WO2016193245A1 - Isocyanate composition and polyurethane rigid foam prepared from the same - Google Patents

Isocyanate composition and polyurethane rigid foam prepared from the same Download PDF

Info

Publication number
WO2016193245A1
WO2016193245A1 PCT/EP2016/062230 EP2016062230W WO2016193245A1 WO 2016193245 A1 WO2016193245 A1 WO 2016193245A1 EP 2016062230 W EP2016062230 W EP 2016062230W WO 2016193245 A1 WO2016193245 A1 WO 2016193245A1
Authority
WO
WIPO (PCT)
Prior art keywords
toluene diisocyanate
isocyanate composition
residue
rigid foam
polyurethane rigid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2016/062230
Other languages
French (fr)
Inventor
Chenxi Zhang
Liqiang LI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Polymers China Co Ltd
Covestro Deutschland AG
Original Assignee
Covestro Polymers China Co Ltd
Covestro Deutschland AG
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 Covestro Polymers China Co Ltd, Covestro Deutschland AG filed Critical Covestro Polymers China Co Ltd
Publication of WO2016193245A1 publication Critical patent/WO2016193245A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/727—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80 comprising distillation residues or non-distilled raw phosgenation products
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • 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

  • the present invention relates to an isocyanate composition comprising a toluene diisocyanate residue , which can be used for preparing a polyurethane rigid foam having favorable insulation properties and compression strength .
  • the present invention also relates to a polyurethane rigid foam prepared from said isocyanate composition .
  • Toluene diisocyanate are usually prepared by reacting toluene diamine (TDA) and phosgene and then purifying the obtained crude product via distillation .
  • TDA toluene diamine
  • phosgene phosgene
  • CN 1064074A discloses a method of reducing the content of hydrolysable chlorides in toluene diisocyanate (TDI ) , in particular in its distillation residues , and polymer made by processing the residues .
  • TDI toluene diisocyanate
  • the present invention provides an isocyanate composition, comprising : al) a toluene diisocyanate residue , wherein the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method, and wherein the toluene diisocyanate residue has a NCO content of 5-45 wt . % , based on the total weight of the toluene diisocyanate residue ; and a2 ) diphenyl methane diisocyanate , poly (diphenyl methane diisocyanate ) or a combination thereof .
  • the isocyanate composition has a NCO content of 30-40 wt . % , based on the total weight of the isocyanate composition .
  • the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method in gas phase .
  • the toluene diisocyanate residue has a content of 15-40 wt . % , based on the total weight of the isocyanate composition .
  • the toluene diisocyanate residue has a content of 20-30 wt.%, based on the total weight of the isocyanate composition .
  • the present invention also relates to a polyurethane rigid foam, wherein the polyurethane rigid foam is prepared from the above-mentioned isocyanate composition .
  • I isocyanate composition
  • the present invention provides an isocyanate composition, comprising : al) a toluene diisocyanate residue , wherein the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method, and wherein the toluene diisocyanate residue has a NCO content of 5-45 wt . % , based on the total weight of the toluene diisocyanate residue ; and a2 ) diphenyl methane diisocyanate , poly (diphenyl methane diisocyanate ) or a combination thereof .
  • the isocyanate composition has a NCO content of 30-40 wt.%, based on the total weight of the isocyanate composition .
  • the isocyanate composition has a viscosity of 350-1100 mPa ⁇ s , preferably 450-1050 mPa ⁇ s and more preferably 550-950 mPa ⁇ s .
  • the toluene diisocyanate residue in the isocyanate composition has a content of 15-40 wt.%, preferably 20-30 wt.%, based on the total weight of the isocyanate composition .
  • the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method .
  • the well-known phosgene method for preparing toluene diisocyanate generally consists of four steps :
  • DNT dinitro-toluene
  • the toluene diisocyanate residue used in the present invention is obtained in step (4 ) of purification by distillation, wherein the toluene diisocyanate residue has a NCO content of 5-45 wt . % , preferably 10-39 wt . % , more preferably 25-38 wt . % , based on the total weight of the toluene diisocyanate residues .
  • the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method in gas phase .
  • Gas-phase phosgene method is characterized in that in said step (3 ) , TDA and phosgene react in gas phase , preferably at a temperature of 200-600 , to obtain the toluene diisocyanate .
  • Isocyanate composition further comprises diphenyl methane diisocyanate (MDI ) , poly (diphenyl methane diisocyanate) (PMDI) or a combination thereof , with a content of 60-85% , preferably 70 -85% , based on the total weight of the isocyanate composition .
  • the polyisocyanate composition may also comprise other organic polyisocyanates , such as aliphatic , alicyclic and aromatic diisocyanate (s) and/or polyisocyanate (s) .
  • the present invention also provides a polyurethane rigid foam prepared from the above-mentioned isocyanate composition .
  • the polyurethane rigid foam system provided by the present invention preferably a conventional block foam and a plywood, has good insulation properties and compressive strength .
  • the composition used for preparing the polyurethane rigid foam also comprises an isocyanate-reactive component .
  • the isocyanate- reactive component may comprise one or more polyether and/or polyester polyol ( s ) having a hydroxy1 number of 150-1200 mgKOH/g and a content of 75-95 wt . % , based on the total weight of the isocyanate-reactive component .
  • the polyether polyols used in the present invention can be prepared by known processes .
  • it can be obtained by the reaction of alkylene oxide and an initiator in the presence of a catalyst .
  • the catalyst is , preferably but not limited to , alkali hydroxides , alkal i alkoxides , ant imony pentachloride , boron fluoride etherate , or a mixture thereof .
  • the alkylene oxide is , preferably but not 1 imited to, tetrahydrofuran, ethylene oxide , propylene oxide, 1 , 2 -butylene oxide , 2 , 3 -butylene oxide , styrene oxide , or a mixture thereof ; in particular preferably ethylene oxide and/or propylene oxide .
  • the initiator is , preferably but not limited to, a polyhydroxy or polyamine compound .
  • the polyhydroxy compound is , preferably but not limited to, water , ethylene glycol , 1 , 2 -propanediol , 1 , 3 -propanediol , diethylene glycol , trimethylolpropane , glycerol , bisphenol A, bisphenol S or a mixture thereof .
  • the polyamine compound is , preferably but not limited to , ethylene diamine , propylene diamine , butylene diamine , hexamethylene diamine , diethylenetriamine , tolylenediamine or a mixture thereof .
  • the polyether polyol has a funct ional ity of 2 -8 , preferably 2 -5.
  • the polyester polyol is obtained by the reaction of a dicarboxylic acid or dicarboxylic acid anhydride with a polyol .
  • the dicarboxylic acid is preferably, but not limited to , an aliphatic carboxyl ic acid containing 2 to 12 carbon atoms , for example , succinic acid, malonic acid , glutaric acid, adipic acid, suberic acid, azelaic acid, capric acid, dodecylic acid, maleic acid, fumaric acid, phthal ic acid, isophthal ic acid, terephthalic acid, and a mixture thereof .
  • the dicarboxylic acid anhydride is preferably, but not limited to, phthalic anhydride , tetrachlorophthalic anhydride , ma1eic anhydride , and a mixture thereof .
  • the polyol is preferably, but not limited to , ethylene glycol , diethylene glycol , 1 , 2 -propanediol , 1 , 3 -propanediol , dipropylene glycol , methyl -1,3 -propanediol , 1 , 4 -butanediol , 1 , 5-pentanediol , 1 , 6 -hexanediol , neopentyl glycol ,
  • the polyester polyol further includes those prepared from lactones .
  • the polyester polyol prepared from lactones is preferably, but not limited to, e - caprolactone .
  • the polyurethane rigid foam according to the present invention may also comprise , but not limited to, a polycarbonate polyol and a polymer polyol .
  • the polycarbonate polyol is preferably, but not limited to , a polycarbonate diol synthesized by the reaction of a diol with a dialkyl or diary1 carbonate or phosgene .
  • the diol is preferably, but not limited to, 1 , 2 -propanediol , 1 , 3 -propanediol , 1 , 4 -butanediol , 1 , 5-pentanediol , 1 , 6 -hexanediol , diethylene glycol , s-Trioxane diol , and a mixture thereof .
  • the dialkyl or diary1 carbonate is preferably, but not limited to, diphenyl carbonate .
  • the polymer polyol is a stable dispersion formed by solid enhanced particles in a polyol liquid. Any known polymer (or dispersion) polyol in the art can be included in the polyol component according to the present invention . It includes , but is not limited to, SAN polymer polyol , PHD polymer polyol and PIPA polymer polyols .
  • the SAN polymer polyol is made by in-situ polymerization of a mixture of acrylonitrile and styrene in a base polyol ;
  • the PHD polymer polyol is made by in-situ polymerization of a isocyanate mixture and a diamine in a base polyol ;
  • the PUPA polymer polyol is made by in-situ polymerization of a isocyanate mixture and a diol and/or diol -amine in a base polyol .
  • the functionality and hydroxy1 number of an organic polyol mean the average functionality and the average hydroxy1 number in each case , unless otherwise indicated .
  • blowing agent a chain extender, a catalyst , a surfactant , a f1ame retardant , a filler or other additives suitable for the preparation of the polyurethane rigid foam according to the present invention .
  • the blowing agent according to the present invention may be a variety of physical blowing agents or chemical blowing agents . Examples of said blowing agent are , preferably but not limited to , water , halogenated hydrocarbons , hydrocarbons and gases .
  • the halogenated hydrocarbons are preferably, but not limited to , monochlorodifluoromethane , dichloromonofluoromethane , dichlorofluoromethane , trichlorof luoromethane , or a mixture thereof .
  • the hydrocarbons are preferably, but not limited to , butane , pentane , cyclopentane , hexane , cyclohexane , heptane , or a mixture thereof .
  • the gases are preferably, but not limited to , air , CO2 or N2.
  • the blowing agent is particularly preferably water The amount of the blowing agent is dependent on the desired density of the polyurethane .
  • the chain extender used in the present invention is usual ly an active hydrogen atom-containing compound having a molecular weight of less than 800 , preferably a molecular weight of 18-400.
  • the active hydrogen atom-containing compound is preferably, but not limited to , alkylene glycols , dialkylene glycols , polyalkylene polyol , or a mixture thereof, for example , ethylene glycol , 1 , 4 -butanediol , 1 , 6 -hexanediol , 1 , 7-heptanediol , 1, 8 -octanediol , 1 , 9 -nonanediol , 1 , 10 -decanediol , diethylene glycol , dipropylene glycol , polyoxyalkylene glycol, or a mixture thereof .
  • the active hydrogen atom-containing compound may also include other grafted or unsaturated alkylene glyco
  • the N-alkyl -dialkanol amine is preferably, but not limited to , ethanol amine, 2-propanol amine, 3 -amino-2 , 2 -dimethylpropanol , N-methyl -diethanol amine, N-ethyl -diethanol amine, or a mixture thereof .
  • the active hydrogen atom-containing compound may further include aliphatic amines , aromatic amines , or a mixture thereof .
  • the aliphatic amines and aromatic amines are preferably, but not limited to, 1 , 2 -ethylenediamine , 1 , 3 -propanediamine , 1 , 4 -butanediamine , hexamethylene diamine , isophorone diamine , 1 , 4 -cyclohexane diamine , ⁇ , ⁇ ' -diethyl -phenylenediamine , 2 , 4 -diaminotoluene , 2 , 6 -diaminotoluene , or a mixture thereof .
  • the catalyst according to the present invention is preferably, but not limited to, amine catalysts , organic metal catalysts , or a mixture thereof .
  • Said amine catalysts are preferably, but not limited to, triethylamine , tributylamine , triethylenediamine , N-ethylmorpholine ,
  • organic metal catalysts are preferably, but not limited to , organotin compounds , for example , tin ( II ) acetate , tin ( II ) octoate , tin ethylhexanoate , tin laurate , dibutyltin oxide , dibutyltin dichloride , dibutyltin diacetate , dibutyltin maleate , dioctyltin diacetate and a mixture thereof .
  • organotin compounds for example , tin ( II ) acetate , tin ( II ) octoate , tin ethylhexanoate , tin laurate , dibutyltin oxide , dibutyltin dichloride , dibutyltin diacetate , dibutyltin maleate , dioctyltin diacetate and a mixture thereof .
  • the surfactant used in the present invention is preferably, but not limited to , ethylene oxide derivatives of siloxanes .
  • the f1ame retardant used in the present invention may be an organic or an inorganic f1ame retardant .
  • the organic f1ame retardant is preferably, but not limited to, tris (2 -chloroethyl ) phosphate (TCEP) , tris (2 -chloropropyl ) phosphate (TCPP) , trischloropropyl phosphate (TDCPP) , dimethyl methylphosphonate (DMMP) , triphenyl phosphate , me1amine orthophosphate (MPP) or a mixture thereof .
  • the inorganic flame retardant is preferably, but not limited to, hydrated aluminum hydroxide , hydrated magnesium hydroxide , monoammonium phosphate , diammonium phosphate , ammonium chloride , boric acid, hydrated zinc borate or a mixture thereof .
  • the filler used in the present invention can be a variety of inorganic fillers or organic fillers .
  • the inorganic filler is preferably, but not limited to, silicate minerals , metal oxides , metal salts , inorganic pigments , natural and synthetic mineral fibers , nano-materials , or a mixture thereof .
  • Non-limiting examples are calcium silicate , calcium carbonate , fumed silica , nano-zinc oxide , barite , zinc sulfide , glass particles and wollastonite .
  • the organic filler is preferably, but not limited to , crystalline wax, polymer polyol , organic microparticles and cork .
  • the inorganic fillers or organic fillers may be used singly or in combination .
  • the filler may serve to enhance the strength of the polyurethane layer, f1ame retardancy and so on .
  • TDI distillation residue NCO content of about 34 wt . % , a viscosity of about 12000 cps ( 25 "' C ) , available from Bayer MaterialScience AG;
  • Desmodur 44V20L PMDI , NCO content of 30.5-32.5 wt . % , available from Bayer MaterialScience AG;
  • Desmophen 4030 M polyether polyol , a hydroxy1 number of 380 , available from Bayer MaterialScience AG;
  • Desmophen 4034B polyether polyol , a hydroxy1 number of 440 , available from Bayer MaterialScience AG;
  • Arcol 1021 polyether polyol, a hydroxy1 number of 56, available from Bayer MaterialScience AG;
  • L-6920 a foam stabilizer available from Moment ive ;
  • Polycat 8 a catalyst available from Air Products ;
  • Polycat 41 a catalyst available from Air Products ;
  • HK 470 Type of conventional high-pressure foaming machine available from Hennecke company .
  • the isocyanate- react ive components used in the amounts shown in Table 1 were mixed and then reacted in HK 470 Type of conventional high-pressure foaming machine based on the amounts shown in Table 2.
  • the liquid polyurethane is poured into a mold of 20 cm * 30 cm * 60 cm, the temperature of the mold is controlled between 25-35 , the temperature of raw materials is 25-30 , the mixing pressure of the high-pressure machine is 120-150 bar .
  • the foam rises substantially freely since there is no cover on the mold .
  • 20 minutes it was demolded and kept at room temperature for 24 hours , and the top part which is uneven is cut off .
  • the remaining lower part is cut into test samples with desired size in accordance with the foam test standards .
  • a group of five samples were tested in terms of mechanical properties (according to GB/T 8813-2008) and heat insulation properties (according to GB/T3399-1982 ) .
  • the test data are shown in Table 2.
  • the polyurethane rigid foams of Examples 2 and 3 have a lower thermal conductivity and therefore better insulation properties
  • the polyurethane rigid foams of Examples 2 and 3 have a higher compression strength in the direction vertical to foaming when compared with that of Example 1 having the same density .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to an isocyanate composition, comprising: a1) a toluene diisocyanate residue, wherein the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method, and wherein the toluene diisocyanate residue has a NCO content of 5-45 wt. %, based on total weight of the toluene diisocyanate residue; and a2) diphenyl methane diisocyanate, poly(diphenyl methane diisocyanate) or a combination thereof. The present invention also relates to a polyurethane rigid foam prepared from the isocyanate composition, wherein the polyurethane rigid foam has favorable insulation property and compression strength.

Description

Isocyanate Composition and Polyurethane
Rigid Foam Prepared from the Same
TECHNICAL FIELD
The present invention relates to an isocyanate composition comprising a toluene diisocyanate residue , which can be used for preparing a polyurethane rigid foam having favorable insulation properties and compression strength . The present invention also relates to a polyurethane rigid foam prepared from said isocyanate composition .
BACKGROUD
Toluene diisocyanate (TDI ) are usually prepared by reacting toluene diamine (TDA) and phosgene and then purifying the obtained crude product via distillation . In practice , there exists a large amount of high-boiling distillation residues during the distillation process of the crude product of toluene diisocyanate (TDI ) . These residues are toxic and difficult to dispose ; thus disposal of these residues leads to a serious problem in industry, which is not only uneconomical , but also poses a safety risk . Therefore , it is a key process of producing TDI how to deal with and utilize these residues .
These distillation residues are usually treated by a method of incineration , wherein the toxic exhaust gases require additional recycling and processing . CN 1064074A discloses a method of reducing the content of hydrolysable chlorides in toluene diisocyanate (TDI ) , in particular in its distillation residues , and polymer made by processing the residues .
SUMMARY OF THE INVENTION The present invention provides an isocyanate composition, comprising : al) a toluene diisocyanate residue , wherein the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method, and wherein the toluene diisocyanate residue has a NCO content of 5-45 wt . % , based on the total weight of the toluene diisocyanate residue ; and a2 ) diphenyl methane diisocyanate , poly (diphenyl methane diisocyanate ) or a combination thereof .
In one embodiment of the present invention, the isocyanate composition has a NCO content of 30-40 wt . % , based on the total weight of the isocyanate composition .
In a preferred embodiment of the present invention, the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method in gas phase .
In another preferred embodiment of the present invention, the toluene diisocyanate residue has a content of 15-40 wt . % , based on the total weight of the isocyanate composition .
In still another preferred embodiment of the present invention, the toluene diisocyanate residue has a content of 20-30 wt.%, based on the total weight of the isocyanate composition .
The present invention also relates to a polyurethane rigid foam, wherein the polyurethane rigid foam is prepared from the above-mentioned isocyanate composition .
DETAINED DESCRIPTION
I . Isocyanate composition The present invention provides an isocyanate composition, comprising : al) a toluene diisocyanate residue , wherein the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method, and wherein the toluene diisocyanate residue has a NCO content of 5-45 wt . % , based on the total weight of the toluene diisocyanate residue ; and a2 ) diphenyl methane diisocyanate , poly (diphenyl methane diisocyanate ) or a combination thereof .
In one embodiment of the present invention, the isocyanate composition has a NCO content of 30-40 wt.%, based on the total weight of the isocyanate composition .
In one embodiment of the present invention, the isocyanate composition has a viscosity of 350-1100 mPa · s , preferably 450-1050 mPa · s and more preferably 550-950 mPa · s .
The toluene diisocyanate residue in the isocyanate composition has a content of 15-40 wt.%, preferably 20-30 wt.%, based on the total weight of the isocyanate composition .
In one embodiment of the present invention, the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method . The well-known phosgene method for preparing toluene diisocyanate generally consists of four steps :
(1) the reaction of toluene and nitric acid to form dinitro-toluene (DNT) ;
(2 ) the reaction of DNT and hydrogen to form toluene diamine (TDA) ;
(3 ) the reaction of TDA and phosgene to form toluene diisocyanate (TDI) ;
(4 ) purification of TDI by distillation .
The toluene diisocyanate residue used in the present invention is obtained in step (4 ) of purification by distillation, wherein the toluene diisocyanate residue has a NCO content of 5-45 wt . % , preferably 10-39 wt . % , more preferably 25-38 wt . % , based on the total weight of the toluene diisocyanate residues .
In a preferred embodiment of the invention, the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method in gas phase . Gas-phase phosgene method is characterized in that in said step (3 ) , TDA and phosgene react in gas phase , preferably at a temperature of 200-600 , to obtain the toluene diisocyanate . Isocyanate composition further comprises diphenyl methane diisocyanate (MDI ) , poly (diphenyl methane diisocyanate) (PMDI) or a combination thereof , with a content of 60-85% , preferably 70 -85% , based on the total weight of the isocyanate composition . In one embodiment of the present invention, the polyisocyanate composition may also comprise other organic polyisocyanates , such as aliphatic , alicyclic and aromatic diisocyanate (s) and/or polyisocyanate (s) . Examples of suitable organic polyisocyanates used in the present invention include , but are not limited to, 1 , 4-butylene diisocyanate , pentane-1, 5-diisocyanate, hexamethylene diisocyanate (HDI ) , isophorone diisocyanate ( IPDI ) , 2,2,4- and/or
2,4, 4 -trimethylhexamethylene diisocyanate , bis (4 , 4 ' - isocyanato-cyclohexyl ) methane or mixtures thereof with other isomers , 1 , 4 -cyclohexylene diisocyanate , 1, 4-phenylene diisocyanate, 1, 5-naphthalene diisocyanate, 1,3- and/or 1 , 4 -tetramethylxylylene diisocyanate (TMXDI ) ,
I , 3 -xylylene diisocyanate (XDI ) .
II . Polyurethane rigid foam
The present invention also provides a polyurethane rigid foam prepared from the above-mentioned isocyanate composition . The polyurethane rigid foam system provided by the present invention, preferably a conventional block foam and a plywood, has good insulation properties and compressive strength . In one embodiment of the present invention, the composition used for preparing the polyurethane rigid foam also comprises an isocyanate-reactive component . The isocyanate- reactive component may comprise one or more polyether and/or polyester polyol ( s ) having a hydroxy1 number of 150-1200 mgKOH/g and a content of 75-95 wt . % , based on the total weight of the isocyanate-reactive component .
The polyether polyols used in the present invention can be prepared by known processes . For example , it can be obtained by the reaction of alkylene oxide and an initiator in the presence of a catalyst . The catalyst is , preferably but not limited to , alkali hydroxides , alkal i alkoxides , ant imony pentachloride , boron fluoride etherate , or a mixture thereof . The alkylene oxide is , preferably but not 1 imited to, tetrahydrofuran, ethylene oxide , propylene oxide, 1 , 2 -butylene oxide , 2 , 3 -butylene oxide , styrene oxide , or a mixture thereof ; in particular preferably ethylene oxide and/or propylene oxide . The initiator is , preferably but not limited to, a polyhydroxy or polyamine compound . The polyhydroxy compound is , preferably but not limited to, water , ethylene glycol , 1 , 2 -propanediol , 1 , 3 -propanediol , diethylene glycol , trimethylolpropane , glycerol , bisphenol A, bisphenol S or a mixture thereof . The polyamine compound is , preferably but not limited to , ethylene diamine , propylene diamine , butylene diamine , hexamethylene diamine , diethylenetriamine , tolylenediamine or a mixture thereof . The polyether polyol has a funct ional ity of 2 -8 , preferably 2 -5.
The polyester polyol is obtained by the reaction of a dicarboxylic acid or dicarboxylic acid anhydride with a polyol . The dicarboxylic acid is preferably, but not limited to , an aliphatic carboxyl ic acid containing 2 to 12 carbon atoms , for example , succinic acid, malonic acid , glutaric acid, adipic acid, suberic acid, azelaic acid, capric acid, dodecylic acid, maleic acid, fumaric acid, phthal ic acid, isophthal ic acid, terephthalic acid, and a mixture thereof . The dicarboxylic acid anhydride is preferably, but not limited to, phthalic anhydride , tetrachlorophthalic anhydride , ma1eic anhydride , and a mixture thereof . The polyol is preferably, but not limited to , ethylene glycol , diethylene glycol , 1 , 2 -propanediol , 1 , 3 -propanediol , dipropylene glycol , methyl -1,3 -propanediol , 1 , 4 -butanediol , 1 , 5-pentanediol , 1 , 6 -hexanediol , neopentyl glycol ,
1, 10 -decanediol , glycerol , trimethylolpropane , and a mixture thereof . The polyester polyol further includes those prepared from lactones . The polyester polyol prepared from lactones is preferably, but not limited to, e - caprolactone .
In addition to the above-mentioned polyether polyol and/or polyester polyol , the polyurethane rigid foam according to the present invention may also comprise , but not limited to, a polycarbonate polyol and a polymer polyol .
The polycarbonate polyol is preferably, but not limited to , a polycarbonate diol synthesized by the reaction of a diol with a dialkyl or diary1 carbonate or phosgene . The diol is preferably, but not limited to, 1 , 2 -propanediol , 1 , 3 -propanediol , 1 , 4 -butanediol , 1 , 5-pentanediol , 1 , 6 -hexanediol , diethylene glycol , s-Trioxane diol , and a mixture thereof . The dialkyl or diary1 carbonate is preferably, but not limited to, diphenyl carbonate .
The polymer polyol is a stable dispersion formed by solid enhanced particles in a polyol liquid. Any known polymer (or dispersion) polyol in the art can be included in the polyol component according to the present invention . It includes , but is not limited to, SAN polymer polyol , PHD polymer polyol and PIPA polymer polyols . The SAN polymer polyol is made by in-situ polymerization of a mixture of acrylonitrile and styrene in a base polyol ; the PHD polymer polyol is made by in-situ polymerization of a isocyanate mixture and a diamine in a base polyol ; the PUPA polymer polyol is made by in-situ polymerization of a isocyanate mixture and a diol and/or diol -amine in a base polyol .
The measurement of hydroxy1 number is known for the skilled as such and described , for example , in Houben Weyl , Methoden der Organischen Chemie , vol . XIV/2 Makromolekulare Stof fe , p. 17 , Georg Thieme Verlag ; Stuttgart 1963 , which is incorporated by reference herein in its entirety .
When used in the present invention , the functionality and hydroxy1 number of an organic polyol mean the average functionality and the average hydroxy1 number in each case , unless otherwise indicated .
The skilled in the art can add, if needed, a blowing agent , a chain extender, a catalyst , a surfactant , a f1ame retardant , a filler or other additives suitable for the preparation of the polyurethane rigid foam according to the present invention . The blowing agent according to the present invention may be a variety of physical blowing agents or chemical blowing agents . Examples of said blowing agent are , preferably but not limited to , water , halogenated hydrocarbons , hydrocarbons and gases . The halogenated hydrocarbons are preferably, but not limited to , monochlorodifluoromethane , dichloromonofluoromethane , dichlorofluoromethane , trichlorof luoromethane , or a mixture thereof . The hydrocarbons are preferably, but not limited to , butane , pentane , cyclopentane , hexane , cyclohexane , heptane , or a mixture thereof . The gases are preferably, but not limited to , air , CO2 or N2. The blowing agent is particularly preferably water The amount of the blowing agent is dependent on the desired density of the polyurethane . The chain extender used in the present invention is usual ly an active hydrogen atom-containing compound having a molecular weight of less than 800 , preferably a molecular weight of 18-400. The active hydrogen atom-containing compound is preferably, but not limited to , alkylene glycols , dialkylene glycols , polyalkylene polyol , or a mixture thereof, for example , ethylene glycol , 1 , 4 -butanediol , 1 , 6 -hexanediol , 1 , 7-heptanediol , 1, 8 -octanediol , 1 , 9 -nonanediol , 1 , 10 -decanediol , diethylene glycol , dipropylene glycol , polyoxyalkylene glycol, or a mixture thereof . The active hydrogen atom-containing compound may also include other grafted or unsaturated alkylene glycol or a mixture thereof , for example , 1 , 2 -propanediol ,
2 -methyl -1,3 -propanediol , 2 , 2 -dimethyl -1,3 -propanediol ,
2 -butyl -2 -ethyl -1 , 3 -propanediol , 2 -butene-1 , 4 -diol ,
2-butyne-l, 4-diol , alkanol amine , N-alkyl -dialkanol amine . The N-alkyl -dialkanol amine is preferably, but not limited to , ethanol amine, 2-propanol amine, 3 -amino-2 , 2 -dimethylpropanol , N-methyl -diethanol amine, N-ethyl -diethanol amine, or a mixture thereof . The active hydrogen atom-containing compound may further include aliphatic amines , aromatic amines , or a mixture thereof . The aliphatic amines and aromatic amines are preferably, but not limited to, 1 , 2 -ethylenediamine , 1 , 3 -propanediamine , 1 , 4 -butanediamine , hexamethylene diamine , isophorone diamine , 1 , 4 -cyclohexane diamine , Ν,Ν' -diethyl -phenylenediamine , 2 , 4 -diaminotoluene , 2 , 6 -diaminotoluene , or a mixture thereof . The catalyst according to the present invention is preferably, but not limited to, amine catalysts , organic metal catalysts , or a mixture thereof . Said amine catalysts are preferably, but not limited to, triethylamine , tributylamine , triethylenediamine , N-ethylmorpholine ,
N, N, ' , ' -tetramethyl -ethylene diamine , pentamethyl -diethylene triamine , N, N-methylaniline ,
N, N-dimethylaniline, or a mixture thereof . Said organic metal catalysts are preferably, but not limited to , organotin compounds , for example , tin ( II ) acetate , tin ( II ) octoate , tin ethylhexanoate , tin laurate , dibutyltin oxide , dibutyltin dichloride , dibutyltin diacetate , dibutyltin maleate , dioctyltin diacetate and a mixture thereof .
The surfactant used in the present invention is preferably, but not limited to , ethylene oxide derivatives of siloxanes . The f1ame retardant used in the present invention may be an organic or an inorganic f1ame retardant . The organic f1ame retardant is preferably, but not limited to, tris (2 -chloroethyl ) phosphate (TCEP) , tris (2 -chloropropyl ) phosphate (TCPP) , trischloropropyl phosphate (TDCPP) , dimethyl methylphosphonate (DMMP) , triphenyl phosphate , me1amine orthophosphate (MPP) or a mixture thereof . The inorganic flame retardant is preferably, but not limited to, hydrated aluminum hydroxide , hydrated magnesium hydroxide , monoammonium phosphate , diammonium phosphate , ammonium chloride , boric acid, hydrated zinc borate or a mixture thereof .
The filler used in the present invention can be a variety of inorganic fillers or organic fillers . The inorganic filler is preferably, but not limited to, silicate minerals , metal oxides , metal salts , inorganic pigments , natural and synthetic mineral fibers , nano-materials , or a mixture thereof . Non-limiting examples are calcium silicate , calcium carbonate , fumed silica , nano-zinc oxide , barite , zinc sulfide , glass particles and wollastonite . The organic filler is preferably, but not limited to , crystalline wax, polymer polyol , organic microparticles and cork . The inorganic fillers or organic fillers may be used singly or in combination . The filler may serve to enhance the strength of the polyurethane layer, f1ame retardancy and so on .
The present invention will be further described below in combination with examples . The specific examples and methods disclosed herein are illustrative and not restrictive . EXAMPLES
The starting materials and devices used in this application are described as follows :
TDI distillation residue : NCO content of about 34 wt . % , a viscosity of about 12000 cps ( 25 "' C ) , available from Bayer MaterialScience AG;
Desmodur 44V20L: PMDI , NCO content of 30.5-32.5 wt . % , available from Bayer MaterialScience AG;
Desmophen 4030 M : polyether polyol , a hydroxy1 number of 380 , available from Bayer MaterialScience AG;
Desmophen 4034B : polyether polyol , a hydroxy1 number of 440 , available from Bayer MaterialScience AG;
Arcol 1021 : polyether polyol, a hydroxy1 number of 56, available from Bayer MaterialScience AG;
L-6920 : a foam stabilizer available from Moment ive ;
Polycat 8 : a catalyst available from Air Products ;
Polycat 41 : a catalyst available from Air Products ;
HK 470 Type of conventional high-pressure foaming machine : available from Hennecke company .
The isocyanate- react ive components used in the amounts shown in Table 1 were mixed and then reacted in HK 470 Type of conventional high-pressure foaming machine based on the amounts shown in Table 2. After the reaction, the liquid polyurethane is poured into a mold of 20 cm * 30 cm * 60 cm, the temperature of the mold is controlled between 25-35 , the temperature of raw materials is 25-30 , the mixing pressure of the high-pressure machine is 120-150 bar . The foam rises substantially freely since there is no cover on the mold . After 20 minutes , it was demolded and kept at room temperature for 24 hours , and the top part which is uneven is cut off . The remaining lower part is cut into test samples with desired size in accordance with the foam test standards . A group of five samples were tested in terms of mechanical properties (according to GB/T 8813-2008) and heat insulation properties (according to GB/T3399-1982 ) . The test data are shown in Table 2.
The polyurethane rigid foams of Examples 2 and 3 have a lower thermal conductivity and therefore better insulation properties In addition, the polyurethane rigid foams of Examples 2 and 3 have a higher compression strength in the direction vertical to foaming when compared with that of Example 1 having the same density .
Table 1: Isocyanate- reactive components
Figure imgf000012_0001
Table 2 : Polyurethane rigid foam and the properties thereof
Examples unit 1* 2 3
isocyanate - reactive
pbw 100 100 100 component
Desmodur 44V20L pbw 100 80 75
TDI residue pbw 0 20 25
Cream time second 147 209 215 Tack - f ree time second 300 387 398
Foam density kg/m3 34.7 34.5 34.7 compression
strength
KPa 131 136 164 (vertical
direction)
Thermal
mW/m. K 22.27 21.67 21.64 conductivity
* comparative example

Claims

Claims
1. An isocyanate composition, comprising :
al) a toluene diisocyanate residue , wherein the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method, and wherein the toluene diisocyanate residue has a NCO content of 5-45 wt.%, based on total weight of the toluene diisocyanate residue ; and a2 ) diphenyl methane diisocyanate , poly (diphenyl methane diisocyanate) or a combination thereof .
2. The isocyanate composition according to claim 1 , wherein the isocyanate composition has a NCO content of 30-40 wt.%, based on total weight of the isocyanate composition .
3. The isocyanate composition according to claim 1 or 2 , wherein the toluene diisocyanate residue is selected from the distillation residue of toluene diisocyanate prepared by phosgene method in gas phase .
4. The isocyanate composition according to claim 3, wherein the toluene diisocyanate residue has a content of 15-40 wt.%, based on total weight of the isocyanate composition .
5. A polyurethane rigid foam, wherein the polyurethane rigid foam is prepared from the isocyanate composition according to any one of claims 1 -4.
PCT/EP2016/062230 2015-06-01 2016-05-31 Isocyanate composition and polyurethane rigid foam prepared from the same Ceased WO2016193245A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510310534.9 2015-06-01
CN201510310534.9A CN106279623A (en) 2015-06-01 2015-06-01 Isocyanate composition and hard polyurethane foam prepared therefrom

Publications (1)

Publication Number Publication Date
WO2016193245A1 true WO2016193245A1 (en) 2016-12-08

Family

ID=56098241

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/062230 Ceased WO2016193245A1 (en) 2015-06-01 2016-05-31 Isocyanate composition and polyurethane rigid foam prepared from the same

Country Status (2)

Country Link
CN (1) CN106279623A (en)
WO (1) WO2016193245A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH571544A5 (en) * 1971-05-11 1976-01-15 Bayer Ag
GB1434917A (en) * 1972-06-02 1976-05-12 Ici Ltd Isocyanates
EP0497538A2 (en) * 1991-01-28 1992-08-05 The Dow Chemical Company Process for reducing hydrolyzable chloride in toluene diisocyanate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH571544A5 (en) * 1971-05-11 1976-01-15 Bayer Ag
GB1434917A (en) * 1972-06-02 1976-05-12 Ici Ltd Isocyanates
EP0497538A2 (en) * 1991-01-28 1992-08-05 The Dow Chemical Company Process for reducing hydrolyzable chloride in toluene diisocyanate
CN1064074A (en) 1991-01-28 1992-09-02 陶氏化学公司 Reduce the method for hydrolyzable chloride in the tolylene diisocyanate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HOUBEN WEYL: "Makromolekulare Stoffe", vol. XIV/2, 1963, GEORG THIEME VERLAG, article "Methoden der Organischen Chemie", pages: 17

Also Published As

Publication number Publication date
CN106279623A (en) 2017-01-04

Similar Documents

Publication Publication Date Title
JP6026518B2 (en) Rigid polyurethane foam
JP4743970B2 (en) Polyol mixture for making rigid polyurethane foam
WO2021023889A1 (en) Improved method of recycling polyurethane materials
JP6470610B2 (en) Method for producing polyurethane foam and polyurethane foam obtained thereby
JP2009537668A (en) Polyurethane elastomer with enhanced hydrolysis resistance
KR20180027489A (en) Preparation of polyurethane foams
KR20170125938A (en) Polybutadiene for the production of glassy polyurethane
CN102449025A (en) Polyester polyols prepared from isophthalic and/or terephthalic acid and oligomeric alkylene oxides
CN1261475C (en) Process for producing rigid polyurethane foams and finished products obtained therefrom
JP2020535254A (en) Manufacture of polyurethane foam
EP3894454A1 (en) Rigid polyisocyanurate and polyurethane foams and methods for preparing the same
US7705063B2 (en) Polyurethane foam and a resin composition
CN114555669A (en) Production of rigid polyurethane foams
JP5866839B2 (en) Rigid polyurethane foam composition
JP2013151635A (en) Raw material blending composition for manufacturing polyurethane foam
JP5767111B2 (en) Viscosity reducing agent for polyether polyol
JP4273815B2 (en) Manufacturing method of rigid foam synthetic resin
WO2016193245A1 (en) Isocyanate composition and polyurethane rigid foam prepared from the same
US20220025144A1 (en) Rigid polyisocyanurate and polyurethane foams and methods for preparing the same
EP4165100B1 (en) Isocyanate-reactive composition and method of preparing polyurethane and polyisocyanurate foams
EP4602099A1 (en) Chemolysis process for polyisocyanurate foams
JPH0372515A (en) Production of rigid foam
TW202546062A (en) A foam composition for producing a polyurethane-based foam comprising an additive to prevent or reduce phenolic yellowing
WO2025114378A1 (en) Polyurethane foam, method for preparing the same, and article thereof
EP4165098A1 (en) Preparation of polyurethane and polyisocyanurate foams using liquid siloxane nucleating additive

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: 16726857

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: 16726857

Country of ref document: EP

Kind code of ref document: A1