Patent Application
20130210950
The present invention relates to a reaction system for preparing polyurethane microcellular foam, a polyurethane microcellular foam and the use thereof.
Polyurethane microcellular foam, which possessed good physical and mechanical properties, has been widely used in the industry, especially for preparing shoe materials.
Polyurethane microcellular foam was usually prepared by reacting isocyanates and polyols, wherein the method thereof can not only be selected a one-step reaction between the isocyanates and polyols, but also a prepolymer approach.
Demould time was one of the key parameters for making polyurethane microcellular foam, for example, the faster the demould time, the higher production efficiency and lower energy consumption. In the prior art, the demould time could be shortened by increasing catalyst amount in the reaction system, as described in <Polyurethane Handbook: Chemistry, Raw Materials, Processing, Application, Properties (2nd Edition)> (Edited by Gunter Oertel, Bayer AG). However, there were several disadvantages caused by increasing amount of catalyst, for example, it would reduce the cream time which results in poor processability; furthermore, and it could deteriorate physical properties such as anti-hydrolysis performance; in addition, the high amount of catalyst was a potential threat to the environment.
Therefore, many efforts have been taken to explore new reaction systems for making polyurethane microcellular foams to shorten the demould time while maintain the processability and physical properties.
The objective of this invention is to provide a reaction system for preparing polyurethane microcellular foam. According to an example of this invention, the reaction system comprises a component A and a component B, wherein
Another objective of this invention is to provide a polyurethane microcellular foam. According to an example of this invention, the polyurethane microcellular foam comprises a reaction product of reaction component A and reaction component B, wherein
Another objective of this invention is to provide an isocyanate terminated prepolymer. According to an example of this invention, the isocyanate terminated prepolymer comprises a reaction product of reaction system containing a1) and a2) as follows:
Another objective of this invention is to provide a use of the reaction system provided in this invention in preparing polyurethane microcellular foam.
Another objective of this invention is to provide a use of the isocyanate terminated prepolymer provided in this invention in preparing polyurethane microcellular foam.
Another objective of this invention is to provide a use of the polyurethane microcellular foam provided in this invention in preparing shoes.
By using the reaction components provided in this invention, the demould time for preparing the polyurethane microcellular foam can be reduced. The obtained polyurethane microcellular foam possesses good physical and mechanical properties. The polyurethane microcellular foam is particularly suitable to prepare shoes.
The reaction system for preparing polyurethane microcellular foam comprises component A and component B. The component A is isocyanate-terminated prepolymer, wherein the isocyanate-terminated prepolymer is a reaction product of a1 and a2, described in details in the section of Reaction System for Preparing Isocyanate Terminated Prepolymer in this Description.
The component B comprises b1, b2 and b3.
The b1is polyol. The second polyol can be one kind of second polyol, or a mixtures of several kinds of second polyols. The second polyol has an average molecular weights of 1,000-10,000, and functionalities of 1 to 5, preferably 1.5 to 3. The said second polyol may prefer, but not limited to, polyester polyols, polyether polyols, polycarbonate polyols, and their mixtures.
The polyester polyol can be produced from the reaction of organic dicarboxylic acids or dicarboxylic acid anhydrides with polyhydric alcohols. The dicarboxylic acids can be selected from, but not limited to, aliphatic carboxylic acids containing 2-12 carbon atoms, for example, 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 their mixtures. The anhydrides can be selected from, but not limited to, for example, phthalic anhydride, terachlorophthalic anhydride, maleic anhydride, or their mixtures. The polyhydric alcohols include ethanediol, diethylene glycol, 1,2-propanediols, 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 their mixtures. The polyester polyols can also be selected from the polyester polyols prepared by lactones. Such polyester polyols, which are prepared by lactones, can be selected from, but not limited to, ε-caprolactone.
The polyether polyols can be produced by known process, for example, by the reaction of alkene oxides with polyhydric alcohol starters in the presence catalysts. The catalysts can be selected from, but not be limited to, alkali hydroxides, alkali alkoxides, antimony pentachloride, boron fluoride etherate, or their mixtures. The alkene oxides, can be selected from, but not be limited to, tetrahydrofuran, ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, or their mixtures. The polyhydric alcohol starters can be selected from, but not be limited to, polyhydric compounds, such as, water, ethylene glycol, 1,2-propanediols, 1,3-propanediols, diethylene glycol, trimethylol-propane, or their mixtures.
The polycarbonate polyols can be selected from, but not be limited to, polycarbonate diols. The polycarbonate diols can be produced by the reaction of diols with dialkyl or diaryl carbonates or phosgene. The diols can be selected from, but not be limited to, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, trioxyethylene glycol, or their mixture. The dialkyl or diaryl carbonates can be selected from, but not be limited to, diphenyl carbonate.
The b2 is catalyst. The catalysts can be selected from, but not be limited to, amine catalysts, organo-metallic compounds, or their mixture. The amine catalysts can be selected from, but not be limited to, triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N′,N′-tetramethyl-ethylenediamine, pentamethyldiethylene-triamine, N,N-methylbenzylamine, N,N-dimethylbenzylamine, or their mixture. The organo-metallic compounds catalysts can be selected from, but not be limited to, organo-tin compounds, such as, tin(II) acetate, tin(II) octoate, tin(II) ethylhexonate, tin(II) laurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate, or their mixture. The amount of the b2 is 0.001-10 wt. %, based on 100 wt. % of the polyurethane microcellular foam.
The b3 is chain extender. The chain extender can be selected from, but not be limited to, active hydrogen atom containing compounds having a molecular weight less than 800, preferably 18-400.The active hydrogen atom containing compounds can be selected from, but not be limited to, alkanediols, dialkylene glycols, polyalkylene polyols, or their mixture, such as, ethanediol, 1,4-butanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, dipropylene glycol, polyoxyalkylene glycols, or their mixtures. The active hydrogen atom containing compounds can also comprises branched chain and/or unsaturated 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-1,4-diol, 2-butyne-1,4-diol, alkanolamines, N-alkyldialkanolamines; the N-alkyldialkanolamines can be selected from, but not be limited to, ethanolamine, 2-aminopropanol, 3-amino-2,2-dimethylpropanol, N-methyl-diethanolamines, N-ethyl-diethanolamines, or their mixture. The active hydrogen atom containing compounds can also includes aliphatic amines, aromatic amines, such as 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,6-hexamethylenediamine, isophoronediamine, 1,4-cyclohexamethylenediamine, N,N′-diethyl-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, or their mixtures.
The component B can further comprise b4 and b5.
The b4 is blowing agent. The blowing agents can be selected from, but not be limited to, water, halohydrocarbons, hydrocarbons, and gases. The halohydrocarbons can be selected from, but not be limited to, monochlorodifuloromethane, dichloromonofluoromethane, dichlorofluoromethane, trichlorofluromethane, or their mixtures. The hydrocarbons can be selected from, but not be limited to, butane, pentane, cyclopentane, hexane, cyclohexane, heptane, or their mixtures. The gases can be selected from, but not be limited to, air, CO2, N2, or their mixtures.
The b5 is surfactant. The surfactant can be selected from, but not be limited to, polyoxyalkylene derivatives of siloxane. The amount of the b5 is 0.01 to 5 wt. %, based on 100 wt. % of the polyurethane microcellular foam.
The polyurethane microcellular foam provided in this invention is a reaction product of the above mentioned reaction system for preparing polyurethane microcellular foam.
The polyurethane microcellular foam can be prepared by the said reaction system in moulds.
The moulds can be selected from conventional moulds used for preparing polyurethane microcellular foam.
The NCO index of the reaction can be optimized by using known method.
The NCO index of the reaction can be selected from, but not limited to, 50-160, preferably 80-120, wherein the NCO index X(%) is defined as below
The isocyanate-terminated prepolymer provided in this invention comprises a reaction product of a reaction system comprising a1 and a2.
The a1 comprises one or more polyisocyanates. The polyisocyanate can be one polyisocyanate or a mixture of several polyisocyanates. The polyisocyanate can be described by the formula, R(NCO)n, wherein R represents an aliphatic hydrocarbon radical containing 2-18 carbon atoms, an aromatic hydrocarbon radical containing 6-15 carbon atoms, or an araliphatic hydrocarbon radical containing 8-15 carbon atoms, n=2-4.
The polyisocyanate can be selected from, but not be be limited to, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 1,2-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane 1,3-diisocyanate, 1,4-diisocyanate, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4-hexahydrotoluene diisocyanate, hexahydro-1,3-phenylene diisocyanate, hexahydro-1,4-phenylene diisocyanate, perhydro-2,4-diphenylmethane diisocyanate, perhydro-4,4′-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,4-durol diisocyanate, 1,4-stilbene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, toluene 2,4-diisocyanate (TDI), 2,6-diisocyanate (TDI), diphenylmethane-2,4′-diisocyanate (MDI), diphenylmethane-2,2′-diisocyanate (MDI), diphenylmethane-4,4′-diisocyanate (MDI), naphthylene-1,5-diisocyanate (NDI), their mixture, their isomer, the mixture of they and their isomer.
The polyisocyanate may also include polyisocyanate modified by carbodiimide, allophanate and isocyanate. The polyisocyanate can be selected from, but not be limited to, diphenylmethane diisocyanate, diphenylmethane diisocyanate modified by carbodiimide, their mixture, their isomer, or the mixture of they and their isomer.
The a2 is one or more polyester polyols. The polyester polyol has an average molecular weight of 1,000-10,000, the functionality is 1-5, preferably 1.5-3. The polyester polyol can be produced from the reaction of organic dicarboxylic acids or dicarboxylic acid anhydrides with polyhydric alcohols. The dicarboxylic acids can be selected from, but not limited to, aliphatic carboxylic acids containing 2-12 carbon atoms, for example, 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 their mixtures. The anhydrides can be selected from, but not limited to, for example, phthalic anhydride, terachlorophthalic anhydride, maleic anhydride, or their mixtures. The polyhydric alcohols include ethanediol, diethylene glycol, 1,2-propanediols, 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 their mixtures. The polyester polyols can also be selected from the polyester polyols prepared by lactones. Such polyester polyols, which are prepared by lactones, can be selected from, but not limited to, α-caprolactone.
The polyester polyol comprises 10-60 wt. % succinic acid units, preferably 20-58 wt. %, most preferably 40-53 wt. %, based on 100 wt. % of the polyester polyols;
The structure of the succinic acid unit (I) is described as below
The NCO content of the said isocyanate prepolymer is 13-30 wt. %, preferably 14-25 wt. %, most preferably 16-20 wt. %, based on 100 wt. % of isocyanate prepolymer
The isocyanate-terminated prepolymer can be prepared by conventional methods, for example, as described below,
The a1 and a2 are charged into a reactor, mixed and reacted. After the completion of reaction at 40-100□, the isocyanate-terminated prepolymer is obtained.
The polyurethane microcellular foam can be used to produce shoe materials.
The Examples and the methods provided in the present invention are illuminative but not restrictive.
4,4′-MDI and polyols were introduced into the reactor in accordance with the materials and amounts thereof listed in Table 1.
After the reactor was cooled to 65° C., CD-MDI was introduced into the reactor and mixed for 30 mins.
After the reactor was cooled to the room temperature, an isocyanate terminated prepolymer A1-A5 had been obtained.
In the Comparative Examples C1, the polyester polyol for preparing isocyanate prepolymer A4 comprised succinate polyester polyol (PESSA-1), wherein, the content of the succinic acid units was 5 wt. %, based on 100 wt. % of polyester polyols.
The isocyanate terminated prepolymers provided in Example E1-E3 and Comparative Examples C1-C2 were marked as Component A.
The other components (such as polyols, chain extenders, blowing agents, catalysts and surfactants) were marked as Component B.
The Component B was mixed by using mechanical stirrer and loaded into a charging bucket of an injection molding machine at 45° C. The amount of the Component B was listed in Table 2.
The Component A was introduced into the charging bucket. The temperature of the charging bucket was 50° C.
The Component A and Component B were mixed by a mixing head, and injected into an aluminum folding mould. The temperature of the mould was 50° C. The NCO index of the reaction can be optimized by the methods known in the prior art.
The mould was closed, and the foam was demoulded after certain minutes to obtain a polyurethane microcellular foam.
The demould time, physical properties and mechanical properties of the obtained polyurethane microcellular foam were listed in Table 2 and Table 3.
According to the Table 2:
The polyurethane microcellular foams were prepared by the prepolymer A1.
The reactivity of process for preparing the polyurethane microcellular foams was good.
Comparing with the traditional reaction system (Comparative Examples C3, 250 seconds), based on the same amount of catalyst, the demould time was reduced to 150 seconds when the cream time was equivalent.
According to the Table 3:
In Example E5-E9, the polyurethane microcellular foams were prepared by the component B with prepolymer A1, A2, A3, respectively.
The reactivity of process for preparing the polyurethane microcellular foams was good.
Comparing with the traditional reaction system (Comparative Examples C3, 250 seconds), the demould time was significantly improved.
In Comparative Examples C5, the polyester polyols for preparing the prepolymer A4 comprised 10 wt. % succinate polyester polyol (PESSA-1), wherein, the amount of the succinic acid units was about 5 wt. %, based on 100 wt. % of the polyester polyols. The demould time of the process preparing the polyurethane microcellular foams was not reduced effectively (Comparative Examples C5, 250 seconds).
In Comparative Examples C6, the polyols for preparing the prepolymer did not comprise succinate polyester polyol, however, the component B comprised polyester polyols (PESSA-2) containing succinic acid units. The demould time of the process preparing the polyurethane microcellular foams was not reduced effectively (Comparative Examples C6, 210 seconds).
Although the present invention is illustrated through Examples, it is not limited by these Examples in any way. Without departing from the spirit and scope of this invention, those skilled in the art can make any modifications and alternatives. And the protection of this invention is based on the scope defined by the claims of this application.
| Number | Date | Country | Kind |
|---|---|---|---|
| 201010242692.2 | Aug 2010 | CN | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP11/63245 | 8/1/2011 | WO | 00 | 4/19/2013 |
