EP0116308A1 - Phenolische Polyole und damit hergestellte feste Schaumzusammensetzungen - Google Patents

Phenolische Polyole und damit hergestellte feste Schaumzusammensetzungen Download PDF

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Publication number
EP0116308A1
EP0116308A1 EP84100380A EP84100380A EP0116308A1 EP 0116308 A1 EP0116308 A1 EP 0116308A1 EP 84100380 A EP84100380 A EP 84100380A EP 84100380 A EP84100380 A EP 84100380A EP 0116308 A1 EP0116308 A1 EP 0116308A1
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EP
European Patent Office
Prior art keywords
phenol
product
mixture
carbon atoms
mole percent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP84100380A
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English (en)
French (fr)
Inventor
John Paul Rupert
John Thomas Patton, Jr.
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BASF Corp
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BASF Wyandotte Corp
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Publication date
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Publication of EP0116308A1 publication Critical patent/EP0116308A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/36—Chemically modified polycondensates by etherifying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C08G18/542—Polycondensates of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0041—Foam properties having specified density
    • C08G2110/005—< 50kg/m3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2115/00—Oligomerisation
    • C08G2115/02—Oligomerisation to isocyanurate groups

Definitions

  • This invention relates to phenol/aldehyde-based polyols and to rigid cellular compositions derived from these polyols. Specifically it deals with modified benzylic ether-containing resole polyols and the rapid curing, low combustibility, low friability, closed cell, rigid cellular plastic compositions obtained by reaction of the polyols with polyisocyanates.
  • Simple phenolic foams obtained by the thermal and acid catalyzed polymerization of resole resins or of novolac resins with added aldehydic compounds are old in the art. Such foams are noted particularly for their excellent fire resistance. However, they also possess the properties of punking, extreme friability, and being opened-cell which make them ill-suited for insulation or any use where the foam must be handled or support weight. There is a long- established desire to use such phenolic resins in cellular polyurethane or polyisocyanurate formations with the hope of improving strength, insulation, and punking properties while retaining the inherent low combustibility of phenolic foams.
  • hydroxymethyl ring substituents of the above "resole” are highly reactive toward unsubstituted ortho or para phenolic ring positions. Thus, such condensates can be easily cross-linked to form infusible solids by heating or acidifying. Acid catalysis is not normally used in the preparation of resoles since cross-linking leading to gelation can easily occur.
  • novolacs Such products are called “novolacs” and, lacking the reactive hydroxymethyl substituent, can be prepared under acid catalysis to benefit from a faster rate of formation.
  • phenol/aldehyde condensates novolacs and resoles
  • modified resoles are etherified with aliphatic polyols (under acid conditions) and the products are used to prepare polyurethane or polyisocyanurate foams.
  • these phenol-formaldehyde derived resins yielded polyurethanes with poor inherent flammability properties.
  • To obtain suitable flame retardant foams required the use of chlorophenol as the phenolic reactant and/or added phosphate-type flame retardant in the foam formulation.
  • This invention is a class of modified benzyl ether-containing resole polyols obtained by a process comprising reacting at 100°C to 130°C (a) a phenol which is free of ortho substituents, (b) a molar excess relative to the phenol of a nonaqeous aldehyde having the formula RCHO where R is hydrogen, an alkyl group of 1 to 6 carbon atoms, or a halogenated alkyl group of 1 to 3 carbon atoms, and (c) less than fifty mole percent relative to the phenol of an aliphatic hydroxyl compound having a functionality of 1 to 4, 1 to 12 carbon atoms, and 0 to 5 ether oxygen atoms in the presence of a catalytic amount of a metal derivative selected from the group consisting of (i) carboxylate salts of divalent ions of Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca, Ba, and (di C -C alkyltin)
  • the polyols are especially suited for reaction with organic polyisocyanates to yield low combustibility, low friability, closed-cell, rigid cellular plastics.
  • the polyurethane foams are rapid curing and do not require post curing to achieve excellent physical properties.
  • modified benzyl ether-containing resole polyols of this invention are prepared by the metal salt or titanate ester catalyzed reaction of a phenol with a molar excess of a nonaqueous aldehyde and a modifying amount of a mono- or polyhydroxyl compound.
  • the general procedure for the production of these polyols is to charge the phenol, nonaqueous aldehyde, catalyst, and modifying hydroxyl compound to a stirred reactor fitted with a condenser system which is suitable for either reflux or distillate removal.
  • the stirred mixture is heated rapidly to about 100°C to 105°C at which point a slight exotherm occurs.
  • the mixture is maintained at 110°C to 115°C for several hours under slow reflux.
  • the reaction temperature is then increased to approximately 120°C and the distillate (essentially water) removed.
  • the mixture is cooled to about 60°C and stripped at reduced pressure to further reduce the water content to less than three, preferably less than one weight percent of the polyol. No effort is made to neutralize or remove residual catalyst which remains in the product.
  • the desired phenol/aldehyde condensate is one possessing hydroxymethyl substituents and, therefore, use of a molar excess of aldehyde is indicated.
  • the useful mole ratio is from 1.1 mole to 2.25 moles of aldehyde per mole of phenol. When the mole ratio falls below 0.9, the condensate becomes more "novolac" in structure (lacking hydroxymethyl substituents) and as the mole ratio approaches three, more para substitution and/or cross-linking occurs.
  • the preferred mole ratios of aldehyde to phenol range from 1.2 to 1.8.
  • the amount of modifying hydroxyl compound used is governed by the amount required to achieve improvement in the normal high friability and opened cell structure of phenolic foams and limited by the amount which would obviate the fire resistance of the phenolic structure. Below about one mole percent of hydroxyl compound based on the amount of phenol used, the hydroxyl compound is ineffective in improving strength and friability properties. Above 50 mole percent on the same basis, the hydroxyl compound causes the loss of the inherent fire retardancy of the phenolic structure. Thus, a useful range of hydroxyl compound is 1 to 50 mole percent of the phenol compound used. The preferred range is 10 to 25 mole percent.
  • Metal derivatives are effective as catalysts at concentration of 0.01 to 0.10 weight percent metal based on the total change.
  • the preferred catalyst level is 0.04 to 0.07 weight percent metal.
  • Phenols which are suitable for use in the preparation of these products are those which are unsubstituted in the ortho positions but which may be substutituted in the meta or para positions with halogen, C 1 to C 12 alkyl, or halogen-substituted alkyl of 1 to 6 carbon atoms.
  • phenols examples include phenol, p-cresol, p-tertiarybutylphenol, p-chlorophenol, p-bromophenol, p-trifluoromethylphenol, p-(2,3-dibromopropyl)phenol; 3,5-xylenol; 3,5-dichlrophenol, p-dodecylphenol, p-trichloromethylphenol, p-nonylphenol, as well as mixtures of any of the foregoing.
  • the preferred phenolic reactant is phenol itself or phenol mixed with a minor amount of the aforementioned substituted phenols.
  • Aldehydes which are suitable for use in the preparation of the polyols of this invention are aliphatic or halogenated aliphatic aldehydes having the formula RCHO where R is hydrogen or alkyl of 1 to 6 carbon atoms, optionally halogenated.
  • aldehydes are formaldehyde, acetaldehyde, pivaldehyde, hexanal, chloral, and 2,3-dibromopropanal.
  • the preferred aldehyde is formaldehyde.
  • the aldehyde is used in a nonaqueous state such as.paraformaldehyde, trioxane, paraldehyde, or chloral.
  • the modifying hydroxyl compound suitable for use in the preparation of the polyols of this invention are aliphatic monols, diols, triols, or tetrols having 1 to 12 carbon atoms and 0 to 5 ether oxygen atoms or mixtures thereof.
  • hydroxyl compounds examples include methanol, ethanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 2,3-butanediol, 1,3-butanediol, 1,12-dodecanediol, 1,2,5-hexanetriol, trimethylolpropane, pentaerythritol, tripropylene glycol, tetrapropylene glycol, hexaethylene glycol.
  • the preferred class of hydroxyl compounds are the diols, especially 1,4-butanediol and diethylene glycol.
  • the catalyst used in the preparation of the modified benzylic ether-containing resole polyols of this invention is selected from derivatives of certain metals. These are the C l -C 20 carboxylic acid salts of the group of divalent metal ions consisting of those of Mg, Ca, Mn, Fe, Co, Ni, Zn, Cd, Ba, and Pb (with or without added PbO); C 1 -C 20 carboxylic acid salts of divalent (dialkyltin) where the alkyl groups each contain 1 to 5 carbon atoms; and alkyl (3 to 8 carbon atoms) ortho titanates.
  • Suitable catalysts include lead naphthenate (with or without added PbO), zinc neodecanoate, cobalt naphthenate, tetrabutyl titanate, tetraoctyl titanate, manganese valerate, ferrous lactate, cadmium acetate, zinc benzoate, zinc acetate, dibutyltin dilaurate, dimethyltin diactate, lead butyrate.
  • the preferred catalysts are zinc neodecanoate, lead naphthenate, and dibutyltin dilaurate. The catalyst used in the polyol preparation is not removed or neutralized and remains in the product.
  • the modified benzyl ether-containing resole polyols prepared with the above indicated preferred materials have viscosities of less than 1,500,000 cps at 25°C and generally in the range of 5000 to 650,000 cps at 25°C.
  • the hydroxyl number values of the products, determined by the phenyl isocyanate method, generally range from 375 to 675, mostly in the 500 to 600 range.
  • the rigid cellular compositions derived from these novel polyols are made by state of the art techniques and are "phenolic" containing polymers with superior properties requiring no special treatment or equipment for their manufacture.
  • they can be reacted with organic polyisocyanates in the presence of the usual urethane catalysts using water or volatile organic blowing agents along with surfactants, plasticizers, fillers, or other additives. Reaction is achieved by intensely mixing the ingredients for a brief period and allowing the mixture to react. The products cure rapidly at room temperature without application of heat.
  • polyols can be used in the manufacture of urethane-modified polyisocyanurate foams by using a large molar excess ("high index") of polyisocyanate, a blowing agent, a surfactant, and an isocyanurate catalyst such as potassium acetate or tris(dimethylaminopropyl)hexahydrotriazine.
  • Suitable polyisocyanates for manufacture of these novel rigid cellular plastics are any organic di- or higher functionality isocyanate which is reactive with Zerewitinoff type hydrogen atoms.
  • isocyanates are hexamethylene diisocyanate, 1,3- or 1,4-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexane isocyanate, 2,2'-, 2,4'-, or 4,4'-dicyclohexylmethane diisocyanate, 1,3- or l,4-bis(isocyanatomethyl)cyclohexane, m- or p-xylylene diisocyanate, 2,4- or 2,6-toluene diisocyanate, 2 - or 4-methyl-l,3-cyclohexane diisocyanate, 1,3,5-tris(6-isocyanatohexyl)isocyanurate, N,N',N"-tri
  • the catalysts used for polyurethane formation are those known in the art and consist of tertiary amines, metal salts, or mixtures thereof.
  • suitable catalylic compounds are triethylamine, dimethylaminoethanol, N,N,N',N'-tetraethylethylenediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, bis(dimethylaminoethyl)ether, N,N-dimethyl-3-dimethylaminopropionamide, l,4-diazo[2.2.2]-bicyclooctane, N-methyl- or ethylmorpholine, stannous oleate, stannous 2-ethylhexanoate, dibutyltin dilaurate, dibutyltin dilauryl mercaptide, dibutyltin diacetate, lead naphthenate, zinc stearate, or mixtures thereof.
  • Blowing agents suitable for use in the preparation of these polyurethanes foams are water (which reacts with the isocyanate to form carbon dioxide) and volatile low boiling organic compounds. Examples of such compounds are alkanes such as pentane or hexane, oxygenated compounds such as methyl formate, halogenated aliphatic compounds such as fluorotrichloromethane or methylene dichloride.
  • the preferred blowing agents are water, methylene dichloride, fluorotrichloromethane (Refrigerant 11), or mixtures thereof.
  • Suitable surfactants to serve as emulsifying agents or cell stabilizers in the manufacture of these polyurethane foams are alkylarylsulfonates such as sodium didecylbenzenesulfonate, alkali metal or ammonium salts of alcohol sulfates such as potassium lauryl sulfate or ammonium salt of sulfated castor oil, oxyethylated fatty alcohols or acids such as oxyethylated tetradecanol containing 63 percent oxyethylene by weight, or silicone surfactants such as polyalkylsiloxane-polyoxyalkylene block copolymers.
  • the preferred surfactants are the silicone surfactants.
  • Plasticizers such as tris(chloroethyl) phosphate or didecylphthalate may be incorporated into the foam if desired.
  • Chain extenders such as low molecular weight diols may be used in quanity of less than 10 percent by weight of the polyol. Such low molecular weight diols can also serve to reduce the polyol viscosity for use in machine foaming.
  • the foams obtained by the practice of this invention are rapid curing, rigid, closed-cell polyurethanes which show good strength and flammability properties.
  • Phenol (634.24 parts), 91 percent paratormaldehyde (364.5 parts), 30 parts of 1,4-butanediol, 0.39 parts of PbO, and 0.88 parts of lead naphthenate solution (24 percent Pb) were charged to a reactor fitted with a mechanical stirrer, thermometer, and a reflux condenser/takeoff assembly. The stirred mixture was heated at 110°C to 116°C for 2 hours with total relux and then the distillate was taken off while the mixture was heated to 126°C to 128°C. When the major portion of the water of reaction had been removed at atmospheric pressure, the pressure was reduced to remove residual water. The stripped resin polyol had a hydroxyl number of 575 mg KOH/g and a water content of 0.5 percent.
  • Example 1 5 To demonstrate the variety of low molecular weight hydroxyl compounds which can be used to modify benzylic- ether containing resole polyols, the procedure of Example 1 5 was repeated with different added hydroxyl compounds and varied catalysts as shown in Table IV. The added hydroxyl compounds were used in an amount ranging from 9.7 mole percent (triethylene glycol) to 19.0 mole percent (1,2-propanediol) based on the phenol used. Each of these 10 modifiers yield a resole polyol having an acceptable viscosity and hydroxy number. Each resole polyol was used (Table V) to prepare a polyurethane foam with good friability, flamability, and insulating properties.
  • Example 20 The use of monohydroxyl compounds is shown in Examples 20 and 21, summarized in Table VI.
  • the procedures and apparatus used were the same as that described in Example 1 except for the differences in reactants charged which is shown in the table. It should be noted that while the methanol charged in Example 20 is much higher (45 mole percent) than that used with other hydroxyl compounds, the effective concentration in the liquid reaction mixture is much smaller due to the volatility of the methanol. Analysis of such products (NMR and infrared spectroscopy) showed that only about one-fourth of the charged methanol reacted with the phenol/aldehyde condensate.
  • Example 2 the performance comparison was made between the product of this invention and that of U. S. 3,485,797. Since the latter product is made without added diol, a product produced by the process of this invention was carefully examined to determine the fate of diol used in the manufacture.
  • Phenol, paraformaldehyde (1.6 moles CH 2 0/mole of phenol), and 1,4-butanediol (16 mole percent of phenol) were reacted in the presence of 0.24 percent of lead naphthenate solution (24 percent Pb) by heating the mixture at 110°C to 117°C for 3 hours under total reflux and then withdrawing the distillate. Over a 3 hour and 35 minute period while the temperature of this reaction mixture rose to 129°C, a total of 185.5 g of water was collected. Over the next 30 minutes, the pressure was reduced to strip off residual volatiles from the product. The final conditions were a . product temperature of 95°C and a pressure of ⁇ 1 mm Hg. The weight of strippings collected was 59.2 g and the product weighted 1427.7 g. Thus, 1667.4 g out of a total charge of 1668 g_was recovered in the three fractions.
  • modified resole polyols shown by proton and C 13 NMR spectroscopy were predominent dibenzyl ether bridging compared to methylene bridging, low methylol phenol (mono cyclic) content, and predominently ortho ring substitution.
  • the first of these was the reaction of a 1.7 mole ratio of paraformaldehyde and phenol in the presence of a molar quantity (based on phenol) of diethylene glycol using potassium hydroxide catalysis followed by further reaction under acid conditions.
  • the second preparation was a repeat of the first except for the use of a slightly lower (1.5) formaldehyde-phenol ratio and the use of 50 mole percent diethylene glycol and 50 mole percent glycerine (both based on phenol).
  • the first product had a viscosity of 560 cps at 25°C while the second product had a viscosity of 170 cps at 25°C.
  • the preparation of the diethylene glycol modified resin was repeated except that the amount of glycol used was reduced from 44 percent of the charge (in the first preparation) to 9 percent (typical of the level used in the present invention). This resulted in a reduction in the amount of free glycol and gave a product having a viscosity of 3400 cps at 25°C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP84100380A 1983-01-17 1984-01-16 Phenolische Polyole und damit hergestellte feste Schaumzusammensetzungen Withdrawn EP0116308A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/458,283 US4448951A (en) 1983-01-17 1983-01-17 Phenolic polyols and rigid cellular compositions derived therefrom
US458283 1983-01-17

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2155487A (en) * 1984-03-05 1985-09-25 Hoechst Co American Catalyzed urethanation of polymers
EP0177871A3 (en) * 1984-10-12 1987-05-13 Acme Resin Corporation Polyurethane binder compositions and process for their preparation
EP0165557A3 (en) * 1984-06-16 1987-11-19 Basf Aktiengesellschaft Process for the preparation of phenol-resol ethers linked by o,o'-methylene ether groups, and their use
EP0179360B1 (de) * 1984-10-12 1991-01-02 Acme Resin Corporation Phenolharzbinder für Anwendung in der Giesserei und bei Feuerfestmaterial
EP0518460A3 (en) * 1991-06-12 1993-02-03 Acme Resin Corporation Low free formaldehyde phenolic polyol formulation
WO2010101689A2 (en) 2009-03-04 2010-09-10 Dow Global Technologies Inc. Sound-dampening polyurethane-based composite
WO2011119329A2 (en) 2010-03-22 2011-09-29 Dow Global Technologies Llc Antistatic or semi-conductive polyurethane elastomers
WO2011123223A1 (en) 2010-03-31 2011-10-06 Dow Global Technologies LLC (Formerly known as Dow Global Technologies Inc.) Polyurethane compositions having improved impact resistance and optical properties
WO2012044878A2 (en) 2010-09-30 2012-04-05 Dow Global Technologies Llc Container modifications to minimize defects during reactive polyurethane flow
WO2014015119A2 (en) 2012-07-18 2014-01-23 Dow Global Technologies Llc Fire department and/or antistatic, non-mercury catalyzed polyurethane elastomer
WO2015042300A1 (en) 2013-09-19 2015-03-26 Dow Global Technologies Llc Vacuum assisted process to make closed cell rigid polyurethane foams using mixed blowing agents

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DE3335933A1 (de) * 1983-10-04 1985-04-18 Rütgerswerke AG, 6000 Frankfurt Mehrkomponenten-bindemittel mit verlaengerter verarbeitbarkeitszeit
US4657950A (en) * 1984-10-12 1987-04-14 Acme Resin Corporation Refractory binders
US4634758A (en) * 1984-10-12 1987-01-06 Acme Resin Corporation Process for preparing alkoxy-modified phenolic resole resins
US4723592A (en) * 1984-10-12 1988-02-09 Acme Resin Corporation Process for preparing foundry cores and molds
US4848442A (en) * 1984-10-12 1989-07-18 Acme Resin Corporation Resin binders for foundry sand cores and molds
JP2857881B2 (ja) * 1988-11-02 1999-02-17 保土谷化学工業株式会社 ウレタン組成物
US4960804A (en) * 1989-03-09 1990-10-02 Mobay Corporation Rigid foams using blends of chlorofluorocarbons and alkyl alkanoates as blowing agent
US5091287A (en) * 1990-04-10 1992-02-25 Minnesota Mining And Manufacturing Company Photoreactive oligomer composition and printing plate
US5264535A (en) * 1991-06-12 1993-11-23 Acme Resin Corp. Low free formaldehyde phenolic polyol formulation
EP0650991B1 (de) * 1993-11-02 1999-03-17 Nisshinbo Industries, Inc. Verfahren zur Herstellung von Polyurethan-Schaumstoffen
US6753357B2 (en) * 2001-12-18 2004-06-22 Foam Supplies, Inc. Rigid foam compositions and method employing methyl formate as a blowing agent
US7591864B2 (en) 2004-01-09 2009-09-22 University Of Central Florida Research Foundation, Inc. Catalysts for the evolution of hydrogen from borohydride solution
HUE037988T2 (hu) * 2004-08-04 2018-09-28 Foam Supplies Inc A reaktivitás idõbeli fennmaradása és a katalizátor lebomlása a poliuretán habban
CN102203158B (zh) * 2008-11-06 2013-11-27 旭有机材工业株式会社 聚氨酯泡沫体用发泡性组合物及聚氨酯泡沫体
MX2018005209A (es) 2015-10-29 2018-08-01 Hexion Inc Nuevas resinas de alquilfenol y metodo para prepararlas.
DE102016123621A1 (de) * 2016-12-06 2018-06-07 Ask Chemicals Gmbh Polyurethan Bindemittel mit verbesserter Fließfähigkeit
US10696838B2 (en) 2017-10-06 2020-06-30 Hexion Inc. Rubber compositions containing tackifiers
US10808068B2 (en) 2018-01-26 2020-10-20 Hexion Inc. Manufacture of novolacs and resoles using lignin
DE102021003264A1 (de) 2021-06-24 2022-12-29 Ask Chemicals Gmbh Zwei-komponenten-polyurethanzusammensetzungen

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US4120847A (en) * 1976-01-09 1978-10-17 Monsanto Company High ortho etherified resole resins
GB2033413A (en) * 1978-10-13 1980-05-21 Baxenden Chem Phenol/aldehyde condensates; polyurethane foams
US4404334A (en) * 1982-11-18 1983-09-13 Georgia-Pacific Corporation Thermosetting resinous polyol

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US4120847A (en) * 1976-01-09 1978-10-17 Monsanto Company High ortho etherified resole resins
GB2033413A (en) * 1978-10-13 1980-05-21 Baxenden Chem Phenol/aldehyde condensates; polyurethane foams
US4404334A (en) * 1982-11-18 1983-09-13 Georgia-Pacific Corporation Thermosetting resinous polyol

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2155487A (en) * 1984-03-05 1985-09-25 Hoechst Co American Catalyzed urethanation of polymers
EP0165557A3 (en) * 1984-06-16 1987-11-19 Basf Aktiengesellschaft Process for the preparation of phenol-resol ethers linked by o,o'-methylene ether groups, and their use
EP0177871A3 (en) * 1984-10-12 1987-05-13 Acme Resin Corporation Polyurethane binder compositions and process for their preparation
AU579406B2 (en) * 1984-10-12 1988-11-24 Borden Chemical, Inc. Polyurethane binder compositions and process for their preparation
EP0179360B1 (de) * 1984-10-12 1991-01-02 Acme Resin Corporation Phenolharzbinder für Anwendung in der Giesserei und bei Feuerfestmaterial
EP0518460A3 (en) * 1991-06-12 1993-02-03 Acme Resin Corporation Low free formaldehyde phenolic polyol formulation
WO2010101689A2 (en) 2009-03-04 2010-09-10 Dow Global Technologies Inc. Sound-dampening polyurethane-based composite
WO2011119329A2 (en) 2010-03-22 2011-09-29 Dow Global Technologies Llc Antistatic or semi-conductive polyurethane elastomers
WO2011123223A1 (en) 2010-03-31 2011-10-06 Dow Global Technologies LLC (Formerly known as Dow Global Technologies Inc.) Polyurethane compositions having improved impact resistance and optical properties
WO2012044878A2 (en) 2010-09-30 2012-04-05 Dow Global Technologies Llc Container modifications to minimize defects during reactive polyurethane flow
WO2014015119A2 (en) 2012-07-18 2014-01-23 Dow Global Technologies Llc Fire department and/or antistatic, non-mercury catalyzed polyurethane elastomer
WO2015042300A1 (en) 2013-09-19 2015-03-26 Dow Global Technologies Llc Vacuum assisted process to make closed cell rigid polyurethane foams using mixed blowing agents

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US4448951A (en) 1984-05-15

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