WO2014037312A1 - A polyurethane modeling composition - Google Patents

A polyurethane modeling composition Download PDF

Info

Publication number
WO2014037312A1
WO2014037312A1 PCT/EP2013/068109 EP2013068109W WO2014037312A1 WO 2014037312 A1 WO2014037312 A1 WO 2014037312A1 EP 2013068109 W EP2013068109 W EP 2013068109W WO 2014037312 A1 WO2014037312 A1 WO 2014037312A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane
modeling
modeling composition
composition according
acid
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/EP2013/068109
Other languages
French (fr)
Inventor
Yuan Cheng
Yongming GU
Ian ZHENG
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 Deutschland AG
Original Assignee
Bayer MaterialScience 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 Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of WO2014037312A1 publication Critical patent/WO2014037312A1/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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
    • C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/6629—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6662—Compounds of group C08G18/42 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • 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
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/28—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2375/00—Polyureas; Polyurethanes

Definitions

  • the present invention relates to a polyurethane modeling composition, and a modeling article prepared from the same which has improved physical and processing property.
  • the present invention also relates to a process of manually preparing the modeling article.
  • Modeling paste is a pasty resin system which is usually made by dispersing fillers like glass microspheses into polyester or epoxy resin. This resin system exhibits excellent physical properties such as good toughness, hardness, dimensional stability, good heat resistance, compressive strength, flexural strength and good machinability when cured with reactive hardener. Modeling paste is used in making a variety of models, molds and checking fixture. Polyurethane modeling paste is a filled pasty polyurethane resin system.
  • EP1332045B 1 discloses a method of making seamless model. This method refers to a polyurethane modeling paste system, which contains a high molecular weight polyol and a low molecular weight polyol containing amine groups.
  • the polyurethane modeling paste is a froth forming paste prepared by injecting inert gas with mechanical stirring into a resin composition to reduce the system density.
  • US7994235B2 discloses a polyurethane modeling paste with a density range from 0.4 -0.9g/cm 3 .
  • This paste system comprises a chemical thixotropic agent to provide sufficient sag resistance, therefore the paste can be applied on vertical or curved surface.
  • the paste system has to be processed with an extrusion machine as the paste system comprises amine polyol and chemical thixotropic agent both of which shorten the pot life of the paste significantly.
  • a polyurethane modeling composition having longer pot life such that the polyurethane model can be prepared manually during the actual operation.
  • the polyurethane model prepared from the polyurethane modeling composition has favorable hardness thus better physic property is provided.
  • the polyurethane modeling composition of the present invention comprises:
  • polyether polyols with a functionality of 2-6 and hydroxyl number of 100-700 which is the copolymerization and/or homopolymerization product of an epoxy compound and a polyol compound which doesn't comprise amine group;
  • (f) optionally one or more microspheres with a density of 20-500 kg/m 3 .
  • the polyether polyol has a functionality of 3-5, and a hydroxyl number of 150-550, preferably 300-500.
  • the epoxy compound is the one or more selected from the group consisting of 1 ,2-propylene oxide, epichlorohydrin, trichloro-butylene oxide, 1,2 - butylene oxide, 2,3 - butylene oxide, styrene oxide, tetrahydrofuran, oxetane or the combination thereof.
  • the polyol compound is the one or more selected from the group consisting of ethylene glycol, propylene glycol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3- butanediol, 1 ,4-butanediol, 1 ,2-pentanediol, 1 ,4- pentanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, 1 ,7-heptanediol, glycerol, 1 , 1 , 1-trimethylolpropane, 1 , 1 , 1 -trimethylol ethane, 1 ,2,6-hexanetriol, pentaerythritol, xylitol, sorbitol, sucrose, bisphenol A, bisphenol S or the combination thereof.
  • the polyol compound is the one or more selected from the group
  • the component (c2) one or more aliphatic acids or derivatives thereof, which comprise straight or branch alkyl or alkenyl with 5-30 carbon atoms.
  • the component (c l) is the one or more selected from the group consisting of glycol, diethyleneglycol, triethylene glycol, tetraethylene glycol, 1 ,2-propanediol, 1,3-propanediol, 1 ,4-butanediol, 3-methyl-l,5- pentanediol, 1,5-pentanediol, 1,6- hexanediol, 1,10-decylenediol, glycerol, 1,2,4- butantriol, 1,2,5- pentantriol, 1,3,5- pentantriol, 1,2,6-hexanetriol, 1,2,5- hexanetriol, 1,3,6-hexanetriol, trimethylolbutane, trimethylolpropane or di(trimethyl
  • the component (c2) is the one or more selected from the group consisting of ⁇ -caprolactone, adipic acid, lauric acid, myristic acid, palmitic acid, ricinoleic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid or derivatives thereof.
  • the polyurethane modeling composition further comprises one or more aromatic polyester polyols with a functionality of 2-4 and a hydroxyl number of 100-450.
  • the thixotropic agents are the one or more selected from fumed silica.
  • the organic polyisocyanates are the one or more selected from the group consisting of polymethylene polyphenlene isocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or poly-4,4'- diphenylmethane diisocyanate or the combination thereof.
  • a modeling article comprising a substrate and a polyurethane modeling layer disposed on the substrate, wherein the polyurethane modeling layer is prepared from the polyurethane modeling composition.
  • the polyurethane modeling layer has a hardness of 45-65 shore D, determined according to ISO868: 2003.
  • the polyurethane modeling layer has a density of 0.3-0.9 g/cm 3 , determined according to ISO2781 : 1996.
  • the substrate is the one selected from the group consisting of woods, steel products, aluminum products, polyurethane foam, styrene foam or the combination thereof.
  • a process of preparing the modeling article comprising the step of: (I) providing a substrate having an exposed outer surface;
  • the polyurethane model of the present invention has better mechanical properties, particular favourable hardness. Moreover, the polyurethane modeling composition has longer pot-life, such that the polyurethane composition can be applied to the substrate manually without using expensive extrusion machine. I. Polyurethane modeling composition
  • the polyurethane modeling composition of the present invention comprises:
  • (f) optionally one or more microspheres with a density of 20-500 kg/m 3 .
  • polyurethane model includes polyurethane model in a form of paste or board.
  • Polyisocyanates suitable for used in the present invention include unmodified isocyanates, modified polyisocyanates, and isocyanate prepolymers.
  • organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136.
  • Examples of such isocyanates include those represented by the formula,
  • n is an integer from 2-5, preferably 2-3, and Q is an aliphatic hydrocarbon group containing 2-18, preferably 6-1 0, carbon atoms ; a cycloaliphatic hydrocarbon group containing 4- 15, preferably 5-10, carbon atoms; an araliphatic hydrocarbon group containing 8-15, preferably 8-13, carbon atoms; or an aromatic hydrocarbon group containing 6-15, preferably 6- 13, carbon atoms.
  • Isocyanates suitable for use in the present invention include 1,2-ethylene diisocyanate; 1 ,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,12- dodecane diisocyanate; cyclobutane-l,3-diisocyanate; cyclohexane-l,3-and -1,4-diisocyanate, and mixtures of these isomers; l-isocyanato-3,3,5- trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate); 2,4- and 2,6-hexahydrotoluene diisocyanate and mixtures of these isomers; dicyclohexylmethane-4,4' -diisocyanate (hydrogenated MDI, or HMDI); 1,3- and 1,4-phenylene diisocyanate; 2,4- and 2,6-toluene diisocyanate
  • isocyanate-containing distillation residues accumulating in the production of isocyanates on a commercial scale, optionally in solution in one or more of the polyisocyanates mentioned above.
  • a person skilled in the art will know that the mixture of the above isocyanates can also be used in the present invention.
  • Isocyanate-terminated prepolymers may also be employed in the preparation of the polyurethane models of the present invention.
  • Prepolymers may be prepared by reacting an excess of organic polyisocyanate or mixtures thereof with a minor amount of an active hydrogen-containing compound as determined by the well-known Zerewitinoff test. These compounds and their methods of preparation are well known to those skilled in the art. In the present invention, any active hydrogen-containing compound can be used to prepared the isocyanate-terminated prepolymer.
  • the organic polyisocyanates are the one or more selected from the group consisting of polymethylene polyphenlene isocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or poly-4,4'- diphenylmethane diisocyanate or the combination thereof.
  • the polyurethane modeling composition further comprises one or more polyether polyol, which is the copolymerization and/or homopolymerization product of an epoxy compound and a polyol compound which doesn't comprise amine group.
  • the preparation process of the polyether polyol has been known to a person skilled in the art, such as those described in EP-A 283 148, US patent 3,278,457, 3,427,256, 3,829,505, 4,472,560, 3,278,458, 3,427,334, 3,941 ,849, 4,721 ,818, 3,278,459, 3,427,335 and 4,355, 188.
  • the polyether polyol has a functionality of 2-6, preferably 3-5, more preferably 4-5 ; and a hydroxyl number of 100-700, preferably 150-550, more preferably 300-500.
  • epoxy compound refers to the compound having the following formula (I):
  • i and R 2 are independently selected from H, C 1 -C6 straight or branch alkyl, phenyl and substituted phenyl.
  • Ri and R 2 are independently selected from H, methyl, ethyl, propyl, and phenyl.
  • epoxy compound suitable for use in the present invention include, but not limited to, ethylene oxide, 1 ,2- propylene epoxide, epichlorohydrin, trichlorobutylene oxide, 1 ,2-butylene oxide, 2,3-butylene oxide, phenylethylene oxide or the combination thereof.
  • epoxy compound further comprises oxacycloalkane, such as, but not limited to, tetrahydrofuran, oxetane or the combination thereof.
  • polyol compound refers to the compound comprising two or more hydroxyls.
  • the polyol compound which doesn't comprise amine group refers to the compound comprising two or more hydroxyls and is free of amine groups, wherein the "amine group” comprises primary amine group (-NH2-), secondary amine group (-NH-) and tertiery amine groups (-N-).
  • the polyol compound can optionally comprise substituents which are not reactive to the reaction between polyol and isocyanate, and the substituent can be unsaturated.
  • Suitable examples of the polyol compound include, but not limited to ethylene glycol, propylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,2-pentanediol, 1 ,6- hexanediol, 1 ,7-heptanediol, glycerol, 1 , 1 , 1- trimethylolpropane, 1 , 1 , 1- trimethylolethane, 1 ,2,6-hexanetriol, pentaerythritol, xylitol, sorbitol, sucrose, bisphenol A, bisphenol S or the combination thereof.
  • aliphatic polyester polyol refers to the product prepared by polyhydroxyl compounds and aliphatic acids and the derivates thereof, wherein the aliphatic acid derivate comprises anhydrides, esters, and acyl halides of the aliphatic acid.
  • the aliphatic polyester polyol has a hydroxyl number of 100-500 and a functionality of 2-4.
  • the aliphatic polyester polyols are prepared from the components comprising: (cl) one or more diols, triols or tetraols;
  • (c2) one or more aliphatic acids or derivatives thereof, which comprise straight or branch alkyl or alkenyl with 5-30 carbon atoms;
  • the (cl) component is selected from the group consisting of glycol, diethyleneglycol, triethylene glycol, tetraethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,4-butanediol, 3-methyl- l ,5- pentanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, 1 , 10-decylenediol, glycerol, 1 ,2,4- butantriol, 1 ,2,5- pentantriol, 1 ,3,5- pentantriol, 1 ,2,6-hexanetriol, 1 ,2,5- hexanetriol, 1 ,3,6-hexanetriol, trimethylolbutane, trimethylolpropane or di(trimethylolpropane), trimethylol ethane, pentaerythritol
  • the (c l ) component is selected from the group consisting of glycerol, diethyleneglycol, glycol, propanediol, trimethylolpropane, diethylene glycol and pentaerythritol.
  • (c2) component is the one or more selected from the group consisting of ⁇ -caprolactone, adipic acid, lauric acid, myristic acid, palmitic acid, ricinoleic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid or derivatives thereof
  • the examples of the aliphatic polyester polyols include, but not limited to, castor oil, poly ⁇ -caprolacloneglycol, polycaprolacton polyol, polyethyleneglycol adipate, and polypropylene glycol adipate.
  • the polyurethane modeling composition further comprises one or more aromatic polyester polyols.
  • the polyurethane model prepared from the polyurethane modeling composition comprising aromatic polyester polyols has higher glass transition temperature (Tg), thus has better heat resistance.
  • aromatic polyester polyol refers to the product prepared by polyhydroxyl compounds and carboxylic acids comprising aromatic groups and the derivates thereof, wherein the derivates of the carboxylic acids comprising aromatic groups comprises anhydrides, esters, and acyl halides of the carboxylic acid.
  • the aromatic polyester polyol has a functionality of 2-4, preferably 2-3, and a hydroxyl value of 100-450, preferably 200-450.
  • the carboxylic acids or the derivates thereof suitable for preparing the aromatic polyester polyols comprise, but not limited to, phthalic acid, isophthalic acid, trimellitic acid, terephthalic acid, phthalic acid anhydride, tetrahydrophthalic acid anhydride, pyromellitic dianhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride, terephthalic acid dimethyl ester and terephthalic acid-bis-glycol ester.
  • the aromatic polyester polyol has a content of 1-40 wt.%, more preferably 10-30 wt.%, further preferably 15-20 wt.%, based on 100% by weight of the polyol component.
  • the polyurethane modeling composition may further comprise one or more thixotropic agents.
  • the thixotropic agent can increase viscosity of liquid, and impart thixotropic property to liquid.
  • the resin comprising it has higher consistency when being standstill, and will have a low consistency under external force.
  • the thixotropic agents commonly used in the art comprise fumed silica, organic bentonite, hydrogenated castor oil and polyamide wax.
  • the thixotropic agent may have a content of 2-8 wt.%, based on 100% by weight of the polyol component.
  • the thixotropic agent can be selected from fumed silica.
  • Fumed silica is generally produced by the vapor phase hydrolysis of silicon tetrachloride in a hydrogen oxygen flame. The combustion process creates silica molecules, which condense to form particles, which in turn sinter together into aggregates. Fumed silica is available in treated and untreated grades. The untreated grades vary in surface area, bulk density, and thickening efficiency in nonpolar systems, examples of the fumed silica may those commercialized by Cabot Corporation Degussa Corporation and Wacker Silicones Corporation.
  • examples of preferred fumed silica include, but not limited to, CAB-O-SILL-90, MS- 55, HS-5, LM-130, LM-150, HDK 30, M-5, and Degussa AE OSIL R200, US200, R202, R972, US202, US204 and US206.
  • the fumed silica has an average particle size of 7-40 nm.
  • the polyurethane modeling composition further comprises one or more water removing agents.
  • the polyurethane modeling composition will be foaming because of the water contained in the commercialized polyol components, and the moisture in the air during the processing, thus the mechanical property of the obtained polyurethane model becomes worse. Therefore, the mechanical property of the polyurethane model can be improved by adding one or more water removing agents to remove the water contained in the composition or moisture.
  • the polyurethane modeling composition of the present invention has a water content of 2-5wt.%, based on 100% by weight of the polyol component.
  • water removing agents suitable for use in the present invention but not limited to, molecular sieve, vinyl silane, such as vmyltrimethoxysilane (for example Silquest A-171) and methyltrimethoxysilane (such as Silquest A- 1630).
  • vmyltrimethoxysilane for example Silquest A-171
  • methyltrimethoxysilane such as Silquest A- 1630.
  • Other suitable examples of water removing agents include, but not limited to, Addtive TI (p-toluene sulfonyl isocyanate) and O F (e ste r c o mp ounds ) commercialized from OMG Borchers.
  • the polyurethane modeling composition further comprises one or more microspheres with a density of 20-500 kg/m 3 .
  • the microspheres can be solid or hollow, and can be prepared by the components: a c ry l i c typ e r e s i n s s u c h a s p o l y a c ry l o n i t r i l e a n d polymethylmethacrylate, acrylic modified styrene, polyvinylidene chloride, copolymers of styrene and methyl methacrylate, phenolic resins, epoxy resins, urea resins, hollow glass, silica, ceramic or carbon spheres.
  • microspheres suitable for use in the present invention include, but not limited to, Expancel, available from Akzo Nobel Corporation; phenolic microspheres, available from Asia Pacific microspheres and Matsumoto microspheres available from Yusht-Seiyaku Company, and hollow glass microspheres K15 K25 and SH38 available from 3M. These microspheres preferably have a diameter of about 5 to about 250 micrometers.
  • the microspheres, or hollow microspheres, suitable for use in the invention are conventional in the art and methods for production of these microspheres are well known. Such microspheres are readily available commercially.
  • the microspheres facilitate machining, lead to reduced density and reduce the coefficient of thermal expansion.
  • the surface of the microspheres may be treated suitably for better compatibility with the resin composition.
  • the polyurethane modeling composition of the present invention may be homogenized by means of manual, for example stirring. Compared to homogenize with an extrusion machine whose injection head tends to be jammed, the process implemented manually allows a polyurethane modeling composition with more microspheres, thus producing a polyurethane model with lower density.
  • the polyurethane modeling composition of the present invention may comprises the microspheres in a content of 40-80 vol.%, preferably 60-80 vol.%, based on 100% by volume of the polyol or the isocyanate component. Microbaloons may be added to the polyol or the isocyanate component or both.
  • the polyurethane modeling composition may further comprise one or more foam stabilizers to prevent the formation of big bubbles which may impair the surface quality of the model.
  • foam stabilizers suitable for use in the present invention comprise silicone foam stabilizer and fluoro-foam stablilizer and the like .
  • Illustrative examples of the silicone foam stabilizer include, but not limit to SRX-274C commercialized from Toray Silicon Co., Ltd., and Niax L-6920 commercialized from Momentive Co., Ltd.
  • the polyurethane modeling composition may further comprise one or more defoamers, the illustrative example s thereof comprise, but not limit to , polysiloxane emulsion, such as Silikon® SRE and Rhodorsil® Rhodia; long chain alcohol, fatty acid or the salts thereof; organic fluorine compounds and the mixture thereof.
  • defoamers such as Silikon® SRE and Rhodorsil® Rhodia
  • long chain alcohol, fatty acid or the salts thereof organic fluorine compounds and the mixture thereof.
  • the polyurethane modeling composition may further comprise auxiliaries and additives commonly used in the art, such as diluents, fillers (e.g. calcium carbonate), fibers, pigments, dyes, flame retardants, surfactants, wetting agents and polymer toughening agents.
  • auxiliaries and additives commonly used in the art, such as diluents, fillers (e.g. calcium carbonate), fibers, pigments, dyes, flame retardants, surfactants, wetting agents and polymer toughening agents.
  • auxiliaries and additives commonly used in the art, such as diluents, fillers (e.g. calcium carbonate), fibers, pigments, dyes, flame retardants, surfactants, wetting agents and polymer toughening agents.
  • a person skilled in the art may choose suitable auxiliaries and additives according to the properties of the final products.
  • the polyurethane model prepared from the polyurethane modeling composition of the present invention has better hardness of 45-65 shore D, determined according to ISO868 : 2003.
  • the polyurethane modeling composition has higher glass transition temperature of 49-100 ° C, thus the polyurethane model prepared from the same has better heat resistance property.
  • the present invention further refers to a modeling article comprising a substrate and a polyurethane modeling layer disposed on the substrate, wherein the polyurethane modeling layer is prepared from the polyurethane modeling composition illustrated above.
  • the polyurethane modeling layer has favorable mechanical properties, such as toughness, hardness, temperature resistance, compressive strength, flexural strength, and excellent dimensional stability, therefore the model or mold prepared from the polyurethane model has higher size precision.
  • the polyurethane model both has higher hardness and flexibility such that less dust is produced during processing and improves the processing environment.
  • the modeling article of the present invention may be prepared by applying the polyurethane modeling composition of the present invention on a substrate, curing the polyurethane modeling composition and machining the cured polyurethane modeling layer to the desired contour, wherein the substrate may be prepared from any material, including but not limit to, wood, steel, aluminum, polyurethane foam or styrene foam.
  • the substrate may be optionally machined to any desired contour before applying to the polyurethane modeling composition of the present invention.
  • the surface of the substrate may be treated, for example polishing to obtain a smooth surface or applying coating according to actual needs.
  • the modeling article of the present invention has a polyurethane modeling layer with favorable mechanical properties, may be used in model design, mold, checking fixture s and the like.
  • the present invention further relates to a process of preparing the modeling article, comprising the step of:
  • the existing preparation process of modeling articles all comprise the step of applying polyurethane modeling composition to the substrate by extrusion machine.
  • the cost of such process is high because of the expensive extrusion machine, furthermore, the modeling article prepared by such process has higher density because low density microsphere is used in a lower content so as to not choke the injection head.
  • the polyurethane composition has a pot life of more than 25 minutes, preferably 40 minutes, such that it may be applied to the substrate manually without using extrusion machine and overcome the deficiency of the existing process.
  • the substrate having an exposed outer surface may have any desire shape, and the exposed outer surface may be machined or not.
  • the continuous layer of the polyurethane modeling composition may be prepare by applying the polyurethane modeling composition to the outer surface of the substrate in a way of extrusion, blade coating, brush coating, roll coating, knife coating and the like. It is well known to a person skilled in the art that one or more layer of the polyurethane composition of the present invention may be applied to the out surface of the substrate.
  • the curing of the continuous layer of polyurethane modeling composition may use the curing method commonly used in the art, such as room temperature curing method, heating method, UV radiation method.
  • heating method is preferably used in the present invention, and the heating temperature may be 50-70 ° C and last 3-5 hours.
  • Machining the cured polyurethane modeling layer may use the apparatus and tools commonly used in the art, such as milling machine, preferably numerically controlled machine. Examples
  • Desmodur 0418 a polymeric MDI having a NCO content of 32% which is commercially available from Bayer materialScience Company Limited;
  • Multranol 9158 a polyether polyol having a functionality of 3 and an -OH mumber of approximately 470 mg KOH/g which is commercially available from Bayer materialScience Company Limited;
  • Arcol A3500 a polyether polyol having a functionality of 3.6 and an OH number of approximately 500 mg KOH/g which is commercially available from Bayer materialScience Company Limited;
  • Arcol S440 a polyether polyol having a functionality of 4.6 and an OH number of approximately 500 mg KOH/g which is commercially available from Bayer materialScience Company Limited;
  • Stepan PS4027 a polyester polyol having a functionality of 2.7 and an - OH number of approximately 400 mg KOH/g which is commercially available from Stepan Company;
  • Castor oil an aliphatic polyester polyol having a functionality of 2.7 and an OH number of approximate 157 which is commercially available from ihao Chemical Co Limited;
  • BYK® 066 N a silicone de former which is commercially available from BYK;
  • Niax L-6920 a surfactant which is commercially available from Momentive;
  • HYD03B a molecular sieves which is commercially available from Hengye Chemical Engineering Co., Ltd;
  • Sipernat® 22LS a thixotropic agent which is commercially available from Deguss; K15: a hollow microsphere having a bulk density of 0. 1 5g/cm 3 which is commercially available from 3M;
  • K25 a hollow microsphere having a bulk density of 0.25g/cm 3 which is commercially available from 3M
  • S38HS a hollow micro sphere having a bulk density of 0.38g/cm 3 which is commercially available from 3M;
  • Example 1 was prepared as following: 1000 grams material was prepared according to weight percentage giving in table 1 and mixed manually until homogenization. All steps including weighting and mixing were conducted in fumed hood at room temperature. (Temperature 20-25 °C, Relative humidity 45%-55%).
  • Examples 2-6 were prepared as Example 1 and shown in table 1.
  • polyurethane modeling composition comprising polyether polyols of different functionality and OH number has low density, high hardness, good sag resistance and long pot life. And as shown in the observation for the surface grain of the machined surface, the polyurethane modeling articles have very fine surface quality and may meet the requirements of model making.
  • aromatic polyol and high functionality polyether polyol can significantly improve Tg and hardness
  • polyurethane model with different density may be prepared by adding corresponding amount of microsphere as filler, and the polyurethane model with higher hardness may be obtained by using high density fillers.

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)

Description

A polyurethane modeling composition
Technical Field
The present invention relates to a polyurethane modeling composition, and a modeling article prepared from the same which has improved physical and processing property. The present invention also relates to a process of manually preparing the modeling article.
Background Modeling paste is a pasty resin system which is usually made by dispersing fillers like glass microspheses into polyester or epoxy resin. This resin system exhibits excellent physical properties such as good toughness, hardness, dimensional stability, good heat resistance, compressive strength, flexural strength and good machinability when cured with reactive hardener. Modeling paste is used in making a variety of models, molds and checking fixture. Polyurethane modeling paste is a filled pasty polyurethane resin system.
EP1332045B 1 discloses a method of making seamless model. This method refers to a polyurethane modeling paste system, which contains a high molecular weight polyol and a low molecular weight polyol containing amine groups. The polyurethane modeling paste is a froth forming paste prepared by injecting inert gas with mechanical stirring into a resin composition to reduce the system density.
US7994235B2 discloses a polyurethane modeling paste with a density range from 0.4 -0.9g/cm3. This paste system comprises a chemical thixotropic agent to provide sufficient sag resistance, therefore the paste can be applied on vertical or curved surface. The paste system has to be processed with an extrusion machine as the paste system comprises amine polyol and chemical thixotropic agent both of which shorten the pot life of the paste significantly. Summary of the Invention
In one aspect of the present invention is provided a polyurethane modeling composition having longer pot life such that the polyurethane model can be prepared manually during the actual operation. In addition, the polyurethane model prepared from the polyurethane modeling composition has favorable hardness thus better physic property is provided.
The polyurethane modeling composition of the present invention comprises:
(a) one or more organic polyisocyanates;
(b) one or more polyether polyols with a functionality of 2-6 and hydroxyl number of 100-700 which is the copolymerization and/or homopolymerization product of an epoxy compound and a polyol compound which doesn't comprise amine group;
(c) one or more aliphatic polyester polyols with a hydroxyl number of 100-500 and a functionality of 2-4; (d) optionally one or more thixotropic agents;
(e) optionally one or more water removing agents; and
(f) optionally one or more microspheres with a density of 20-500 kg/m3.
In various embodiments of the present invention, the polyether polyol has a functionality of 3-5, and a hydroxyl number of 150-550, preferably 300-500.
In various embodiments of the present invention, the epoxy compound is the one or more selected from the group consisting of 1 ,2-propylene oxide, epichlorohydrin, trichloro-butylene oxide, 1,2 - butylene oxide, 2,3 - butylene oxide, styrene oxide, tetrahydrofuran, oxetane or the combination thereof. In various embodiments of the present invention, the polyol compound is the one or more selected from the group consisting of ethylene glycol, propylene glycol, 1 ,3-propanediol, 1 ,2-butanediol, 1 ,3- butanediol, 1 ,4-butanediol, 1 ,2-pentanediol, 1 ,4- pentanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, 1 ,7-heptanediol, glycerol, 1 , 1 , 1-trimethylolpropane, 1 , 1 , 1 -trimethylol ethane, 1 ,2,6-hexanetriol, pentaerythritol, xylitol, sorbitol, sucrose, bisphenol A, bisphenol S or the combination thereof. In various embodiments of the present invention, the one or more aliphatic polyester polyols can be prepared from the components comprising:
(cl) one or more diols, triols or tetraols;
(c2) one or more aliphatic acids or derivatives thereof, which comprise straight or branch alkyl or alkenyl with 5-30 carbon atoms. In various embodiments of the present invention, the component (c l) is the one or more selected from the group consisting of glycol, diethyleneglycol, triethylene glycol, tetraethylene glycol, 1 ,2-propanediol, 1,3-propanediol, 1 ,4-butanediol, 3-methyl-l,5- pentanediol, 1,5-pentanediol, 1,6- hexanediol, 1,10-decylenediol, glycerol, 1,2,4- butantriol, 1,2,5- pentantriol, 1,3,5- pentantriol, 1,2,6-hexanetriol, 1,2,5- hexanetriol, 1,3,6-hexanetriol, trimethylolbutane, trimethylolpropane or di(trimethylolpropane), trimethylol ethane, pentaerythritol, dipentaerythritol and sorbitol; Preferably, the component (c l) is the one or more selected from the group consisting of glycerol, diethyleneglycol, glycol, pentanediol, trimethylolpropane, diethylene glycol and pentaerythritol. In various embodiments of the present invention, the component (c2) is the one or more selected from the group consisting of ε-caprolactone, adipic acid, lauric acid, myristic acid, palmitic acid, ricinoleic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid or derivatives thereof.
In various embodiments of the present invention, wherein the polyurethane modeling composition further comprises one or more aromatic polyester polyols with a functionality of 2-4 and a hydroxyl number of 100-450.
In various embodiments of the present invention, the thixotropic agents are the one or more selected from fumed silica.
In various embodiments of the present invention, the organic polyisocyanates are the one or more selected from the group consisting of polymethylene polyphenlene isocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or poly-4,4'- diphenylmethane diisocyanate or the combination thereof.
In one aspect of the present invention is provided a modeling article, comprising a substrate and a polyurethane modeling layer disposed on the substrate, wherein the polyurethane modeling layer is prepared from the polyurethane modeling composition. The polyurethane modeling layer has a hardness of 45-65 shore D, determined according to ISO868: 2003. The polyurethane modeling layer has a density of 0.3-0.9 g/cm3, determined according to ISO2781 : 1996. In various embodiments of the present invention, the substrate is the one selected from the group consisting of woods, steel products, aluminum products, polyurethane foam, styrene foam or the combination thereof.
In one aspect of the present invention is provided a process of preparing the modeling article, comprising the step of: (I) providing a substrate having an exposed outer surface;
(II) applying manually the polyurethane modeling composition according to any one of the claims 1-13 to the outer surface of the substrate, to form a continuous layer of the polyurethane modeling composition;
(III) curing the continuous layer of polyurethane modeling composition to form a polyurethane modeling layer; and
(IV) machining the cured polyurethane modeling layer to the desired contour.
Detailed Description
Compared to the polyurethane model in the art, the polyurethane model of the present invention has better mechanical properties, particular favourable hardness. Moreover, the polyurethane modeling composition has longer pot-life, such that the polyurethane composition can be applied to the substrate manually without using expensive extrusion machine. I. Polyurethane modeling composition
The polyurethane modeling composition of the present invention comprises:
(a) one or more organic polyisocyanates; (b) one or more polyether polyols with a functionality of 2-6 and hydroxyl number of 100-700 which is the copolymerization and/or homopolymerization product of an epoxy compound and a polyol compound which doesn't comprise amine group;
(c) one or more aliphatic polyester polyols with a hydroxyl number of 100-500 and a functionality of 2-4;
(d) optionally one or more thixotropic agents;
(e) optionally one or more water removing agents; and
(f) optionally one or more microspheres with a density of 20-500 kg/m3.
As used herein, the term "polyurethane model" includes polyurethane model in a form of paste or board.
Polyisocyanates suitable for used in the present invention include unmodified isocyanates, modified polyisocyanates, and isocyanate prepolymers. Such organic polyisocyanates include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136. Examples of such isocyanates include those represented by the formula,
Q(NCO)„ in which n is an integer from 2-5, preferably 2-3, and Q is an aliphatic hydrocarbon group containing 2-18, preferably 6-1 0, carbon atoms ; a cycloaliphatic hydrocarbon group containing 4- 15, preferably 5-10, carbon atoms; an araliphatic hydrocarbon group containing 8-15, preferably 8-13, carbon atoms; or an aromatic hydrocarbon group containing 6-15, preferably 6- 13, carbon atoms. Isocyanates suitable for use in the present invention include 1,2-ethylene diisocyanate; 1 ,4-tetramethylene diisocyanate; 1,6-hexamethylene diisocyanate; 1,12- dodecane diisocyanate; cyclobutane-l,3-diisocyanate; cyclohexane-l,3-and -1,4-diisocyanate, and mixtures of these isomers; l-isocyanato-3,3,5- trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate); 2,4- and 2,6-hexahydrotoluene diisocyanate and mixtures of these isomers; dicyclohexylmethane-4,4' -diisocyanate (hydrogenated MDI, or HMDI); 1,3- and 1,4-phenylene diisocyanate; 2,4- and 2,6-toluene diisocyanate and mixtures of these isomers ("TDI"); diphenylmethane-2,4'- and/or -4,4'-diisocyanate (MDI); naphthylene-l,5-diisocyanate; triphenylmethane-4,4',4"-triisocyanate; polyphenyl-polymethylene-polyisocyanates of the type which may be obtained by condensing aniline with formaldehyde, followed by phosgenation (crude MDI or polymeric MDI, PMDI, which are described, for example, in GB 878,430 and GB 848,671); norbornane diisocyanates, such as described in U.S. Pat. No.3,492,330; m- and p-isocyanatophenyl sulfonylisocyanates of the type described in U.S. Pat. No.3,454,606; perchlorinated aryl polyisocyanates of the type described, for example, in U.S. Pat. No. 3,227,138; modified polyisocyanates containing carbodiimide groups of the type described in U.S. Pat. No.3,152,162; modified polyisocyanates containing urethane groups of the type described, for example, in U.S. Pat. Nos. 3,394,164 and 3,644,457; modified polyisocyanates containing allophanate groups of the type described, for example, in GB 994,890, BE 761,616, and NL 7,102,524; modified polyisocyanates containing isocyanurate groups of the type described, for example, in U.S. Pat. No.3,002,973, German Patent 1,022,789, 1,222,067 and 1,027,394, and German patent application 1,919,034 and 2,004,048; modified polyisocyanates containing urea groups of the type described in German Patent 1,230,778; polyisocyanates containing biuret groups of the type described, for example, in German Patent 1,101,394, U.S. Pat. Nos.3,124,605 and 3,201,372, and in GB 889,050; polyisocyanates obtained by telomerization reactions of the type described, for example, in U.S. Pat. No.3,654.106: polyisocyanates containing ester groups of the type described, for example, in GB 965,474 and GB 1,072,956. in U.S. Pat. No.3,567,763, and in German Patent 1,231,688; reaction products of the above-mentioned isocyanates with acetals as described in German Patent 1,072,385; and polyisocyanates containing polymeric fatty acid groups of the type described in U.S. Pat. No.3,455,883. It is also possible to use the isocyanate-containing distillation residues accumulating in the production of isocyanates on a commercial scale, optionally in solution in one or more of the polyisocyanates mentioned above. A person skilled in the art will know that the mixture of the above isocyanates can also be used in the present invention.
Isocyanate-terminated prepolymers may also be employed in the preparation of the polyurethane models of the present invention. Prepolymers may be prepared by reacting an excess of organic polyisocyanate or mixtures thereof with a minor amount of an active hydrogen-containing compound as determined by the well-known Zerewitinoff test. These compounds and their methods of preparation are well known to those skilled in the art. In the present invention, any active hydrogen-containing compound can be used to prepared the isocyanate-terminated prepolymer.
In one preferable embodiment of the present invention, the organic polyisocyanates are the one or more selected from the group consisting of polymethylene polyphenlene isocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or poly-4,4'- diphenylmethane diisocyanate or the combination thereof.
The polyurethane modeling composition further comprises one or more polyether polyol, which is the copolymerization and/or homopolymerization product of an epoxy compound and a polyol compound which doesn't comprise amine group. The preparation process of the polyether polyol has been known to a person skilled in the art, such as those described in EP-A 283 148, US patent 3,278,457, 3,427,256, 3,829,505, 4,472,560, 3,278,458, 3,427,334, 3,941 ,849, 4,721 ,818, 3,278,459, 3,427,335 and 4,355, 188. The polyether polyol has a functionality of 2-6, preferably 3-5, more preferably 4-5 ; and a hydroxyl number of 100-700, preferably 150-550, more preferably 300-500.
As used herein, the term "epoxy compound" refers to the compound having the following formula (I):
Figure imgf000008_0001
Wherein i and R2 are independently selected from H, C 1 -C6 straight or branch alkyl, phenyl and substituted phenyl.
In some embodiment of the present invention, Ri and R2 are independently selected from H, methyl, ethyl, propyl, and phenyl.
It is well known to a person skilled in the art for the preparation process of the "epoxy compound", for example prepared by the oxidating of alkene.
The examples of epoxy compound suitable for use in the present invention include, but not limited to, ethylene oxide, 1 ,2- propylene epoxide, epichlorohydrin, trichlorobutylene oxide, 1 ,2-butylene oxide, 2,3-butylene oxide, phenylethylene oxide or the combination thereof. As used herein, the term "epoxy compound" further comprises oxacycloalkane, such as, but not limited to, tetrahydrofuran, oxetane or the combination thereof.
As used herein, the term "polyol compound" refers to the compound comprising two or more hydroxyls. The term "the polyol compound which doesn't comprise amine group" refers to the compound comprising two or more hydroxyls and is free of amine groups, wherein the "amine group" comprises primary amine group (-NH2-), secondary amine group (-NH-) and tertiery amine groups (-N-). The polyol compound can optionally comprise substituents which are not reactive to the reaction between polyol and isocyanate, and the substituent can be unsaturated.
Suitable examples of the polyol compound include, but not limited to ethylene glycol, propylene glycol, 1 ,3-propanediol, 1 ,4-butanediol, 1 ,2-pentanediol, 1 ,6- hexanediol, 1 ,7-heptanediol, glycerol, 1 , 1 , 1- trimethylolpropane, 1 , 1 , 1- trimethylolethane, 1 ,2,6-hexanetriol, pentaerythritol, xylitol, sorbitol, sucrose, bisphenol A, bisphenol S or the combination thereof.
As used herein, the term "aliphatic polyester polyol" refers to the product prepared by polyhydroxyl compounds and aliphatic acids and the derivates thereof, wherein the aliphatic acid derivate comprises anhydrides, esters, and acyl halides of the aliphatic acid. The aliphatic polyester polyol has a hydroxyl number of 100-500 and a functionality of 2-4.
In a preferable embodiment of the present invention, the aliphatic polyester polyols are prepared from the components comprising: (cl) one or more diols, triols or tetraols;
(c2) one or more aliphatic acids or derivatives thereof, which comprise straight or branch alkyl or alkenyl with 5-30 carbon atoms;
Preferably, the (cl) component is selected from the group consisting of glycol, diethyleneglycol, triethylene glycol, tetraethylene glycol, 1 ,2-propanediol, 1 ,3-propanediol, 1 ,4-butanediol, 3-methyl- l ,5- pentanediol, 1 ,5-pentanediol, 1 ,6- hexanediol, 1 , 10-decylenediol, glycerol, 1 ,2,4- butantriol, 1 ,2,5- pentantriol, 1 ,3,5- pentantriol, 1 ,2,6-hexanetriol, 1 ,2,5- hexanetriol, 1 ,3,6-hexanetriol, trimethylolbutane, trimethylolpropane or di(trimethylolpropane), trimethylol ethane, pentaerythritol, dipentaerythritol and sorbitol. More preferably, the (c l ) component is selected from the group consisting of glycerol, diethyleneglycol, glycol, propanediol, trimethylolpropane, diethylene glycol and pentaerythritol.
(c2) component is the one or more selected from the group consisting of ε-caprolactone, adipic acid, lauric acid, myristic acid, palmitic acid, ricinoleic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid or derivatives thereof
The examples of the aliphatic polyester polyols include, but not limited to, castor oil, poly ε-caprolacloneglycol, polycaprolacton polyol, polyethyleneglycol adipate, and polypropylene glycol adipate. In a preferable embodiment, the polyurethane modeling composition further comprises one or more aromatic polyester polyols. The polyurethane model prepared from the polyurethane modeling composition comprising aromatic polyester polyols has higher glass transition temperature (Tg), thus has better heat resistance. As used herein, the term "aromatic polyester polyol" refers to the product prepared by polyhydroxyl compounds and carboxylic acids comprising aromatic groups and the derivates thereof, wherein the derivates of the carboxylic acids comprising aromatic groups comprises anhydrides, esters, and acyl halides of the carboxylic acid. The aromatic polyester polyol has a functionality of 2-4, preferably 2-3, and a hydroxyl value of 100-450, preferably 200-450. In one embodiment of the present invention, the carboxylic acids or the derivates thereof suitable for preparing the aromatic polyester polyols comprise, but not limited to, phthalic acid, isophthalic acid, trimellitic acid, terephthalic acid, phthalic acid anhydride, tetrahydrophthalic acid anhydride, pyromellitic dianhydride, hexahydrophthalic acid anhydride, tetrachlorophthalic acid anhydride, endomethylene tetrahydrophthalic acid anhydride, glutaric acid anhydride, terephthalic acid dimethyl ester and terephthalic acid-bis-glycol ester. In one preferable embodiment of the present invention, the aromatic polyester polyol has a content of 1-40 wt.%, more preferably 10-30 wt.%, further preferably 15-20 wt.%, based on 100% by weight of the polyol component.
The polyurethane modeling composition may further comprise one or more thixotropic agents. The thixotropic agent can increase viscosity of liquid, and impart thixotropic property to liquid. The resin comprising it has higher consistency when being standstill, and will have a low consistency under external force. The thixotropic agents commonly used in the art comprise fumed silica, organic bentonite, hydrogenated castor oil and polyamide wax. In the polyurethane modeling composition of the present invention, the thixotropic agent may have a content of 2-8 wt.%, based on 100% by weight of the polyol component.
In one preferred embodiment of the present invention, the thixotropic agent can be selected from fumed silica. Fumed silica is generally produced by the vapor phase hydrolysis of silicon tetrachloride in a hydrogen oxygen flame. The combustion process creates silica molecules, which condense to form particles, which in turn sinter together into aggregates. Fumed silica is available in treated and untreated grades. The untreated grades vary in surface area, bulk density, and thickening efficiency in nonpolar systems, examples of the fumed silica may those commercialized by Cabot Corporation Degussa Corporation and Wacker Silicones Corporation.
In one embodiment of the present invention, examples of preferred fumed silica include, but not limited to, CAB-O-SILL-90, MS- 55, HS-5, LM-130, LM-150, HDK 30, M-5, and Degussa AE OSIL R200, US200, R202, R972, US202, US204 and US206. Preferably, the fumed silica has an average particle size of 7-40 nm.
In one embodiment of the present invention, the polyurethane modeling composition further comprises one or more water removing agents. Generally, the polyurethane modeling composition will be foaming because of the water contained in the commercialized polyol components, and the moisture in the air during the processing, thus the mechanical property of the obtained polyurethane model becomes worse. Therefore, the mechanical property of the polyurethane model can be improved by adding one or more water removing agents to remove the water contained in the composition or moisture. The polyurethane modeling composition of the present invention has a water content of 2-5wt.%, based on 100% by weight of the polyol component. The examples of water removing agents suitable for use in the present invention, but not limited to, molecular sieve, vinyl silane, such as vmyltrimethoxysilane (for example Silquest A-171) and methyltrimethoxysilane (such as Silquest A- 1630). Other suitable examples of water removing agents include, but not limited to, Addtive TI (p-toluene sulfonyl isocyanate) and O F (e ste r c o mp ounds ) commercialized from OMG Borchers.
In one embodiment of the present invention, the polyurethane modeling composition further comprises one or more microspheres with a density of 20-500 kg/m3. The microspheres can be solid or hollow, and can be prepared by the components: a c ry l i c typ e r e s i n s s u c h a s p o l y a c ry l o n i t r i l e a n d polymethylmethacrylate, acrylic modified styrene, polyvinylidene chloride, copolymers of styrene and methyl methacrylate, phenolic resins, epoxy resins, urea resins, hollow glass, silica, ceramic or carbon spheres.
Illustrative examples of microspheres suitable for use in the present invention include, but not limited to, Expancel, available from Akzo Nobel Corporation; phenolic microspheres, available from Asia Pacific microspheres and Matsumoto microspheres available from Yusht-Seiyaku Company, and hollow glass microspheres K15 K25 and SH38 available from 3M. These microspheres preferably have a diameter of about 5 to about 250 micrometers. The microspheres, or hollow microspheres, suitable for use in the invention are conventional in the art and methods for production of these microspheres are well known. Such microspheres are readily available commercially. The microspheres facilitate machining, lead to reduced density and reduce the coefficient of thermal expansion. The surface of the microspheres may be treated suitably for better compatibility with the resin composition.
In the present invention, by virtue of long pot life, the polyurethane modeling composition of the present invention may be homogenized by means of manual, for example stirring. Compared to homogenize with an extrusion machine whose injection head tends to be jammed, the process implemented manually allows a polyurethane modeling composition with more microspheres, thus producing a polyurethane model with lower density. The polyurethane modeling composition of the present invention may comprises the microspheres in a content of 40-80 vol.%, preferably 60-80 vol.%, based on 100% by volume of the polyol or the isocyanate component. Microbaloons may be added to the polyol or the isocyanate component or both.
The polyurethane modeling composition may further comprise one or more foam stabilizers to prevent the formation of big bubbles which may impair the surface quality of the model. The foam stabilizers suitable for use in the present invention comprise silicone foam stabilizer and fluoro-foam stablilizer and the like . Illustrative examples of the silicone foam stabilizer include, but not limit to SRX-274C commercialized from Toray Silicon Co., Ltd., and Niax L-6920 commercialized from Momentive Co., Ltd.
The polyurethane modeling composition may further comprise one or more defoamers, the illustrative example s thereof comprise, but not limit to , polysiloxane emulsion, such as Silikon® SRE and Rhodorsil® Rhodia; long chain alcohol, fatty acid or the salts thereof; organic fluorine compounds and the mixture thereof.
The polyurethane modeling composition may further comprise auxiliaries and additives commonly used in the art, such as diluents, fillers (e.g. calcium carbonate), fibers, pigments, dyes, flame retardants, surfactants, wetting agents and polymer toughening agents. A person skilled in the art may choose suitable auxiliaries and additives according to the properties of the final products.
The polyurethane model prepared from the polyurethane modeling composition of the present invention has better hardness of 45-65 shore D, determined according to ISO868 : 2003. The polyurethane modeling composition has higher glass transition temperature of 49-100 °C, thus the polyurethane model prepared from the same has better heat resistance property.
Modeling article and the preparation thereof
The present invention further refers to a modeling article comprising a substrate and a polyurethane modeling layer disposed on the substrate, wherein the polyurethane modeling layer is prepared from the polyurethane modeling composition illustrated above. The polyurethane modeling layer has favorable mechanical properties, such as toughness, hardness, temperature resistance, compressive strength, flexural strength, and excellent dimensional stability, therefore the model or mold prepared from the polyurethane model has higher size precision. Moreover, the polyurethane model both has higher hardness and flexibility such that less dust is produced during processing and improves the processing environment.
The modeling article of the present invention may be prepared by applying the polyurethane modeling composition of the present invention on a substrate, curing the polyurethane modeling composition and machining the cured polyurethane modeling layer to the desired contour, wherein the substrate may be prepared from any material, including but not limit to, wood, steel, aluminum, polyurethane foam or styrene foam. The substrate may be optionally machined to any desired contour before applying to the polyurethane modeling composition of the present invention. The surface of the substrate may be treated, for example polishing to obtain a smooth surface or applying coating according to actual needs.
The modeling article of the present invention has a polyurethane modeling layer with favorable mechanical properties, may be used in model design, mold, checking fixture s and the like. The present invention further relates to a process of preparing the modeling article, comprising the step of:
(I) providing a substrate having an exposed outer surface;
(II) applying manually the polyurethane modeling composition illustrated above to the outer surface of the substrate, to form a continuous layer of the polyurethane modeling composition; (III) curing the continuous layer of polyurethane modeling composition to form a polyurethane modeling layer; and
(IV) machining the cured polyurethane modeling layer to the desired contour. The existing preparation process of modeling articles all comprise the step of applying polyurethane modeling composition to the substrate by extrusion machine. The cost of such process is high because of the expensive extrusion machine, furthermore, the modeling article prepared by such process has higher density because low density microsphere is used in a lower content so as to not choke the injection head. Regarding the process of the present invention, the polyurethane composition has a pot life of more than 25 minutes, preferably 40 minutes, such that it may be applied to the substrate manually without using extrusion machine and overcome the deficiency of the existing process.
In one embodiment of the present invention, the substrate having an exposed outer surface may have any desire shape, and the exposed outer surface may be machined or not.
The continuous layer of the polyurethane modeling composition may be prepare by applying the polyurethane modeling composition to the outer surface of the substrate in a way of extrusion, blade coating, brush coating, roll coating, knife coating and the like. It is well known to a person skilled in the art that one or more layer of the polyurethane composition of the present invention may be applied to the out surface of the substrate.
The curing of the continuous layer of polyurethane modeling composition may use the curing method commonly used in the art, such as room temperature curing method, heating method, UV radiation method. In one embodiment of the present invention, heating method is preferably used in the present invention, and the heating temperature may be 50-70°C and last 3-5 hours.
Machining the cured polyurethane modeling layer may use the apparatus and tools commonly used in the art, such as milling machine, preferably numerically controlled machine. Examples
The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by the following examples.
The materials used in the examples
Desmodur 0418: a polymeric MDI having a NCO content of 32% which is commercially available from Bayer materialScience Company Limited;
Multranol 9158: a polyether polyol having a functionality of 3 and an -OH mumber of approximately 470 mg KOH/g which is commercially available from Bayer materialScience Company Limited;
Arcol A3500: a polyether polyol having a functionality of 3.6 and an OH number of approximately 500 mg KOH/g which is commercially available from Bayer materialScience Company Limited;
Arcol S440: a polyether polyol having a functionality of 4.6 and an OH number of approximately 500 mg KOH/g which is commercially available from Bayer materialScience Company Limited;
Stepan PS4027: a polyester polyol having a functionality of 2.7 and an - OH number of approximately 400 mg KOH/g which is commercially available from Stepan Company;
Castor oil: an aliphatic polyester polyol having a functionality of 2.7 and an OH number of approximate 157 which is commercially available from ihao Chemical Co Limited;
BYK® 066 N: a silicone de former which is commercially available from BYK;
Niax L-6920: a surfactant which is commercially available from Momentive;
HYD03B: a molecular sieves which is commercially available from Hengye Chemical Engineering Co., Ltd;
Sipernat® 22LS: a thixotropic agent which is commercially available from Deguss; K15: a hollow microsphere having a bulk density of 0. 1 5g/cm3 which is commercially available from 3M;
K25: a hollow microsphere having a bulk density of 0.25g/cm3 which is commercially available from 3M; S38HS: a hollow micro sphere having a bulk density of 0.38g/cm3 which is commercially available from 3M;
Examples 1-6
Example 1 was prepared as following: 1000 grams material was prepared according to weight percentage giving in table 1 and mixed manually until homogenization. All steps including weighting and mixing were conducted in fumed hood at room temperature. (Temperature 20-25 °C, Relative humidity 45%-55%).
300 grams mixture was coated to the surface of a foam substrate vertically placed with a thickness of 20mm, 30mm, 40mm and 50mm to evaluate its sag resistance properties.
500 grams mixture was coated to a foam substrate with a thickness of 30mm, cured at room temperature for 12 hours, machined to a pre-de signed shape with numerically controlled machine and observe the surface grain quality with electron magnifying glass. 200 grams mixture was used to prepare the modeling article, and Shore D hardness and density were determined according to ISO 868 : 2003 and ISO 278 1 : 1996 respectively.
Examples 2-6 were prepared as Example 1 and shown in table 1.
Table 1 : polyurethane modeling composition and properties thereof
Figure imgf000018_0001
Examples above illustrate that the polyurethane modeling composition comprising polyether polyols of different functionality and OH number has low density, high hardness, good sag resistance and long pot life. And as shown in the observation for the surface grain of the machined surface, the polyurethane modeling articles have very fine surface quality and may meet the requirements of model making.
Examples above also indicate that aromatic polyol and high functionality polyether polyol can significantly improve Tg and hardness, and polyurethane model with different density may be prepared by adding corresponding amount of microsphere as filler, and the polyurethane model with higher hardness may be obtained by using high density fillers.
It should be understood that after reading the disclosure of the present application, a person skilled in the art can make many changes and modifications which may also fall into the scope of the present invention as claimed by the following claims

Claims

1 . A polyurethane modeling composition comprising:
(a) one or more organic polyisocyanates;
(b) one or more polyether polyols with a functionality of 2-6 and hydroxyl number of 100-700, wherein the polyether polyol is the copolymerization and/or homopolymerization product of an epoxy compound and a polyol compound that doesn't comprise amine group;
(c) one or more aliphatic polyester polyols with a hydroxyl number of 100-500 and a functionality of 2-4;
(d) optionally one or more thixotropic agents;
(e) optionally one or more water removing agents; and
(f) optionally one or more microspheres with a density of 20-500 kg/m3.
2. The polyurethane modeling composition according to claim 1, wherein the one or more polyether polyols have a functionality of 3-5.
3. The polyurethane modeling composition according to claim 1, wherein the one or more polyether polyols have a hydroxyl number of 150-550.
4. The polyurethane modeling composition according to claim 3, wherein the one or more polyether polyols have a hydroxyl number of 300-500.
5. The polyurethane modeling composition according to claim 1, wherein the epoxy compound is the one or more selected from the group consisting of ethylene oxide, 1,2- propylene epoxide, epichlorohydrin, trichlorobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, phenylethylene oxide, tetrahydrofuran, oxetane or the combination thereof.
6. The polyurethane modeling composition according to claim 1 or 5, wherein the polyol compound is the one or more selected from the group consisting of ethylene glycol, propylene glycol, 1,3-propanediol, 1 ,2-butanediol, 1,3- butanediol, 1 ,4-butanediol, 1 ,2-pentanediol, 1 ,4- pentanediol, 1,5-pentanediol, 1 ,6- hexanediol, 1 ,7-heptanediol, glycerol, 1,1,1-trimethylolpropane, 1 , 1 , 1 -trimethylol ethane, 1 ,2,6-hexanetriol, pentaerythritol, xylitol, sorbitol, sucrose, bisphenol A, bisphenol S or the combination thereof.
7. The polyurethane modeling composition according to claim 1, wherein the one or more aliphatic polyester polyols are prepared from the components comprising:
(cl) one or more diols, triols or tetraols;
(c2) one or more aliphatic acids or derivatives thereof, which comprise straight or branch alkyl or alkenyl with 5-30 carbon atoms;
8. The polyurethane modeling composition according to claim 7, wherein the component (cl) is the one or more selected from the group consisting of glycol, diethyleneglycol, triethylene glycol, tetraethylene glycol, 1 ,2-propanediol, 1,3-propanediol, 1 ,4-butanediol, 3-methyl-l,5- pentanediol, 1,5-pentanediol, 1,6- hexanediol, 1,10-decylenediol, glycerol, 1 ,2,4- butantriol, 1,2,5- pentantriol, 1,3,5- pentantriol, 1 ,2,6-hexanetriol, 1,2,5- hexanetriol, 1,3,6-hexanetriol, trimethylolbutane, trimethylolpropane or di(trimethylolpropane), trimethylol ethane, pentaerythritol, dipentaerythritol and sorbitol.
9. The polyurethane modeling composition according to claim 8, wherein the component (cl) is the one or more selected from the group consisting of glycerol, diethyleneglycol, glycol, propanediol, trimethylolpropane, diethylene glycol and pentaerythritol.
10. The polyurethane modeling composition according to claim 7, wherein the component (c2) is the one or more selected from the group consisting of ε-caprolactone, adipic acid, lauric acid, myristic acid, palmitic acid, ricinoleic acid, stearic acid, arachidic acid, behenic acid, oleic acid, linoleic acid, linolenic acid or derivatives thereof.
11. The polyurethane modeling composition according to claim 1, wherein the polyurethane modeling composition further comprises one or more aromatic polyester polyols with a functionality of 2-4 and a hydroxyl number of 100-450.
12. The polyurethane modeling composition according to claim 1 , wherein the thixotropic agents are the one or more selected from fumed silica.
13. The polyurethane modeling composition according to claim 1, wherein the organic polyisocyanates are the one or more selected from the group consisting of polymethylene polyphenlene isocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate or poly-4,4'- diphenylmethane diisocyanate or the combination thereof.
14. A modeling article, comprising a substrate and a polyurethane modeling layer disposed on the substrate, wherein the polyurethane modeling layer is prepared from the polyurethane modeling composition according to any one of the claims 1-13.
15. The modeling article according to claim 14, wherein the polyurethane modeling layer has a hardness of 45-65 shore D, determined according to ISO868: 2003.
16. The modeling article according to claim 14, wherein the polyurethane modeling layer has a density of 0.3-0.9 g/cm3, determined according to ISO2781 : 1996.
17. The modeling article according to claim 14, wherein the substrate is the one selected from the group consisting of woods, steel products, aluminum products, polyurethane foam, styrene foam or the combination thereof.
18. A process of preparing the modeling article, comprising the step of:
(I) providing a substrate having an exposed outer surface;
(II) applying manually the polyurethane modeling composition according to any one of the claims 1-13 to the outer surface of the substrate, to form a continuous layer of the polyurethane modeling composition;
(III) curing the continuous layer of polyurethane modeling composition to form a polyurethane modeling layer; and
(IV) machining the cured polyurethane modeling layer to the desired contour.
PCT/EP2013/068109 2012-09-07 2013-09-02 A polyurethane modeling composition Ceased WO2014037312A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201210346427.8A CN103665313A (en) 2012-09-07 2012-09-07 Polyurethane wood substitution composition
CN201210346427.8 2012-09-07

Publications (1)

Publication Number Publication Date
WO2014037312A1 true WO2014037312A1 (en) 2014-03-13

Family

ID=49118507

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2013/068109 Ceased WO2014037312A1 (en) 2012-09-07 2013-09-02 A polyurethane modeling composition

Country Status (2)

Country Link
CN (1) CN103665313A (en)
WO (1) WO2014037312A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017207523A1 (en) * 2016-05-31 2017-12-07 Akzo Nobel Coatings International B.V. Two-component putty, method for coating a substrate with such putty, substrates coated with such putty
CN108912297A (en) * 2018-07-20 2018-11-30 滁州市玉林聚氨酯有限公司 A kind of preparation method of high temperature resistant polyurethane material
CN114045023A (en) * 2021-11-18 2022-02-15 浙江华峰新材料有限公司 Polyurethane resin containing biomass filling material and preparation and application thereof
WO2022061337A1 (en) * 2020-09-21 2022-03-24 Saint-Gobain Performance Plastics Corporation Polyurethane foam and methods of forming the same
US12031005B2 (en) 2020-09-21 2024-07-09 Saint-Gobain Performance Plastics Corporation Polyurethane foam and methods of forming the same
WO2024182964A1 (en) * 2023-03-06 2024-09-12 Dow Global Technologies Llc Low viscosity polyurethane pottant compositions

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106336503B (en) * 2016-08-25 2018-02-06 广州市九合化工科贸有限公司 A kind of preparation method of bio-compatible type hyper-dispersant
CN106632946B (en) 2017-01-03 2019-07-16 华南理工大学 Using diisocyanate as low-viscosity terminal hydroxy group resin of core and the preparation method and application thereof
CN107033314A (en) * 2017-04-27 2017-08-11 南宁珀源能源材料有限公司 Buddha's warrior attendant wire cutting polyurethane lightweight resin plate host, preparation method and application
CN110330631A (en) * 2019-07-16 2019-10-15 华北电力大学（保定） A preparation method of inner core filling material for composite insulating cross-arm
CN115873291A (en) * 2022-12-23 2023-03-31 郑州圣莱特空心微珠新材料有限公司 Substitute wood and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4275172A (en) * 1980-01-28 1981-06-23 Union Carbide Corporation Frothable polyurethane composition and a cellular foam produced therefrom suitable for use in joints between wallboards
US5401785A (en) * 1990-05-31 1995-03-28 Sanyo Chemical Industries, Ltd. Foamed polyurethane-forming composition, foamed polyurethane and process making the same
US6221929B1 (en) * 1996-10-24 2001-04-24 Sanyo Chemical Industries, Ltd. Rigid foamed polyurethane-forming compositions, foamed polyurethane moldings and models made of the same
WO2003051649A2 (en) * 2001-12-14 2003-06-26 Huntsman Advanced Materials (Switzerland) Gmbh Method of making models

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4275172A (en) * 1980-01-28 1981-06-23 Union Carbide Corporation Frothable polyurethane composition and a cellular foam produced therefrom suitable for use in joints between wallboards
US5401785A (en) * 1990-05-31 1995-03-28 Sanyo Chemical Industries, Ltd. Foamed polyurethane-forming composition, foamed polyurethane and process making the same
US6221929B1 (en) * 1996-10-24 2001-04-24 Sanyo Chemical Industries, Ltd. Rigid foamed polyurethane-forming compositions, foamed polyurethane moldings and models made of the same
WO2003051649A2 (en) * 2001-12-14 2003-06-26 Huntsman Advanced Materials (Switzerland) Gmbh Method of making models

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017207523A1 (en) * 2016-05-31 2017-12-07 Akzo Nobel Coatings International B.V. Two-component putty, method for coating a substrate with such putty, substrates coated with such putty
US10647859B2 (en) 2016-05-31 2020-05-12 Akzo Nobel Coatings International B.V. Two-component putty, method for coating a substrate with such putty, substrates coated with such putty
CN108912297A (en) * 2018-07-20 2018-11-30 滁州市玉林聚氨酯有限公司 A kind of preparation method of high temperature resistant polyurethane material
WO2022061337A1 (en) * 2020-09-21 2022-03-24 Saint-Gobain Performance Plastics Corporation Polyurethane foam and methods of forming the same
US12031005B2 (en) 2020-09-21 2024-07-09 Saint-Gobain Performance Plastics Corporation Polyurethane foam and methods of forming the same
CN114045023A (en) * 2021-11-18 2022-02-15 浙江华峰新材料有限公司 Polyurethane resin containing biomass filling material and preparation and application thereof
CN114045023B (en) * 2021-11-18 2023-01-24 浙江华峰新材料有限公司 Polyurethane resin containing biomass filling material and preparation and application thereof
WO2024182964A1 (en) * 2023-03-06 2024-09-12 Dow Global Technologies Llc Low viscosity polyurethane pottant compositions

Also Published As

Publication number Publication date
CN103665313A (en) 2014-03-26

Similar Documents

Publication Publication Date Title
WO2014037312A1 (en) A polyurethane modeling composition
JP6942139B2 (en) Reactive flame retardants for polyurethane foams and polyisocyanurate foams
JP6808488B2 (en) Polyurethane type with long pot life and free hardness
EP2512768B1 (en) Polyurethane composite having high compressive strength and stiffness
JP6869191B2 (en) Polyurethane-polyisocyanurate compounds with excellent mechanical properties
CN105026497B (en) Isocyanate-based polymer foams with improved flame retardancy
JP2018516295A5 (en)
EP3783042A1 (en) Rigid polyurethane foam containing reactive flame retardant
RU2703255C1 (en) Resins based on polyurethane for winding fiber
KR102199919B1 (en) Composition for forming eco-friendly polyurethane foam with improved air permeability and antioxidant properties and method for preparing the polyurethane foam
KR101876155B1 (en) Vibration-damping urethane resin composition, vibration-damping molded urethane resin object, and method for forming said molded object
KR101737764B1 (en) Polyurethane resin composition for a microporous foam sheet used bio-polyol
KR102211997B1 (en) Polyol composition for forming polyurethane foam and method for preparing the polyurethane foam
WO2011073066A1 (en) Athletic device comprising a polyurethane composite system
JP6429864B2 (en) Aldehyde-containing compounds suitable for the production of curable polyisocyanate compositions
DE10351268A1 (en) Modified foliated silicates obtained by modification with ammonium compound with acid group and esterification with di- or polyol are used for producing polyurethanes containing exfoliated foliated silicates e.g. for insulating foam
KR102867652B1 (en) Composition for forming eco-friendly polyurethane foam with improved heat insulation property and method for preparing the polyurethane foam
JP6714053B2 (en) Polyurethane resin composition for cutting
JP2006335944A (en) Polyol composition for rigid polyurethane foam, rigid polyurethane foam and method for producing the same, and insulation for building materials
WO2024070635A1 (en) Cyclic phosphazene compound, additive for resin, composition, and resin foam body

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: 13759166

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: 13759166

Country of ref document: EP

Kind code of ref document: A1