021-01-15 苏州烯时代材料科技有限公司 一种氧化石墨烯-类水滑石复合薄膜的制备方法
CN110918051B (zh) * 2018-09-20 2021-08-06 中国科学院上海硅酸盐研究所 一种可用于污水处理的强吸附型石墨烯基复合材料
CN110918051A (zh) * 2018-09-20 2020-03-27 中国科学院上海硅酸盐研究所 一种可用于污水处理的强吸附型石墨烯基复合材料
CN110305443A (zh) * 2019-06-03 2019-10-08 泰能环保科技（浙江）有限公司 一种石墨烯复合导热材料及其制备方法
CN110305467A (zh) * 2019-07-12 2019-10-08 常州大学 一种石墨烯协效阻燃抑烟材料及其制备方法
CN110437500A (zh) * 2019-08-15 2019-11-12 浙江宇翔生物科技有限公司 一种提高橡胶刚度的橡胶加工助剂及其生产工艺
CN110437500B (zh) * 2019-08-15 2021-09-07 浙江蓝色海洋生物科技有限公司 一种提高橡胶刚度的橡胶加工助剂及其生产工艺
CN111716619A (zh) * 2020-06-03 2020-09-29 南通市众惠模具有限公司 一种高清理效率的发泡模具加工方法
CN111944193A (zh) * 2020-07-23 2020-11-17 马鞍山市金韩防水保温工程有限责任公司 一种轻质耐用建筑保温板及其制备方法
CN112409757A (zh) * 2020-10-21 2021-02-26 江苏科化新材料科技有限公司 一种高功率模块封装用高导热环氧塑封料及其制备方法
CN112724447A (zh) * 2020-12-14 2021-04-30 苏州圣杰特种树脂有限公司 一种墙面保温酚醛树脂发泡材料及其制备方法
CN117283743A (zh) * 2023-11-23 2023-12-26 绵阳华远同创科技有限公司 一种树脂生产成型加工流程预测控制系统及方法
CN117283743B (zh) * 2023-11-23 2024-02-02 绵阳华远同创科技有限公司 一种树脂生产成型加工流程预测控制系统及方法

Similar Documents

Publication Publication Date Title
WO2017096423A1 (fr) Procédé de formation de mousse phénolique
Pilato Phenolic resins: 100 Years and still going strong
JP5203944B2 (ja) 発泡成形体の製造方法、これにより得られた発泡体及びその使用法
KR101028523B1 (ko) 고단열성 발포성 폴리스티렌 입자 및 그 제조방법
JP2009506149A5 (fr)
JP2017206714A5 (fr)
CN103834056A (zh) 聚苯乙烯保温板的生产方法
JP2013504511A (ja) 機能性無機ボード及びその製造方法
WO2012053493A1 (fr) Plaque expansée de résine phénolique
CN104072939A (zh) 一种改性聚苯板及其制备方法
CN105431480A (zh) 泡沫复合材料
CN105452357A (zh) 用于制备泡沫复合材料的方法
CN105482357A (zh) 一种酚醛树脂组合物及其制备的发泡材料和成型材料
CN105482243A (zh) 一种酚醛树脂组合物及其制备的发泡材料和成型材料
CN112585182A (zh) 粘合剂和形成粘合剂的方法
CN105462161A (zh) 一种酚醛树脂组合物及其制备的发泡材料和成型材料
CN105754253A (zh) 一种具有保温功能的硅藻泥地板
CN108779283A (zh) 泡沫复合材料
CN106630837A (zh) 一种复合聚多巴胺膜改性再生eps粒子‑硅酸盐水泥复合发泡保温板及其制备方法
JPS6071508A (ja) 微細孔径炭素多孔体の製造法
EP3802112A1 (fr) Métamatériaux à base phénolique et procédés de formation de métamatériaux à base phénolique
CN108864469A (zh) 一种干法发泡制备酚醛泡沫的方法
CN101171207B (zh) 板状轻量无机聚集制件、其制造方法和所得的板
JPH0571621B2 (fr)
JP2001058815A (ja) 高分子量化した水性造膜性無機化合物成型前駆物とその成型法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16871819

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16871819

Country of ref document: EP

Kind code of ref document: A1