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
  • C08G18/65—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
  • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
• • 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
  • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
  • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
  • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
  • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
• • 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
  • C08G18/089—Reaction retarding 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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • 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
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• the present invention relates to polyurethane field, particular to polyurethane, its preparation process and uses thereof.
• polyester-polyurethanes have been a concern in its application. This is because during application, the ester bonds within their structure are hydro lyzed by the exposure to moisture or by direct contact with water, thus leading to breaking of polymer chain and gradual, even complete loss of their physical properties. Therefore, it has always been a research topic in material science to improve hydrolysis resistance of these polyester-polyurethanes.
• the hydrolysis resistance of polyurethane may be improved by adding certain amount of anti-hydrolysis additive, which is widely used due to its simplicity and convenience.
• GB 1205257A disclosed that alkylene carbonates can effectively improve hydrolysis resistance of polyurethanes.
• US 6737471B2 disclosed that ester(s) of (mono)carboxylic acid is an effective anti-hydrolysis additive for polyurethanes as long as the (first) dissociation constant (pKa) of the respective carboxylic acid is between 0.5 and 4.0.
• the resulted polyurethane has the best hydrolysis resistance when the amount of the carboxylate added falls into a specified range.
• One object of the present invention is to provide a polyurethane having improved hydrolysis-resistance., according to an embodiment of the invention, such
• polyurethane is the reaction product prepared by reacting the components comprising A)-G):
• the polyester polyol has a hydroxyl number of 20-280 mgKOH/g and a functionality of 1-3.
• the carbonate is cyclic carbonate and/or linear carbonate.
• the carbonate is one or more cyclic carbonate selected from the group consisting of ethylene carbonate, propylene carbonate, 1 ,2-butene carbonate, 2,3-butene carbonate, 1 ,2-cyclohexene carbonate and styrene carbonate.
• the carboxylate is one or more selected from the group consisting of dimethyl oxalate, diethyl oxalate , dibutyl oxalate, ⁇ -butyro lactone, ⁇ - valerolactone, ⁇ -caprolactone, ⁇ , ⁇ -dimethyl butyrolactone, ⁇ , ⁇ -dimethyl
• butyro lactone ⁇ , ⁇ -dimethyl butyrolactone and a-ethyl-y-methyl butyrolactone.
• polyurethane is 40-100% of the retention of tensile strength, determined according to
• a second object of the present invention is to provide a process for preparing polyurethane, which comprises a step of reacting the components comprising A)-G):
• the polyester polyol has a hydroxyl number of 20-280 mgKOH/g and a functionality of 1-3.
• the carbonate is cyclic carbonate and/or linear carbonate.
• the carbonate is the one or more cyclic carbonate selected from the group consisting of ethylene carbonate, propylene carbonate, 1 ,2-butene carbonate, 2,3-butene carbonate, 1 ,2-cyclohexene carbonate and styrene carbonate.
• the carboxylate is the one or more selected from the group consisting of dimethyl oxaloacetate, diethyl oxaloacetate, dibutyl oxaloacetate, ⁇ - butyro lactone, ⁇ -valero lactone, s-caprolactone,a,y-dimethyl butyro lactone, ⁇ , ⁇ - dimethyl butyrolactone, ⁇ , ⁇ -dimethyl butyro lactone and a-ethyl-y-methyl
• polyurethane is 40-100% of the retention of tensile strength, determined according to SATRA TM344.
• a third object of the present invention is to provide a use of the polyurethane in preparing polyurethane foams, microcellular elastomers and elastomers.
• Polyurethanes prepared with the process of the present invention possess good physical mechanical properties, especially good hydrolysis resistance.
• Polyurethanes of the present invention are particularly suitable for preparing polyurethane foams, microcellular elastomers and elastomers.
• polyurethanes obtained by adding both carbonate and carboxylate in the preparation process has improved hydrolysis resistance.
• the hydrolysis resistance of the polyurethane is further improved when the molar ratio of the carbonate groups in the carbonate to the carboxylate groups in the carboxylate is 0.85-3.40.
• Polyurethanes provided in the present invention is the reaction product prepared by reacting the components comprising A)-G):
• prepolymer prepared by reacting isocyanate with a first polyol
• G optionally one or more blowing agent and/or surfactant; wherein at least one of the first polyol and the second polyol is polyester polyol.
• the polyester polyol has a hydroxyl number of 20-280 mgKOH/g and a functionality of 1-3.
• the measurement of hydroxyl number is well known to a person skilled in the art, for example, as disclosed in Houben Weyl, Methoden der
• Component A) comprises one or more diisocyanate and/or polyisocyanate, such diisocyanate and/or polyisocyanate may be one diisocyanate and/or polyisocyanate, or the mixture of more than one diisocyanate and/or polyisocyanate.
• diisocyanate and/or polyisocyanate examples include but not limited to
• ethylene diisocyanate 1 ,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 1,2-dodecane diisocyanate, eye lo butane- 1,3-diisocyanate, cyclohexane-1,3- and 1,4-diisocyanates, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotoluene diisocyanates, hexahydro-1,3- and 1 ,4-phenylene diisocyanate, perhydro-2,4- and 4,4-diphenylmethane diisocyanate, 1,3-and 1 ,4-phenylene diisocyanate, 1 ,4-durol-diisocyanate, 4,4'-stilbene diisocyanate, 3,3-dimethyl-4,4-biphenylene di
• the diisocyanate and/or polyisocyanate may also include those modified by
• carbon diamine, allophanate and isocyanate which are preferably but not limited to diphenylmethane diisocyanate modified by diphenylmethane diisocyanate and allophanate, , their isomers, and the mixtures thereof.
• the isocyanante-terminated prepolymer of the present invention is the reaction product of the isocyanate and the first polyol, wherein the isocyanate may be any isocyanate monomer mentioned above.
• the first polyol may further comprise polyester polyol, polyether polyol, polycarbonate diol and mixtures thereof.
• the polyester polyols may be produced from the reaction of organic dicarboxylic acids or dicarboxylic acid anhydrides with polyhydric alcohols.
• Suitable dicarboxylic acids are preferably, but not limited to aliphatic carboxylic acids containing 2 to 12 carbon atoms, which in turn are preferably, but not limited to succinic acid, malonic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decane- dicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid or mixtures thereof.
• Suitable anhydrides are, preferably but not limited to phthalic anhydride, terachlorophthalic anhydride, maleic anhydride or mixtures thereof.
• Said polyhydric alcohols are preferably, but not limited to ethanediol, diethylene glycol, 1 ,2- and 1 ,3-propanediols, dipropylene glycol, 1 ,3- methylpropanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, neopentyl glycol, 1 , 10-decanediol, glycerol, trimethylol-propane, or mixtures thereof.
• Polyester polyols of lactones are preferably, but not limited to ⁇ -caprolactone,.
• the polyether polyols may be produced by known process, for example, through the reaction of alkylene oxides with polyhydric alcohol starters in the presence of catalysts.
• Said catalysts are preferably, but not limited to alkali hydroxides, alkali alkoxides, antimony pentachloride, boron fluoride etherate or mixtures thereof.
• Said alkylene oxides are preferably, but not limited to tetrahydrofuran, ethylene oxide, 1 ,2-propylene oxide, 1 ,2-and 2,3-butylene oxide, styrene oxide or mixtures thereof.
• Suitable starter molecules are preferably, but not limited to polyhydric compounds, such as water, ethylene glycol, 1 ,2-and 1 ,3-propanediols, 1 ,4-butanediol, diethylene glycol, trimethylol-propane or mixtures thereof.
• the polycarbonate polyols may be produced from the reaction of diols such as 1 ,2- and 1 ,3-propanediols, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, diethylene glycol, trioxyethylene glycol, with dialkyl or diaryl carbonates, eg. diphenyl carbonate, or phosgene.
• the component B) comprises one or more second polyol.
• the second polyol is as defined as the first polyol, which may be the same as the first polyol or different, and at least one of the first polyol and the second polyol is polyester polyol.
• the polyester polyol has a hydroxyl value of 20-280 mgKOH/g and a functionality of 1-3.
• the component C) comprises one or more carbonate.
• the carbonate may be the one selected from the group consisting of cyclic carbonate or linear carbonate, more preferably cyclic carbonate.
• the carbonate may be the one or more selected from the group consisting ethylene carbonate, propylene carbonate, 1 ,2-butene carbonate, 2,3- butene carbonate, 1 ,2-cyclohexene carbonate and styrene carbonate, more preferably ethylene carbonate or propylene carbonate, the most preferably ethylene carbonate.
• the amount of the carbonate may be 0.5-15% based on 100% by weight of the polyurethane.
• the component D) comprises one or more carboxylate which has a dissociation constant of carboxylic acid of 0.5-4.
• the dissociation constant refers to the first dissociation constant when the carboxylate is dicarboxylate or polycarboxylate.
• the component E) comprises one or more catalyst which is preferably, but not limited to, amines and organic metal compounds and their mixtures.
• the amine catalyst is preferably, but not limited to, triethylamine, tributylamine, triethylene diamine, N-ethylmorpholine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-ethylenediamine, pentamethyl diethylene-triamine, N,N-methylaniline, ⁇ , ⁇ -dimethylaniline and mixtures thereof.
• the organic metal catalyst is preferably, but not limited to, stannous diacetate, stannous dioctoate, stannous diethylhexoate, and dibutyltin diacetate, dibutyltin dilaurate, ditutyltin maleate, and dioctyltin diacetate and mixtures thereof.
• the catalyst dosage is 0.001-10wt.%> based on 100 % by weight of the polyurethane.
• the component F) comprises one or more chain extender, which typically is
• active hydrogen atoms comprising compounds with molecular weights lower than 800, preferably from 18 to 400.
• the active hydrogen atoms comprising compounds are preferably, but are not limit to alkanediols, dialkylene glycols, and polyalkylene polyols and their mixtures.
• the examples are ethanediol, 1 ,4- butanediol, 1 ,6-hexanediol, 1 ,7- heptane diol, 1 ,8-octanediol, 1 ,9-nonanediol, 1 , 10- decanediol, diethylene glycol, dipropylene glycol, and polyoxyalkylene glycols.
• alkanediols such as 1 ,2- propanediol, 2-methyl- 1 ,3-propanediol,2,2-dimethyl- 1 ,3-propanediol, 2-butyl-2- ethyl- 1 ,3-propanediol, 2-butene-l ,4-diol and 2-butyne- l ,4-diol, alkanolamines and N- alkyldialkanolamines such as ethanolamine, 2-aminopropanol and 3-amino-2,2- dimethylpropanol, N-methyl and N- ethyl- diethanolamines, as well (cyclo) aliphatic and aromatic amines, e.g.
• the component G) comprises one or more blowing agent and/or surfactant.
• Suitable blowing agent is preferably but not limited to water, halohydrocarbons, hydrocarbons and gases. Examples of halohydrocarbons are
• hydrocarbons include butane, pentane, cyclopentane, hexane, cyclohexane, and heptane.
• Blowing gases include, but not limited to, air, C0 2 , and N 2 .
• the surfactants are selected preferably from but not limited to polyoxyalkylene derivatives of siloxane, in an amount of 0.01 to 5%, based on 100% by weight of the polyurethanes.
• reaction components can be a high-pressure or low-pressure mixing-head machine, preferably low-pressure mixing-head machine.
• the mixing process can be a two- component mixing or multi-component mixing.
• handbook Koreanststoff Handbuch, Volume VII, Polyurethanes, 1994 by Dr. G. Oertel, Carl-Hanser-Verlag, Kunststoff.
• the molds described herein are those frequently used in the existing technology to prepare polyurethanes, in which the reaction system can react to provide the polyurethanes of the present invention.
• the polyurethane molding technology and equipment are those well-known in related fields. For details, please refer to "Polyurethanes Chemistry and Technology"
• the process of preparing polyurethane provided in the present invention comprises a step of reacting the components comprising A)-G):
• prepolymer prepared by reacting the isocyanate with the first polyol; B) one or more the second polyol;
• G optional one or more blowing agent and/or surfactant, wherein at least one of the first polyol and the second polyol is polyester polyol.
• the first polyol and the second polyol may be the same or different, and at least one of the first polyol and the second polyol is polyester polyol.
• the polyester polyol has a hydroxyl value of 20-280 mgKOH/g and a functionality of 1-3.
• the molar ratio of the carbonate groups in the carbonate to the carboxyl groups in the carboxylate is 0.85-3.40
• the molar ratio of the carbonate groups in the carbonate to the carboxyl groups in the carboxylate is defined as following: l ⁇ (mass of the carbonate ⁇ molecular weight of the carbonate)
• mole ratio — ⁇ — ⁇ ⁇ ⁇ — ⁇ —— ⁇ - ⁇ —
• reaction component comprising A)-G) can react in molds to provide the reaction
• polyurethane of the present invention may be also obtained by the way of spraying, rolling and brushing the mixture comprising component A)-G).
• the model may be those generally used in the prior art or designed according to special requirements.
• NCO Index X(%) is defined as:
• the NCO Index of the reaction is preferred but not limited to be 50-160, particularly preferred 80-120, and may be optimized by the method well-known in prior art.
• Adipate polyester polyol having an average
• composition II The other components (such as polyols, chain extenders, blowing agents, catalysts and surfactants) were marked as Component II.
• hydrolysis-resistance properties of the polyurethane samples prepared according to the method described in this invention were evaluated by measuring the retention of tensile strengths before and after subjecting the polyurethane samples to hydrolysis conditions. Tensile strength was tested according to DIN53504. Hydrolysis conditions were established according to SATRA TM344, specifically, the samples were placed under 70 ° C, 95% relative humidity, for certain periods (one week and two weeks). The samples were placed in room temperature for 24 hours before testing.
• Component Bayflex 2003E 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100- II (parts by weight)
• Dabco EG parts by 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 weight
• Examples E1-E5 showed better hydrolysis-resistance properties in comparison to C2, which indicated that the combination of ethylene carbonate and diethyl oxalate can significantly improve the hydrolytic stability of the obtained polyurethane samples.
• E5 the polyurethane sample obtained at optimum ratio of ethylene carbonate to diethyl oxalate, showed significant improvement of hydrolytic stability after two weeks of hydrolysis.

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• Engineering & Computer Science (AREA)
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• Polyurethanes Or Polyureas (AREA)

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Citations (4)

• 2011
  • 2011-10-11 CN CN201110307048.3A patent/CN103044648B/zh not_active Expired - Fee Related
• 2012
  • 2012-10-08 WO PCT/EP2012/069853 patent/WO2013053665A1/en active Application Filing

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