WO1997008230A1 - Procede de production de mousses phenoliques - Google Patents

Procede de production de mousses phenoliques Download PDF

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Publication number
WO1997008230A1
WO1997008230A1 PCT/US1996/013387 US9613387W WO9708230A1 WO 1997008230 A1 WO1997008230 A1 WO 1997008230A1 US 9613387 W US9613387 W US 9613387W WO 9708230 A1 WO9708230 A1 WO 9708230A1
Authority
WO
WIPO (PCT)
Prior art keywords
resol
foam
density
process according
blowing agent
Prior art date
Application number
PCT/US1996/013387
Other languages
English (en)
Inventor
Byron J. Hulls
Vyacheslav S. Grinshpun
Jennifer M. Willson
Original Assignee
Owens Corning
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Owens Corning filed Critical Owens Corning
Priority to AU67785/96A priority Critical patent/AU6778596A/en
Priority to JP9510368A priority patent/JPH11512131A/ja
Publication of WO1997008230A1 publication Critical patent/WO1997008230A1/fr

Links

Classifications

    • 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
    • C08J9/12—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 physical blowing agent
    • C08J9/14—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 physical blowing agent organic
    • 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
    • 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

Definitions

  • TECHNICAL FIELD This invention relates to a process for producing low-density phenolic foams having good thermal properties, high thermal retention, and good fire performance.
  • the process uses non-ozone-depleting blowing agents.
  • Phenolic foams have been used for years as insulating materials. Their good thermal and aged thermal performance is well known. Closed-cell phenolic foams retain blowing agent gases longer and have slower air ingress than urethane, isocyanurate, and polystyrene foams. The retention of thermal conductivity over time, due to the lower permeability ofthe phenolic foam to the blowing agent and atmospheric gases, provides improved thermal insulating performance over the life span ofthe product. Phenolic materials have also been recognized as having excellent fire properties and low smoke evolution compared to other types of foam materials.
  • a foaming composition of: (a) a phenol formaldehyde resol resin having little or substantially no free formaldehyde and having a water content of 4 to 8% and a viscosity ranging from 5,000 cps to 40,000 cps at 40°C, (b) a blowing agent, (c) a surfactant, and (d) a catalyst; mixing the composition to initiate foaming and to produce a resol foam; and curing the resol foam to a density ranging from 0.5 to 9.0 pounds per cubic foot (8.01 to 144.166 kg m 3 ).
  • This process allows us to foam phenol formaldehyde resins which have a high viscosity, and cure the foams to a very low density.
  • blowing agents we use generally are hydrocarbons, including aliphatic and alicyclic alkanes.
  • Preferred blowing agents are aliphatic alkanes, including pentane.
  • the aliphatic alkanes contain at least 4, but no more than 7 carbon atoms. Examples include pentane, hexane, heptane, isobutane, and isopentane. Unsaturated hydrocarbons such as pentene and hexene also are included.
  • the cycloaliphatic (or alicyclic) hydrocarbons containing at least 4, but no more than 7 carbon atoms can be saturated or unsaturated.
  • Illustrative saturated cycloaliphatic hydrocarbons are cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane.
  • Illustrative unsaturated cycloaliphatic hydrocarbons are cyclopentene, cyclohexene, and 1,3-cyclohexadiene.
  • foams are prepared from resols which have been made using conventional starting mole ratios of phenol to formaldehyde, in the present case in the range of 1 : 1 to 1 :4.5, preferably 1 : 1.5 to 1 :2.5.
  • the high mole ratio materials are the basis for resins which are substantially free of phenol and which can be treated with a formaldehyde co-reactant or scavenger, to reduce the initially high free formaldehyde content.
  • the resin is concentrated to reduce the free water content ofthe resin.
  • a typical resin used for manufacturing resol foam has a viscosity in the order of 4,000 to 40,000 cps and a free water content of 4 to 8%.
  • the resin utilized will preferably have a viscosity in the order of 5,000 to 20,000 cps at 40°C.
  • the foamable resol mixture (resin, surfactant, blowing agent, catalyst) can be dispensed in either a batch or continuous process.
  • the foamable mixture is poured into an 80°C preheated mold, enclosed, and cured in an oven at 80°C for 20 minutes. Following demolding, the foam is additionally cured for 2 hours at 80°C.
  • the foamable composition is dispensed from evenly spaced tubes and nozzles onto a moving carrier sheet. Parallel lines of foam froth knit together as the froth expands to form a continuous sheet which moves through a conveyor oven at approximately 80°C. The boards are transferred to a separate oven for additional curing.
  • the cured resol foam has a density ranging from 0.5 to 9.0 pounds per cubic foot (8.01 to 144.166 kg/m 3 ).
  • Example 1 Preparation of Resol
  • the resol resin used in the production of these foams used a formaldehyde:phenol (F P) mole ratio of 2.3:1, using 52% formaldehyde and 99% phenol.
  • the reaction was carried out under basic conditions at elevated temperatures with 50% caustic solution. When the Ostwald viscosity ofthe resin reached 62cst (measured at 25°C), the reaction was cooled and neutralized with 50% aqueous aromatic sulphonic acid. Urea was added as a formaldehyde scavenger at a level of 77% by mole ofthe residual formaldehyde.
  • the resin was passed through a thin film evaporator to reduce the water content from about 30% to 4-8%.
  • the final viscosity ofthe resin was 4,000-12,000 cps (measured at 40°C).
  • Example 2 Preparation of Resol Foam
  • a phenolic resol prepared according to Example 1 having a formaldehyde/phenol ratio of 2.3, containing 7% water and having a viscosity of 5,200 cps at 40°C and mixed it with 2.25g of a surfactant blend of 1:1 (w:w) ethoxylated alkylphenol, Harfoam PI (Huntsman Chemical Co.) and ethylene oxide-propylene oxide block copolymer Pluronic F127 (BASF).
  • a surfactant blend 1:1 (w:w) ethoxylated alkylphenol, Harfoam PI (Huntsman Chemical Co.) and ethylene oxide-propylene oxide block copolymer Pluronic F127 (BASF).
  • the foam had a density of 1.54 pcf (24.668 kg/m 3 ) and had a thermal conductivity of 0.145 Btu.in/hft ⁇ F (0.021 w/m.K). After 200 days of room-temperature aging, the thermal conductivity was 0.145 Btu.in/hft ⁇ F (0.021 w/m.K). After 200 days of room-temperature aging, the thermal conductivity was 0.145 Btu.in/hft ⁇ F (0.021 w/m.K). After 200 days of room-temperature aging, the thermal conductivity was
  • Example 3 Preparation of Resol Foam We also blended 38.0g ofthe resol of Example 1 with 1.7g ofthe surfactant
  • Example 2 15 in Example 2. To this was added 5. lg of n-pentane which was then stirred until the pentane was equally distributed. To the blend, we added quickly with stirring 5g ofthe catalyst material of Example 2. The resultant blend was transferred to the mold as in Example 2 preheated to 70°C. The mold was placed in an oven at 70°C for 20 minutes, demolded, and further cured at 70°C for 3 hours. The foam had a density of 1.12 pcf (17.941 kg/m 3 ), an
  • Example 4 Preparation of Resol Foam We also blended 30.0g of a blend ofthe resol of Example 1 and the surfactant in Example 2
  • Example 5 Preparation of Foam fcontroD
  • Alkapol SOR 490 Rhone Poulenc
  • Mondur MR Mobay
  • DabcoT9 Air Products
  • Table 1 shows that low-density resol foams can be produced with non- ozone-depleting alkane blowing agents. Both the initial thermal conductivity and the thermal performance after 200 days are excellent, illustrating the high thermal efficiency of the low-density resol foam. Furthermore, as Table 1 shows, the foam in Example 2 had excellent flame-resistant properties, extinguishing on removal of a flame source, whereas comparative Example 5, a rigid polyisocyanurate foam, continued to burn upon removal of the flame.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne la production de mousses résol de faible densité à partir de résines résol. Les mousses résol ont une densité de 144,166 kg/m3 ou moins et sont produites à l'aide d'agents d'expansion hydrocarburés non halogénés tels que le pentane.
PCT/US1996/013387 1995-08-28 1996-08-19 Procede de production de mousses phenoliques WO1997008230A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU67785/96A AU6778596A (en) 1995-08-28 1996-08-19 Process for producing phenolic foams
JP9510368A JPH11512131A (ja) 1995-08-28 1996-08-19 フェノール樹脂フォームの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US52012295A 1995-08-28 1995-08-28
US08/520,122 1995-08-28

Publications (1)

Publication Number Publication Date
WO1997008230A1 true WO1997008230A1 (fr) 1997-03-06

Family

ID=24071296

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/013387 WO1997008230A1 (fr) 1995-08-28 1996-08-19 Procede de production de mousses phenoliques

Country Status (4)

Country Link
JP (1) JPH11512131A (fr)
KR (1) KR19990044126A (fr)
AU (1) AU6778596A (fr)
WO (1) WO1997008230A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013689A (en) * 1997-05-02 2000-01-11 Jiffy Foam, Inc. Method for making a closed-cell phenolic resin foam, foamable composition, and closed-cell phenolic resin foam
US6492432B1 (en) 1999-11-09 2002-12-10 American Foam Technologies, Inc. Novolac-epoxy resin foam, foamable composition for making novolac-epoxy resin foam and method of making novolac-epoxy resin foam
JP2009293033A (ja) * 1997-09-03 2009-12-17 Asahi Kasei Construction Materials Co Ltd フェノール樹脂発泡体
US9120904B2 (en) 2008-11-07 2015-09-01 Asahi Kasei Contruction Materials Corporation Expandable phenolic resin composition, phenolic resin foam, and method for producing the phenolic resin foam
WO2020025544A1 (fr) 2018-07-30 2020-02-06 Kingspan Holdings (Irl) Limited Mousse phénolique et son procédé de fabrication

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4601855B2 (ja) * 2001-05-18 2010-12-22 旭有機材工業株式会社 発泡性フェノール系レゾール樹脂組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4207400A (en) * 1977-11-16 1980-06-10 Monsanto Company Foamable resole resin composition
US4207401A (en) * 1978-06-05 1980-06-10 Monsanto Company Foamable resole resin composition
US4216295A (en) * 1976-12-20 1980-08-05 Monsanto Company Foamable resole resin composition
US4303758A (en) * 1976-06-07 1981-12-01 Gusmer Frederick E Method of preparing closed cell phenol-aldehyde foam and the closed cell foam thus prepared

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4303758A (en) * 1976-06-07 1981-12-01 Gusmer Frederick E Method of preparing closed cell phenol-aldehyde foam and the closed cell foam thus prepared
US4216295A (en) * 1976-12-20 1980-08-05 Monsanto Company Foamable resole resin composition
US4207400A (en) * 1977-11-16 1980-06-10 Monsanto Company Foamable resole resin composition
US4207401A (en) * 1978-06-05 1980-06-10 Monsanto Company Foamable resole resin composition

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013689A (en) * 1997-05-02 2000-01-11 Jiffy Foam, Inc. Method for making a closed-cell phenolic resin foam, foamable composition, and closed-cell phenolic resin foam
JP2009293033A (ja) * 1997-09-03 2009-12-17 Asahi Kasei Construction Materials Co Ltd フェノール樹脂発泡体
JP4711469B2 (ja) * 1997-09-03 2011-06-29 旭化成建材株式会社 フェノール樹脂発泡体
US6492432B1 (en) 1999-11-09 2002-12-10 American Foam Technologies, Inc. Novolac-epoxy resin foam, foamable composition for making novolac-epoxy resin foam and method of making novolac-epoxy resin foam
US6610754B1 (en) 1999-11-09 2003-08-26 American Foam Technologies, Inc. Novolac-epoxy resin foam, foamable composition for making novolac-epoxy resin foam and method of making novolac-epoxy resin foam
US6727293B2 (en) 1999-11-09 2004-04-27 American Foam Technologies, Inc. Novolac-epoxy resin foam, foamable composition for making novolac-epoxy resin foam and method of making novolac-epoxy resin foam
US9120904B2 (en) 2008-11-07 2015-09-01 Asahi Kasei Contruction Materials Corporation Expandable phenolic resin composition, phenolic resin foam, and method for producing the phenolic resin foam
WO2020025544A1 (fr) 2018-07-30 2020-02-06 Kingspan Holdings (Irl) Limited Mousse phénolique et son procédé de fabrication
US11898020B2 (en) 2018-07-30 2024-02-13 Kingspan Holdings (Irl) Limited Phenolic foam and method of manufacture thereof

Also Published As

Publication number Publication date
KR19990044126A (ko) 1999-06-25
JPH11512131A (ja) 1999-10-19
AU6778596A (en) 1997-03-19

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