Patent Application
20130274365
The present invention pertains to polyurethane, in particularly, pertains to a polyurethane with improved abrasion resistance, the method for preparing the same and use thereof.
Polyurethane (in particularly polyurethane elastomer), which possesses good tear strength, good flex fatigue resistance and relative low density, is a kind of material having extensive use, such as footwear, carpet, roller, coating and soft parts used in automotive. Especially in the industry of footwear making, shoe-soles made from polyurethane (especially from polyurethane elastomers) possess a lot of advantages such as light weight, slip resistance, good rebound, high strength, oil resistance, etc.
Isocyanate compounds with react active hydrogen-containing compounds (for example, polyester polyols or polyether polyols), in the presence of a catalyst and/or blowing agent. The polyester-based polyurethanes possess good mechanical properties, however, the low temperature properties, hydrolysis resistance properties and antimicrobial properties of the polyester-based polyurethanes are bad, furthermore the processing technology of the polyester-based polyurethanes are relatively complicated. On the other hand, the polyether-based polyurethanes possess good hydrolysis resistance properties, good low temperature properties, however, the mechanical properties, especially the abrasion resistance, of the polyether-based polyurethanes are relatively bad. In addition, preparing polyurethane by use of non-aqueous inert physical blowing agent, such as fluorine-containing blowing agent, might pollute the environment; preparing polyurethane by using of water as blowing agent, will bring negative influence to the mechanical properties of the polyurethane, especially the abrasion resistance.
In the prior art, several trials have been applied to improve the mechanical properties of polyurethanes (especially polyurethane elastomers). For example, CN1092210C disclosed a method for preparing a polyurethane elastomer in presence of liquid polybutadiene to improve the mechanical properties of polyurethane elastomer. However, in accordance with the method, the amount of the liquid polybutadiene was 0.1-10 weight parts based on 100 weight parts of the polyols, wherein in the polybutadiene the amount of the 1,2-butene was less than 50%, the amount of the 2,3 (cis)-butene was higher than the amount of the 2,3-(trans) butane, the abrasion resistance of the polyurethane elastomer obtained according to this method was 81-270 mg (tested according to ISO4649).
In addition, U.S. pat. No. 4,242,468 disclosed a method for preparing polyurethanes by adding a monohydroxylated polybutadiene as a nonmigratory plasticizer, U.S. Pat. No. 5,079,270 disclosed a method for preparing polyurethanes by adding a liquid polybutadiene as an internal mold release agent.
The present invention pertains to polyurethanes with improved abrasion resistance and methods for preparing the same. The polyurethanes obtained in this invention possess good abrasion resistance and surface appearance.
One objective of this invention is to provide a polyurethane. One embodiment of the present invention includes polyurethanes comprising the reaction product of a mixture comprising:
Preferably, the amount of the polyisoprene is from 0.5 to 2 wt. %, based on 100 wt. % of A), B), C) and D).
Preferably, the molecular weight of the polyisoprene is from 1000 to 80000.
Preferably, the density of the polyurethane is from 100 to 1200 kg/m3.
Preferably, the abrasion resistance of the polyurethane is from 30 to 200 mg, tested according to ISO4649.
Another objective of this invention is to provide a method of preparing polyurethanes, comprising reacting a mixture comprising:
Preferably, the amount of the polyisoprene is from 0.5 to 2 wt. %, based on 100 wt. % of A), B), C) and D).
Preferably, the molecular weight of the polyisoprene is from 1000 to 80000.
Preferably, the density of the polyurethane is from 100 to 1200 kg/m3.
Preferably, the abrasion resistance of the polyurethane is from 30 to 200 mg, tested according to ISO4649.
Another objective of this invention is to provide a use of the polyurethanes in preparing polyurethane elastomers.
Another objective of this invention is to provide a use of the polyurethane in preparing microcellular polyurethane elastomers.
Another objective of this invention is to provide a use of the polyurethane in preparing shoe sole, carpet, roller, sealing strip, coating, tire, wiper, steering wheel or gasket.
In the present invention, preparing the polyurethanes by adding a polyisoprene in accordance with the described characteristics into the polyols and/or isocyanates will significantly improve the abrasion resistance thereof. Furthermore, comparing to the prior art, the polyurethane obtained in this invention does not have obvious pin holes, but possesses good surface quality.
The present invention provides a method for preparing polyurethane with improved abrasion resistance by adding a polyisoprene with special characteristics. In this invention, the polyisoprene with special characteristics can be used to prepare polyols and/or isocyanates for preparing polyurethane.
In the present invention, the molecular weight of the polyisoprene is preferably 1000-80000, the amount of the polyisoprene is 0.05-5 wt. %, based on 100% by weight of A), B), C) and D), wherein the polyisoprene comprises one or more polyisoprene structural units as following,
The amount of the polyisoprene is 0.05-5 wt. % , preferably 0.5-2 wt. %, based on 100 wt. % of A), B), C) and D).
In the present invention, the isocyanate can be specified by a general formula R(NCO)n, wherein R represents (cyclo) aliphatic alkylene comprising 2-18 carbon atoms, aromatic alkylene comprising 6-15 carbon atoms or (cyclo) aliphatic aromatic alkylene comprising 8-15 carbon atoms, n=2-4.
The isocyanate can be selected from, but not 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 carbon diamine, 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 polyisocyanate may also include isocyanate prepolymer. The NCO content of the isocyanate prepolymer can be selected from, but not be limited to, 5-30 wt. %, preferably 10-25 wt. %, based on 100 wt. % of the prepolymer.
In the present invention, the polyol can comprise one or more polyols, the average molecular weight of the polyol can be selected from, but not be limited to, 1000-10000, and the functionality of the polyol can be selected from, but not be limited to, 1-5, preferably 1.8-3.2.
In the present invention, the polyol can be selected from, but not be limited to, polyester polyols, polyether polyols, polycarbonate polyols, polymer polyols or their mixtures.
The polyester polyols can be produced from the reaction of dicarboxylic acids or dicarboxylic acid anhydrides with polyhydric alcohols. The dicarboxylic acids can be selected from, but not be limited to, aliphatic carboxylic acids containing 2 to 12 carbon atoms, such as 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, and their mixture. The dicarboxylic acid anhydrides can be selected from, but not be limited to, phthalic anhydride, terachlorophthalic anhydride, maleic anhydride, and their mixture. The polyhydric alcohols can be selected from, but not be limited to, ethanediol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,3-methylpropanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, glycerol, trimethylol-propane, or their mixture. The polyester polyols, can also includes the polyester polyols prepared by lactones, for example, polyester polyols prepared by lactones can be selected from, but not be limited to, e-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 mixture. 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 mixture. The polyhydric alcohol starters can be selected from, but not be limited to, polyhydric compounds, such as, water, ethylene glycol, 1,2-propanediols or 1,3-propanediols, diethylene glycol, trimethylolpropane, or their mixture.
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 polymer polyols can be selected from, but not be limited to, polymer-polyether polyols, polymer-polyester polyols, or their mixture.
The polymer-polyester polyols are graft polymer polyols based on polyesters or polyetheresters, preferably graft polymer polyol and polyester polyol dispersion. The graft polymer polyol can be selected from, but not be limited to, graft polymer polyol based on styrene and/or acrylonitrile; The styrene and/or acrylonitrile can be produced by the in situ polymerisation of acrylonitrile, styrene, or the mixture of styrene and acrylonitrile; In the mixture of styrene and acrylonitrile, the ratio by weight between the styrene and acrylonitrile is 90:10-10:90, preferably 70:30-30:70. The polymer polyester polyol dispersion comprises disperse phase, for example, containing inorganic fillers, polyureas, polyhydrazides, polyurethane containing tertiary amino groups in bonded form and/or melamine. The amount of the disperse phase is 1-50 wt. %, preferably 1-45 wt. %, based on 100 wt. % of the polymer-polyester polyol.
The polymer-polyether polyols are polymer-modified polyether polyols, preferably graft polyether polyols and polyether polyol dispersion. The graft polyether polyols can be selected from, but not be limited to, graft polymer polyol based on styrene and/or acrylonitrile; The styrene and/or acrylonitrile can be produced by the in situ polymerisation of acrylonitrile, styrene, or the mixture of styrene and acrylonitrile; In the mixture of styrene and acrylonitrile, the ratio by weight between the styrene and acrylonitrile is 90:10-10:90, preferably 70:30-30:70. The polymer polyether polyol dispersion comprises disperse phase, for example, containing inorganic fillers, polyureas, polyhydrazides, polyurethane containing tertiary amino groups in bonded form and/or melamine. The amount of the disperse phase is 1-50 wt. %, preferably 1-45 wt. %, based on 100 wt. % of the polymer-polyester polyol.
In the present invention, the chain extenders are 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 mixture. 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 mixture. The amount of the chain extenders is 1-50 wt. %, based on 100 wt. % of the polyols and chain extenders used in the reaction system.
In the present invention, the blowing agents can be selected from physical blowing agents or chemical blowing agents, preferably 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 mixture. The hydrocarbons can be selected from, but not be limited to, butane, pentane, cyclopentane, hexane, cyclohexane, heptane, or their mixture. The gases can be selected from, but not be limited to, air, CO2, and N2. Preferably, the blowing agent is water. The amount of the blowing agent is determined by the density of polyurethanes.
In the present invention, 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 said catalyst is 0.001-10 wt. %, based on 100 wt. % of the polyols used in the reaction system.
In the present invention, the surfactants can be selected from, but not be limited to, polyoxyalkylene derivatives of siloxane. The amount of the said surfactants is 0.01 to 8 wt. %, based on 100 wt. % of the polyols and chain extenders used in the reaction system.
In the present invention, the pigments and/or fillers can be selected from, but not be limited to, calcium carbonate, graphite, carbon black, titanium dioxide, iron oxide, alumina trihydrate, wollastonite, glass fibers, polyester fibers, polymeric fibers.
The density of the polyurethane provided in the present invention is 100-1200 kg/m3, preferably 400-1000 kg/m3.
The abrasion resistance of the polyurethane provided in the present invention is 30-200 mg, preferably 35-150 mg, more preferably 35-100 mg, tested in accordance with ISO4649.
The polyurethane provided in the present invention can be used to prepare shoe sole, carpet, roller, sealing strip, coating, tyre, wiper, steering wheel or gasket.
The Examples and the methods provided in the present invention are illuminative but not restrictive.
In the Examples, PENDRAULIK agitator purchased from PENDRAULIK Company was used as a mixing device.
Reaction components B, C and D (and the optional E) were blended using a stirrer to obtain a blend.
The blend could be mixed and reacted with component A by two methods. In the first method, the blend was mixed and reacted with component A using a stirrer. In the second method, the blend was mixed and reacted with component A using a two components or a multi components mixing device. The mixing device could be a high pressure machine or a low pressure machine, preferably low pressure machine. The mixing process could be a double-stream mixing process or a multi-stream mixing process. For example, the pigment could be introducing as a third stream to change the color of the mixture quickly.
Molding techniques and equipments of polyurethane compounds were well known to those skilled in the art, especially using such learned treatises as Saunders and Fish, Polyurethane Chemestry and Technology (Part II) and Oertel, Polyurethane Handbook.
The density result of the polyurethane provided in this invention was tested in accordance with DIN EN ISO 845.
The hardness result of the polyurethane provided in this invention was tested in accordance with DIN 53505.
The abrasion resistance result of the polyurethane provided in this invention was tested in accordance with ISO4649.
The tensile strength result of the polyurethane provided in this invention was tested in accordance with DIN 53504.
The elongation result of the polyurethane provided in this invention was tested in accordance with DIN 53504.
The trouser tear result of the polyurethane provided in this invention was tested in accordance with DIN ISO 34.
The rocs flex result of the polyurethane provided in this invention was tested in accordance with ISO 5423.
Preparing the polyurethanes in Example E1-E8 and Comparative Examples 1-4 in accordance with the materials and amounts thereof listed in Table 1 and Table 2.
Firstly, mixing the polyols and the additives in accordance with the amounts listed in the Table 1 and Table 2 at speed of 1400 rpm equably (the additives may optionally comprise chain extenders, blowing agents, surfactants, pigments or fillers). Thereafter, mixing the obtained mixture, which comprises the polyols and the additives, with the isocyanates listed in accordance with the amounts listed in the Table 1 and Table 2 at speed of 4200 rpm at 25° C., then introducing into a sheet-shaped aluminum mold with dimensions approximately 200 mm×200 mm×10 mm, wherein the mold was controlled at 50° C., closing the mold, foaming and curing for 5 minutes, removing from the mold and obtaining a polyurethane. The obtained polyurethane was left at room temperature for at least 48 hours before undergoing testing, the properties of the polyurethane was listed in the Table 1 and Table 2.
In Example E1-E5, the polyurethane was prepared by adding the polyisoprene in accordance with the requirements of this invention into the polyols for preparing the polyurethane. The test results illustrated that the obtained polyurethanes possess improved abrasion resistance.
In Example E6, the polyurethane was prepared by adding the polyisoprene in accordance with the requirements of this invention into the isocyanates for preparing the polyurethane. The test results illustrated that the obtained polyurethanes possess improved abrasion resistance.
In Example E2, E4 and E5, different polyurethane with different densities were prepared by adding the polyisoprene in accordance with the requirements of this invention. The test results illustrated that the obtained polyurethanes possess improved abrasion resistance.
In Example E7 and E8, polyurethanes were prepared by adding the polyisoprene with different average molecular weights in accordance with the requirements of this invention. The test results illustrated that the obtained polyurethanes possess improved abrasion resistance.
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 |
|---|---|---|---|
| 201010240242.X | Jul 2010 | CN | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP11/62831 | 7/26/2011 | WO | 00 | 5/23/2013 |
