TWI338698B - Thermoplastic polyurethane, and method and apparatus for producing the same - Google Patents

Description

1338698 BRIEF DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to thermoplastic polyurethanes and methods and apparatus for making thermoplastic polyurethanes. In particular, the present invention relates to a process for producing a thermoplastic polyurethane by a reaction extrusion die, a device using the same, and a thermoplastic polyurethane prepared by the method. [Prior Art] Various methods for continuously producing thermoplastic polyaminocarboxylic acid vinegar by using a reaction extrusion die have been proposed so far. A typical method is a method in which a hot earth lanthanum polyurethane is continuously produced from a mixture by using a twin-screw extruder after mixing a polyisocyanate, a large polyol, and a chain extender, for example, for example, Japanese disclosure (not Approved by the Patent Gazette No. 5-214062 and No. 6_1 92368. ^Another typical method is where the polyisocyanate is mixed with a large polyol to make this foot. The material is passed through a static mixer to promote the prepolymerization reaction, and then the key is kneaded therein, and then the thermoplastic 彳生松# △ ^' urethane is continuously produced from the mixture by using a twin-screw extruder. The method is, for example, the one disclosed in Japanese published (uncensored) patent Platinum. θ, Report No. 5-27-27, and Ping 〇 _8 725. And mixing the polyisochloric acid I 2 in two static cleaners connected to each other to make the alcohol and the chain extender in the first static full, ., % S in the second static mixer The thermoplastic machine is continuously produced from the uncensored (unexamined) patent of the hydrazine hydrazide, for example, as disclosed in Japanese Laid-Open No. Hei 8-337630 and No. 2000-344855 No. 5 315225 1338698. In the method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Taking substantially the same procedure 'wherein after mixing the chain extender in the polyisocyanate with the macropolyol', the twin-screw extruder is used to react with each other while promoting the reaction and the mixture. Due to this, it is easy to produce a cauterization deposit caused by mechanical shearing of the screw of the extruder and a gelled substance (fish eye) caused by the mixture remaining in the screw groove of the extruder. Further, in these methods, since a large amount of catalyst is required to promote the reaction, when the obtained polyamino phthalic acid is molded by extrusion molding or an injection mold, it is impossible to avoid the agricultural retreat of its nature. Deterioration in decomposition caused by a large amount of catalyst contained therein and deterioration of the molded product over time. On the other hand, in the method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Sediment and the production of gelled material caused by the mixture remaining in the screw groove of the machine, but due to the direct introduction of polyisocyanate, large polyol and chain extender into the static mixer, it is often insufficiently stirred , by which the gelatinous substance is easily produced. In particular, when a high melting point large polyol or a high melting chain extender is used, the reaction with the polyisocyanate precipitates, making it easier to produce a gelled substance. In addition, this method is also the same, since a large amount of catalyst is required to promote the reaction, as in the case of the above method, it is also inevitable that the deterioration of the property is caused by a large amount of catalyst contained in the polyurethane obtained. Deterioration on the decomposition 315225 6 1J38698 and the deterioration of the molded product over time. SUMMARY OF THE INVENTION ^ = The object of the invention is to provide a chain extender 'and a slow-reacting polyisocyanate vinegar and a slow-reacting polyisocyanate vinegar by using a high-melting-point multi-component f Hfi a method for producing a thermoplastic polyamine 曱s" by a catalyst of an acid ester, whereby a gelatinous substance and a cautery deposit are provided, and the shell is less degraded and less deteriorated over time; A method for producing a thermoplastic polyurethane; and a thermoplastic polyamino phthalate obtained by the method for producing a thermoplastic polyurethane. The present invention provides a method for producing a thermoplastic, polyamine A new method of carboxylic acid, which comprises pre-mixing at least a mixture of a polyisocyanic acid vinegar and a macropolyol and a chain extender reaction material when reacting through a static mixer. According to this method, due to the premixed state In the polyisoacid acid and large polyol introductory static mixer, those components can be uniformly reacted with each other by searching in a static mixer. This can effectively prevent the generation of gelatinous substances, which can be used by using High melting Large polyol, high melting chain extender, and slowly reacting polyisocyanate to continuously produce thermoplastic polyurethane. Vinegar. Moreover, since the method of the present invention does not use a twin screw extruder, it does not The production of thermoplastic polyamines can be reduced by the formation of a cauterization deposit caused by the mechanical shearing of the screw of the twin-screw extruder and the mixture caused by the mixture remaining in the screw groove of the twin-screw extruder The use of a carboxylic acid ester catalyst. This makes it possible to produce a thermoplastic polyaminomethacrylate having less deterioration in properties and less deterioration over time and low hardness. In the method, preferably 7 315225 ^ 38698 by mixing at least a polyisocyanate with a large polyol by a high speed mixer. By mixing at least a polyisocyanate with a large polyol by using a high speed mixer, these components can be more uniformly reacted with each other, thus - It is more versatile to prevent the generation of gelatinous substances. In the method for producing a thermoplastic polyaminophthalate of the present invention, the anti-stag material can be mixed by polyisocyanate at the same time. And a chain extender: the residue is prepared by first mixing a polyisocyanate with a large polyol, and then blending the chain length agent into the obtained mixture. Further, the latter is included after the polyisocyanate is mixed with the large polyol. The mixture obtained by mixing with a high-speed mixer is mixed with the chain extender by 2 after the polyisocyanate is mixed with the large polyol, and the obtained mixture is reacted by passing the mixture through a static mixer, and then a method of blending a supply line of a static mixer in a manner that allows the chain extender to be blended in the mixture. & In addition, in the method of producing a thermoplastic polyaminophthalate of the present invention, The portion of the static mixer that is in contact with the reactive material is preferably formed of a material that is substantially non-metallic. The structure of the contact portion of the static mixer and the reactive material formed by the material of the non-metallic material on the shell may be more Effectively prevent the formation of cautery deposits. In the process for producing a thermoplastic polyaminophthalate of the present invention, the static mixer preferably comprises a plurality of static mixers each capable of independently performing a series of connections for temperature control inside the static mixer. The static mixer can be constructed by changing the temperature inside the static mixer to y 315 225 8 1 338 698 according to the composition of the reaction material, and reducing the amount of catalyst by y while producing thermoplastic polyamine under optimal reaction conditions. Carbamate. Further, the present invention provides a novel apparatus for producing a thermoplastic polyurethane comprising mixing a mixture of at least a polyisocyanate and a macropolyol to blend a chain extender with at least a polyisocyanate mixed by a mixing member. A chain mixer blending member in a mixture with most of the alcohols and a static mixer for reacting the reaction materials of the chain extender blended in the mixture. When the thermoplastic polyurethane is produced by the device, the chain extender is further blended by the 5 component corpse & at least the polyisocyanate and the large polyol and by the chain extender blending member. The reaction materials can be uniformly reacted with each other by stirring in a static mixer by mixing the mixture of the components and reacting the thus prepared reaction materials in a static mixer. This can effectively prevent the generation of gelatinous substances. The thermoplastic polyaminophthalate can be continuously produced by using a high-alcoholic alcohol, a chain-chain extender of Nanxuan, and a slow-reacting poly-acidic acid. Moreover, since the twin-screw extruder is not used, the burning deposit caused by the mechanical nucleus of the screw of the twin-screw extruder and the mixture remaining in the screw groove of the twin-screw extruder are not produced. The resulting gelatinous substance. Furthermore, the amount of the catalyst for the manufacture of the thermoplastic oxime phthalate is reduced. This makes it possible to produce a thermoplastic polyurethane which is less deteriorated in nature and which is less deteriorated by the father and has a low hardness. Furthermore, the present invention provides a novel thermoplastic polymer obtained by reacting a reaction material comprising a premixed mixture of at least polyisocyanuric acid and a mixture of a large polyhydric alcohol and a chain extender through a static, > Amino phthalate. 315225 9 1338698 Since the thermoplastic polyamino phthalate can be prepared by uniformly reacting the reaction material by stirring in a static mixer, it can provide less cautery deposits and gelled substances and its properties are better. Less decay and less deterioration over time. Furthermore, it has excellent mechanical properties such as tensile strength, elongation after fracture, tear resistance, and compression set characteristics, and has the advantage of being manufactured so that it has such a wide range of brightness temperature and the same hardness. In other words, it begins to fluidize at a low temperature in the car. Furthermore, it provides a soft, gelatinous substance (fish eye) on the charred and granular structure. Further, since the amount of the catalyst can be reduced in production, even when a non-yellowing polyisocyanate is used, it is excellent in the tendency to cause yellowing. [Embodiment] Fig. 1 is a view showing a configuration of a first example of an apparatus for producing a thermoplastic polyaminophthalate by applying the method for producing a thermoplastic polyaminophthalate of the present invention. In the following, a first example of the method for producing a thermoplastic decanoic acid phthalate of the present invention will be explained with reference to Fig. 1. In Fig. 1, the apparatus 1a is a device for continuously producing a thermoplastic polyaminophthalate by a reaction extrusion molding method. The apparatus 1a includes a raw material tank member 2' mixing member 3, a static mixer member 4, and a granulation member 5. The raw material tank member 2 includes a polyisocyanate storage tank 6, a polyol storage tank 7, and a chain extender storage tank 8. The polyisocyanate as a raw material of the thermoplastic polyaminophthalate is stored in the polyisocyanate storage tank 6. The polyisocyanate used is an organic compound such as an aromatic, aliphatic, and alicyclic polyisocyanate having at least two isocyanate groups in one molecule. The aromatic polyisocyanate which can be used comprises, for example, 2,4-indole diisocyanate, 2,6-toluene diisocyanate and its weight ratio of 80:20 (TDI-80/20) to weight ratio of 65:35 ( Isobaric mixture of TDI-65/35), 4,4'-diphenylmethyl diisocyanate, 2,4'-diphenyldecane diisocyanate, 2,2'-diphenyldecane diisocyanate Any isovosic mixture of these diphenylmethane diisocyanates 'methyl benzo diisocyanate, diphenyl phenyl diisocyanate, tetramethyl dimethyl diisocyanate, p-phenylene diisocyanate and naphthalene diisocyanate. Aliphatic polyisocyanates which may be used include, for example, ethylene diisocyanate, triterpene diisocyanate, tetradecyl diisocyanate, hexamethylene diisocyanate, octadecyl diisocyanate, hexamethylene diisocyanate , 2,2,-di-pentyl pentane diisocyanate, 2,2, cardiotrimethyl hexane diisocyanate, decamethyl diisocyanate, butylene diisocyanate, 1,3-butadiene-1,4- Diisocyanate '2,4,4-trimethylhexamethylene diisocyanate' 1,6,1 1- +-methylene triisocyanate, anthracene, 3,6-hexamethylene triisocyanate, 1,8-diisocyanate 4-Iocyanate mercaptooctane, 2,5,7-trimethyl-1,8-diisocyanate·5-isocyanate methyloctane' bis(isocyanate g ethyl)carbonate, bis(isocyanate B) Ether 'ether, 4 · butanediol dipropyl ether - w, w, - diisocyanate 'lysine isocyanate decyl ester, lysine triisocyanate ' 2 - isocyanate ethyl 2,6 _Diisocyanate hexanoate, 2-isocyanate propyl-2,6-diisocyanate hexanoate and bis(4-isodecanoate-n-butylidene) pentaerythritol. The alicyclic polyisocyanate which can be used includes, for example, 'isophorone diisohydro acid cool' bis (isolactic acid® fluorenyl) cyclohexane pit, two 315225 cyclohexylmethane diisocyanate, cyclohexane two Isocyanurate, nonylcyclohexane diisocyanate, 2,2,-dimethyldicyclohexyldecane diisocyanate, dimer acid diisocyanate, 2,5-diisocyanate methyl-bicyclo[ 2,2,1]-Gengyuan' and its 2,6-diisocyanate decyl bicycloalkane isomer' 2-isocyanate s-methyl-2_(3-isocyanohydrin propyl; % different Cyanate S is methyl-bicyclo[mouth, ~ heptane, 2 • isocyanate methyl 2 - (3 - isocyanate propyl)-6-isocyanate fluorenyl _ bicyclo [2, 2, 丨] heptane, 2_ Isocyanate methyl-3-(3-isocyanatepropyl)_5_(2-isoyl)-bicyclo[m]-heptene' 2' isocyanate methyl hydrazine (3 iso-acid propyl)-6-( 2-Isocyanic acid S is ethyl) _ bicyclo [^ Bu Gengyuan, 2_isoacid S is methyl-2-(3-isocyanatopropyl)_5_(2-iso & acid § Ethyl)bicyclo[^,丨]-heptane, and 2-isocyanurate methyl-2-(3-isocyanatepropyl)> 6-(2-isocyanateethyl)-bicyclic [m]·Heptane. The polyisocyanate that can be used contains, for example, a modified substance such as a modified polycarbamic acid capable of 'modified carbodiimide, modified urea uretimine' The quality of the biuret, the modified urea-formic acid vinegar' and the modified trimeric isocyanate. The above-mentioned polyisocyanate s is exemplified by 4,4, diphenylmethane diisocyanate (hereinafter referred to as , MDI"), hydrogenated MDI (dicyclohexylmethane diisocyanate, hereinafter referred to as ', HMDIe), benzoic diisocyanate (hereinafter referred to as, PPDI"), naphthalene diisocyanate (hereinafter referred to as NDI), hexamethylene diisocyanate (hereinafter referred to as HDI//), isophorone diisocyanate (hereinafter referred to as 'IpDI〃), 2,5-diisodecanoic acid methyl-bicyclo[2 , 2, Xiao Gengkeng, and its 2,6• diisocyanate methyl _ 315225 12 1338698 clothing [2'2, U-heptane isomer (hereinafter referred to as NBDI,) as a comparison More preferred are MDI, Hm, hmdi, ppDi and Nbdi, and their modified products such as modified urethane modified carbodiimide? These polyisocyanuric acid can be used alone or in combination of two or more. When two or more polyisocyanates are used in combination, they can be stored in a single yoglycolic acid. The mixture of the tank & φ + and the Japanese t T tank 6 is stored separately and can be separately stored in the individual polyisophthalic acid storage tank 6. The thermoplastic polyamine group is used in the polyol storage tank 7. "Most of the original family (4) is a large polyol that can be used for storage, for example, the two hydroxyl groups are flat, and the knife 3 has at least a sulfhydryl compound such as polyoxane and polycarbonate diol.多 曰 兀 兀 , , , , 可 可 可 可 可 可 可 可 可 可 可 可 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多 多Oxygen: two and the corresponding polyoxyl diol (including bismuth propylene glycol obtained from the phenyl epoxy component, especially, preferably:: = polymerization as the epoxy plant. Polyoxygen can be used Burning two: coated with C: with epoxy ethyl alcohol - alcohol, polyethylene glycol, another s & For example, polypropanol. ... Copolymerization with Ethylene Ethylene is used in the manufacture of thermoplastic "oxygen" in the present invention. The number of polyols in the building is average? (10) The method is 1〇, _, or preferably 5〇0 to 8, 〇〇〇. ^佳为_至

31522S 13 1338698 In the method for producing a thermoplastic polyurethane of the present invention, from the viewpoint of lowering the glass transition point and improving the flow property, it is preferred to use two kinds of molecular weights and oxygen base groups different from each other or More polyoxyalkylene glycols. Further, the polyoxyalkylene glycol preferably contains a small amount of a unit alcohol which has an unsaturated group at its molecular terminal due to a side reaction of the propylene oxide pit. The content of the monol in the polyoxyalkylene polyol can be measured by the refractive index of the total unsaturation provided by JIS Κ - 15 5 . The total degree of unsaturation in the polyoxopolyhydric alcohol is preferably 〇 3 meq / g or less ' or preferably 0.02 meq. / g or less. When the total degree of unsaturation is more than 0.03 meq. / g, the polyoxyalkylene polyol has a tendency to lower heat resistance and durability. From the viewpoint of industrial production of polyoxyethylene polyol, the lower limit of total unsaturation is preferably at the level of 〇. 〇 1 rneq./g. The alkali metal compound such as cesium hydroxide and cesium hydroxide, and a compound having a P=N bond (for example, a cyanohydrin compound, a phosphine oxide compound, and a phosphazene compound) may be mentioned as the use for producing the polyoxyalkylene polyol. A preferred polymerization catalyst for alkylene oxide. By using this alkylene oxide polymerization catalyst, a polyoxyl polyol having a low total unsaturation can be obtained. A polytetramethylene ether glycol (hereinafter referred to as PTMEG®) obtained by ring-opening polymerization of tetrahydrofuran may be mentioned as the polyoxyalkylene polyol. The number average molecular weight of PTMEG used in the process for producing a thermoplastic polyurethane of the present invention is preferably from 250 to 4, and the grade of 〇〇〇 or preferably is from 250 to 2,000. A polyoxygenated 315225 1338698 polyol obtained by PTMEG addition polymerization with the above alkylene oxide can also be used.

Multi-ester polyols which may be used include, for example, by at least one or at least two low molecular weight polyols such as ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentyl Glycol, 1,6-hexanediol, glycerol, trihydroxydecylpropane, neopentyl glycol, 3-methyl-1,5-pentanediol, hydrogenated bisphenol A, and hydrogenated bisphenol B' Obtained by condensation polymerization with, for example, glutaric acid, adipic acid, sebacic acid, terephthalic acid, meta-diacid, and dimer acid' or other low molecular weight dicarboxylic acid or oligo diacid acid Polyacetate polyol. Further, a polyhydric diol which is obtained by ring-opening polymerization of ε-caprolactone may be mentioned as a polyhydric polyol. Preferably, the number average molecular weight of the polyester polyol used in the method for producing a thermoplastic polyurethane of the present invention is from 500 to 3,0 ' or preferably from 8 〇〇 to 2,000 level. Φ The polycarbonate diol which can be used includes, for example, a diol such as 1,4-butanediol and iota-6-hexanediol, and dimethyl carbonate, diethyl carbonate or the like. Polycarbonate diol obtained by condensation polymerization. Preferably, in the method t for producing a thermoplastic polyurethane of the present invention, the number average molecular weight of the polycarbonate diol is from 5 Å to 3, and the 嶋 grade is 'or preferably 8 〇〇. Up to 2,000. These large polyhydric alcohols may be used singly or in combination of two or more kinds: when two or more large polyhydric alcohols are used in combination, they may be stored in a mixture of a single sterol bead storage tank 7 Alternatively, the individual storage tanks 7 can be separately stored. The bond growth agent as a raw material for the thermoplastic polyamine (IV) is stored in a chain extender storage tank 315225 15 1338698. Ethylene glycol, ???, 5-pentanediol, 16_ can be used as a chain extender comprising, for example, eight aliphatic, aromatic, and - hydroxy groups containing at least a compound. Aliphatic polyols that can be used: alicyclic anthracene low molecular weight propylene glycol, hydrazine, 3-propylene glycol, hydrazine, 4 • butanediol. Containing 'for example' diol, glycerol, and trimethylolpropane. Aromatic, heterocyclic or alicyclic rings which may be used are, for example, p-dimethyl diol diols. ·Hydroxyl-containing 'bis(2-hydroxyethyl) ester of diacid, 丨4_ soil) 间, m-phenyldioxy) stupin 'm-phenyldicyclohexyl) propyl... bis-dimethyl-ethyl 1 〇-tetraoxohetero[5,5] deca-carbon, ring-burned-methanol V cyclohexanediol. Shen Yijia and 丨, 4- These bond extenders may be used singly or in combination of two or more. When two or more chain extenders are used in combination, they may be stored in the form of a mixture in the single chain extender storage tank 8 or may be separately stored in the individual chain extender storage tanks 8. The catalyst and the auxiliary agent may be mixed with the above-mentioned components in the production of the thermoplastic resin of the present invention in accordance with the intended purpose and application thereof. The catalyst and auxiliaries can then be stored in storage sumps 6, 7, 8 with the above ingredients or can be stored in a different storage tank (not shown) so that they can be fed as needed. The auxiliaries can be blended after the manufacture of the thermoplastic polyurethane. Catalysts which can be used include, for example, the use of known catalysts for the manufacture of polyurethane 315225 16 such as amine compounds and organometallic compounds. Preferably, an organometallic compound is used. The organometallic compound which can be used includes, for example, tin acetate, tin octoate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dihydrate, lead octoate, lead tetraallate , nickel naphthenate, and cobalt naphthenate. These catalysts may be used singly or in combination of two or more. The catalyst is usually stored in the polyol storage tank 7 and/or the chain extender: storage tank, rather than the polyisocyanate storage tank 6. The catalyst is preferably stored in the polyol storage tank 7. The mixed vehicle is used in an amount of 90 ppm or less or preferably 3 ppm by weight or less based on the weight of the large polyol. Additives that can be used in South include, for example, mold release agents, coupling agents, coloring lubricants, weathering agents, antioxidants, UV absorbers, foaming Μ 'anti-moisture agent' opacifiers, and fillers, each of which is known As an auxiliary. The agent is usually stored in the polyol storage tank 7 and/or the chain extender storage medium instead of the polyisocyanate storage tank 6. It is preferably stored in the polyol storage tank 7. .... Bay 7 tanks 6, 7 and 8 are each equipped with a heater (or jacket), temperature sense J and 'mixed and burned (all not shown), and designed to be stored in storage, 6, 7, 8 The raw material (polyisocyanate (four) township is said to be a bond growth agent, etc.) 'while keeping it at a predetermined temperature. For example, the polyisocyanate storage tank 6 is set, for example, to 3 Torr; the polyol storage tank 7 is set at ', for example, 60 illus; and the key extender storage tank 8 is set at 30 to i3 〇 °C. Each of the storage tanks 6, 7, 8 is constructed to be connected to an inert gas line such as a nitrogen gas (not shown) 315225 1338698, and the atmosphere in the interior of each of the storage tanks 7, 8 is replaced with an inert gas atmosphere. High speed mixer 9. The pitch diameter of the 4Cm0 and the mixing member 3 are provided as a mixing member including the agitating vessel 10a and having a peripheral length of, for example, 12 cm and capable of rotating at 3 Torr to 5 Torr per minute (peripheral speed = 100 to 60 〇) m/min), or preferably a high speed mixer 9 of 1⁄3 to 35 rpm (peripheral speed: 120 to 420 m/min), which is a high speed feeder The mixer 9 is not particularly limited as long as it can stir and mix the raw materials at a high speed. Moreover, the high speed 9 step includes a heater (or jacket) and a temperature sensor (not shown) and is designed to control the heater based on the temperature detected by the temperature sensor to control the stirring container L〇a temperature. _ If necessary, the mixing member 3 may be provided with a reaction vessel 6 (as indicated by a broken line) to temporarily store the reaction material (described later) mixed in the high-speed mixer 9 to promote the reaction. This reaction dad 16 is preferably designed to adjust the temperature. Then, the reaction dad 16 is connected between the high speed agitator 9 and the first mash mixer 丨7a (described later) located at the uppermost side of the static mixer unit 4. The polyisocyanate storage tank 6 is connected to the high speed agitator 9 via a polyisocyanate supply line i j . The gear pump 2a is connected to the middle part of the multi-discrete vinegar supply line extending between the tank 6 and the mixer 9 on the side of the gear pump i2a. The staghorn alcohol storage tank 7 is connected to the high-speed visual machine 9 via a polyol supply line 14. The gear pump 1 2b is located on the downstream side of the gear pump 2b. The 3b is connected to the intermediate portion of the 315225 18 1338698 line extending between the tank 7 and the mixer 9. The chain storage tank 8 is passed through a wide flowmeter as a chain extender mixing member = chain extender supply line 5 and a high speed and position under the gear pump 12c, and a cutting machine is used. The UC system is connected to the intermediate portion of the key extender supply line b extending between the slots 8 and the static mixer unit 4 includes a preparation unit. The system 连接j is connected to a plurality of static quiescences. Machine 7 (the static mixer configuration (described later) in the flow direction from upstream to downstream, is the 4th machine 17a, the second static mixer i7b, ... the nth quiet person. Each has a configuration in the static green mix Human machine ^ Λ & machine 1 7η) The mixer component in the inside of the pipe. ~ The 7L piece can have any shape and shape; there are any special restrictions. For example, the mixer components can be (4) various (four) shapes including as described in, Chemical Engineering Advanced, " No. 4, mixing and symposium; (in the Chemical Engineering Association, D. W branch editor, by M - Ten published, I" 0 years 1 month 2〇曰 'first edition', page 155 of the first page, u figure company - N-type (COmpany_N Ding ype), company _τ• type company' and Company _ Ding · type. Preferably, the right and left elements are alternately arranged, and if desired, a straight tube can be placed between adjacent static mixers 7. Each of the static mixers 17 used has, for example, a center of 3.6 m, preferably 〇3 to 2 〇m, or more preferably a length of 〇5 to I, and preferably 10 to 300 mm. 13 to 15 〇 _, = more preferably 15 to 50 _ inner diameter; and 3 to 25, or more than quot; 315225 19 1338698 to 15 tube length / inner diameter (hereinafter referred to as L / D) The ratio. The static mixer 丨7 used is preferably formed of a substantially non-metallic material such as fiber reinforced plastic (FRP), or the surface of the inner tube which is in contact with the reaction material (described later) is fluorine such as polytetrafluoroethylene. The carbon resin is applied. The contact region with the static mixer 17 of the reaction material (described later) is formed of a substantially non-metallic material, and the generation of the cauterization deposit of the thermoplastic polyaminophthalic acid ester can be effectively prevented. It is preferred to use a static mixer 17 having a contact area coated with a fluorocarbon resin such as polytetrafluoroethylene. More specifically, a static mixer 17 or a commercial product MX series manufactured by Noritake Co., Ltd. in which a tube formed of a fluorocarbon resin such as polytetrafluoroethylene is embedded may be used. Furthermore, each static mixer 17 is provided with a heater (or jacket) and a temperature sensor (not shown), and is designed to control the heater based on the temperature detected by the temperature sensor to independently Adjust the tube temperature. This makes it possible to change the temperature of each of the static mixers according to the composition of the reaction material (described later). This enables the manufacture of thermoplastic polyurethanes with reduced catalyst usage under optimal reaction conditions. The first static mixer 1 7 a of the uppermost side of the static mixer component 4 is connected to the high speed mixer 9 (or reaction dad 6) of the mixing component 3, and is located at the lowermost side of the static mixer component 4. The nth static mixer 1 7n is connected to a strand die 19 (or a single screw extruder) 8 (described later) in the granulation member 5. 315225 20 1338698 The number of connected static mixers 17 can be suitably determined depending on the intended purpose and the composition of the raw materials. Static mixer (4) Connect with & column, such as 歹 丨 | 丨 > ns / 巧 / 10 to 50 static mixers, or preferably 1 5 to 3 5 static. At the beginning, the U static squeezing machine, the static mixer connected by the whole length of 3 to 25, is 5 to 20 m. In the vicinity

The static mixer 1 7 g · quot; VL > 丄 _ L ... 胄 17 _ set (four) into a gear rate to adjust the flow rate (not shown). The granulation member 5 is provided with a wire strand mold 19 and a cutter 2 。. The granulation member 5 may be in the form of a known granulator (including an underwater cutter), and there is no particular limitation on the strand mold 19 and the cutter 2G. If necessary, a single screw extruder 8 can be provided between the static mixer part 4 and the granulation unit 5, as shown by the broken line, to further knead the reaction material discharged from the static mixer part 4. The single screw extruder 18 is configured with a transition device at its front end to remove particles and gel from the reactive material. The m device is made to contain a 'for example' polymer filter. Next, a method of producing a thermoplastic polyaminophthalic acid ester by the manufacturing apparatus la shown in the second drawing will be described. In this method, first, the polyisocyanur cool poly-alcohol and chain extender are stored in the poly-amp; vinegar storage tank 7 and the chain extender storage tank 8, respectively. The high-speed transfer machine 9 is further mixed by a high-speed mixer 9 四 (4) to prepare a reaction material. 315225 21 1338698 In order to supply polyisocyanate from the polyisocyanate storage tank 6, the gear train (2) is controlled based on the flow rate measured by the flow rate t+13a, such that, for example, 2 to 1 〇〇 kg/h 'Or a flow rate of preferably 2 5 to 6 〇 _ is supplied to the high speed search machine 9 from a polyisocyanuric acid supply line. In order to supply the large polyol from the multi-S alcohol storage tank 7, the gear recording is controlled based on the flow rate detected by the flow meter 13b so as to be, for example, 10 to 200 kg/h, or preferably 15 to 1 Torr. The kg/h2 flow rate supplies the large polyol from the polyol supply line 14 to the high speed feeder 90. To supply the chain extender from the chain extender storage tank 8, the gear is controlled based on the flow rate measured by the flow meter Uc. The a is such that the chain extender is supplied from the chain growth difficult ride 15 to the high speed agitator 9 at a flow rate of, for example, 0.2 to 5 〇 kg/h, or more preferably 〇3 to 3 〇. In the high-speed mixer 9 which is in a stable state, the equivalent ratio (NCO/OH) of the polyhydric alcohol and the bond extender to the polyisocyanate-derived isophthalic acid group is set to, for example, 〇9. Magic 2, or preferably ... to 1.05 and the weight ratio of the large polyol to the genus of the chain is set to, for example, 2 to 90 times, or preferably 3 to 5 times. The high-speed batcher 9 mixes the poly-alcohol and chain extender in the agitated container] 〇a under the following conditions to prepare a reverse 315225 22 1338698 material: residence time: 0.05 to 0.5 minutes, Or preferably 〇1 to 〇4 minutes' temperature: 7〇 to 13〇〇c, or preferably 8〇 to i2(rc, and a paddle diameter of 4cm0 and a peripheral length of 12cm Stirring: 500 to 4,000 revolutions per minute (peripheral speed: 6 〇 to 48 〇 m/min) or preferably 2,000 to 3,000 rpm (peripheral speed · 240 to 36 〇 m/min). It is desirable to 'react the obtained reaction material at 7 Torr to 14 ° C, or preferably 8 Torr to 12 Torr, in the reaction dad 16 for example 〇 1 to 15 minutes, or preferably 〇 5 to 1 〇 The reaction material is then supplied to the static mixing component 4 and forced through an individual static mixer 17 to react its components with each other. For example, from 100 to 300 t, or preferably from 14 to 25 ( The rCi temperature range is suitable for selecting the tube temperature of the static mixer ,7, and the passing speed is, for example, 20 to 300 kg/h, or preferably 30 to 15 〇kg/h. Then 'if necessary' is squeezed by a single screw The press 1 8 further kneads the reaction material discharged from the static mixer part 4. Then, the strand material is pressed from the strand mold 19 in the granulating part 5 and then cooled by a known method. Thereafter, by cutting The machine 2 is cut to form granules, thereby producing a thermoplastic polyurethane. According to this method, the reaction materials including the polyisocyanate, the macropolyol and the chain length agent are premixed by the high speed mixer 9. Introduced into the static mixer part 4, the components of the reaction material can be reacted with each other in a static mixer of 315225 23 1338696 state. This can effectively prevent the generation of colloidal shells. Make zinc> Examples of the use of large polyol polyols which are still in the melting point include polyhydric hydrazines which are arsenic (small... scorpion decanoic acid, such as p-benzoquinone and bismuth and low molecular _ _ 7 Sterols, and the polyalkylates in the polyhydric alcohols listed above), interchain melting chain extenders (examples of bond lengthants are the above-mentioned aromatic producers - c 0 million knows % An alcohol, a heterocyclic polyol, or an alicyclic cyclic polyol, which comprises, for example, p-dimethyl diol, terephthalic acid bis(2-transethyl) styrene, m-dibenzoic acid double & Ethyl)ester, n-bis(2-hydroxyethoxy)benzene,], 3·bis(2-hydroxyethoxy)benzene, isophthalic acid, hydroquinone, 2,2, double (4_jing Base ring hexyl) propyl, 3, 9 • double (],! Dimethyl-2-reductive ethyl)_2,4,8,1〇_tetraoxo[5,5]undecal, ^%hex-methanol-methanol, and 4•cyclohexanediol) And a slow-reacting polyisocyanate (examples of polyisocyanates are so-called non-yellowing (NY) polyisocyanates such as the above-mentioned aliphatic polyisocyanates and alicyclic polyisocyanates) to continuously produce thermoplastic polyurethanes. Moreover, since the method of the present invention does not use a twin-screw extruder, there is no burning deposit caused by mechanical shearing of the screw of the twin-screw extruder and by the screw groove remaining in the twin-screw extruder The gelled substance caused by the mixture. Furthermore, there is no need for catalysts for the manufacture of thermoplastic polyamine phthalates or a significant reduction in the amount of catalyst required. This makes it possible to produce thermoplastic polyurethanes which are less inferior in nature and less subject to deterioration over time and low hardness. Fig. 2 is a view showing the configuration of a second apparatus of the present invention for producing a thermoplastic polyamino phthalate according to the method of the present invention for producing a thermoplastic polyamino phthalate. In the following, a second example of the method (4) for producing a thermoplastic polyamine according to the present invention will be described with reference to Fig. 2. In the same drawing, the same reference numerals are used to refer to the corresponding elements of Fig. 1 to omit the detailed description of the corresponding elements. In Fig. 2, the apparatus 113 includes a material tank member 2, a mixing member 3, a static mixer member 4', and an ostomy unit 5, as in the first! Figure 1 is not the case of the device 1 a. Storage tank 6, polyol storage device 1 shown in Fig. 1 The raw material tank member 2 comprises a polyisocyanate storage tank 7 and a chain length agent storage tank 8, as in the first case. The above polyisocyanate (IV) is stored in the polyisocyanate storage tank 6, and most of the above 7L alcohols are stored in the polyol storage tank 7; and the chain extender described above is stored in the chain extender storage tank 8. . The mixing member 3 is provided with two high-speed agitators 9a and % which are identical to the high (four) mixer 9 shown in Fig. 1 and which are connected in series. First, the 'Kunkou component 3 can be equipped with the name of the idling search machine 9 a below the dotted line, and the lower ancient, hit the monument, the Buwan same speed mixer 9b and the downstream of the high speed loss machine 9b The continuous storage of the reactors I 6a and 16b is carried out to temporarily expand the reaction materials mixed in the high-speed mixers 9a and 94 to promote the reaction. These reaction dads 16a, 16b are preferably designed to adjust the temperature as described above for the dad 16. It is possible to provide the reactors I6a, 6b, or both on an as-needed basis. 315225 25 1338698 The oxime isocyanate storage tank 6 is connected to the upper high-speed mixer 9a via a polyisocyanate supply line 1 1 . The gear pump 12a is connected to the flow meter 13a located downstream of the gear pump 12a at an intermediate portion of the polyisocyanate supply line 11 extending between the tank 6 and the upper mixer. The polyol storage tank 7 is connected to the upper high speed mixer 9a via a polyol supply line 14. The gear pump 12b is connected to the flow meter 13b located downstream of the gear pump Ub at a portion of the sterol supply line 14 extending between the tank 7 and the upper mixer 9a. The key extender storage tank 8 is connected to the lower high speed mixer 9b via a chain extender supply line 15. The gear pump 12c is connected to the flow meter 13c located downstream of the gear pump 12c at an intermediate portion of the key extender supply line 15 extending between the tank 8 and the lower mixer 9b. The static mixer component 4 includes a plurality of static mixers 17' connected in series, such as the device la of the Figure 1. The first static static mixer amp& is connected to the lower high speed mixer 9b (or the reactor 16b) of the mixing unit 3, and is located at the lowermost side of the static mixing machine 4. The η static mixer 1 7 η is connected to the strand mold 19 (or the single screw extruder 18) (described later) in the granulation member 5. The number of connected static mixers 1 7 can be suitably determined depending on the intended purpose and the application and composition of the materials. The static mixer 1 7 is connected in a row, such as 1 to 50 static mixers, or preferably 15 to 35 static mixers, and the static mixture is connected 315225 26 The entire length of the machine is 3 near static mixer 1 wheel pump (not shown). Up to 25 m ' or preferably 5 to 20 m. A tooth k designed to adjust the flow rate is interposed between the adjacent 7 . The case of the 5th wire stock mold i 9 and the cutting machine 2 is set. If necessary, a single-screw extruder 提供 can be provided between the static mixer 4: and the component 5, as indicated by the dashed line: the step is mixed from the static mixer component 4 and the single screw (four) machine is discharged. 18 can be equipped with self-reactive material particles and gel at the front end. The (4) device package 3 used is, for example, a 'polymer filter. ...man, children, by means of the manufacturing device shown in Fig. 2, the method of plastic polyurethane. In this method, firstly, 'they will be stored in the polyiso-acid vinegar storage U and the polyol storage, and the large & alcohol supply to the top and the speed mixer 9a and then the upper high-speed mixer %;; combine 'and then' (four) obtained mixture and stored in chain extender storage ^

The chain extender in 8 is supplied to the lower high speed (four) machine % and further mixed by a high speed mixer 9b to prepare a reaction material. The S polyiso-fl-acid ester is supplied from the polyisocyanate storage shovel 6 to the upper high-speed agitator 9a at a flow rate of, for example, 2 to i 〇〇 kg/h, or more than 俨 to a melting point. The macropolyol is supplied from the polyol storage tank 7 to the upper south speed feeder 9a at a flow rate of, for example, 丨❹ to 2 〇〇, or preferably 15 to 1 () 〇 kg/h. As a result, in the high-speed transfer mechanism above the steady state, the equivalent ratio (NCO/OH) of the base to polyisocyanate isocyanate S group of 315225 27 1338698 large polyol is set to, for example, i 〇5 to 6, or preferably ”” to 5. Then, the upper high-speed mixer 9a stirs the polyisocyanate and the large polyol in a stirring vessel 〇a under the following conditions to prepare a mixture: residence time: 0.05 to 0.5 minutes, or preferably 〇j to 〇 4 minutes, Knitting degree: 60 to i5 〇 C, or preferably 8 〇 to, and stirring with a purple diameter of *(10) 0 and a peripheral length of 12 cm: stirring per minute to 4, just turning (peripheral speed: 6 〇) It is preferably 2, _ to 3, _ revolutions per minute (peripheral speed: 24 〇 to 360 m/min). After that, the obtained mixture can be obtained at (9) to 15 〇. : ' or preferably from 9 to 14 generations, for example, 〇ι to 6 〇 minutes, or preferably 1 to 30 minutes, in the reaction dad. Then, the mixture is supplied to the lower high speed mixer 9b. For example, the flow rate of (7) to hired, or preferably 20 to earn g/h, is supplied from the upper high speed picker 9a to the lower high speed picker 9b. It can be located in the high speed picker 9a (or the reaction dad 16a) The downstream gear train adjusts the flow rate. The chain extender is, for example, 〇2 to 5 〇kg/h, or preferably 〇3 to 3 〇kg/h. The flow rate is supplied from the chain extender storage tank 8 to the lower high-speed tax machine 9b. As a result, in the high-speed mixer 9b under the steady state, the chain-growth agent is based on the isocyanic acid vinegar isocyanate. The acidity equivalent ratio (NCO/OH) is set to, for example, 〇9 to j 2, or preferably 〇^ to 28 315225 1338698 1.05 and the weight ratio of the large polyol to the chain extender is set to, for example, 2 to 9 〇.倍' or preferably 3 to 50 times. Then, the lower high-speed mixer 9b stirs the polyisocyanate, the large polyol and the chain extender in the stirring vessel i 〇a under the following conditions to prepare a reaction material: residence time: 0.05 to 〇. 5 minutes, or preferably 〇ι to 〇·4 minutes' temperature: 6 〇 to 15 〇 < t, or preferably 8 〇 to, and a paddle (10) having a paddle diameter of 4 cm0 and a peripheral length of 12 cm Mixing: 500 to 4,000 revolutions per minute (peripheral speed: 6〇 to 48〇m/min), or preferably 2〇〇〇 to 3〇〇〇 revolutions per minute (peripheral speed: 240 to 36〇n /min). After that, it is necessary to make the obtained reaction material in the reaction at 70 to 14 〇C' or preferably 8G to 12 generations. In Example 16b, the sample is kept for 5 minutes, or preferably 0.5 to 10 minutes. Then, the reaction material is supplied to the static separation; g Α ~, 0 machine part 4 and forced to pass through the individual static mixer 17 The components are reacted with each other. The static mixer or preferably has a throughput speed of, for example, 150 kg/h °

The tube temperature of 1 7 can be, for example, from 〇 〇 to 3 〇 〇.匚, the temperature range of 2 50 °C is suitably selected, and 20 to 300 kg / h. Or preferably 30 to after 'right need' can be performed by a single screw extrusion 胄 18 - mixing from a static mixer. The reaction material emitted from the component 4. After the granules, the self-granulating part 5 is etched into the reaction material and then cooled by the method. >, after cutting by the cutter 20 to form particles, thereby making the heterogeneous & thermoplastic polyurethane. 29 315225 1338698 According to this method, because of the first high-speed mixing machine 9 a mixed

Mixing polyisocyanate with large poly-fermentation to prepare a mixture; then, preparing a reaction material by mixing the obtained mixture with a bond growth agent by a lower high-speed mixer 9b; and introducing the reaction material thus prepared into static In the mixer part 4, the components of the reaction material can be uniformly reacted with each other in the individual static mixers 17. This effectively prevents the generation of gelatinous substances. This can be accomplished by continuously producing a thermoplastic polyamino phthalate by using a high-alloy macropolyol, a high-strength bond extender', and a slow-reacting polyisocyanate. Moreover, since the method of the present invention does not use a twin-screw extruder, the burning deposit caused by the mechanical shearing of the screw of the twin-screw extruder and the screw groove left in the twin-screw extruder are not generated. A gelled substance caused by a mixture in it. Furthermore, for the manufacture of thermoplastic polyurethanes, there is no need for catalysts or a significant reduction in the amount of catalyst, which results in less degradation in properties and less deterioration over time and low hardness. Thermoplastic polyamino phthalate.

Fig. 3 is a structural view showing a third example of the apparatus for producing a thermoplastic polyurethane using the method for producing a thermoplastic polyurethane of the present invention. In the following, a third example of the method for producing a thermoplastic polyurethane for use in the present invention will be described with reference to Fig. 3. In Fig. 3, the same reference numerals will be used (the values of the corresponding elements in the figure 1 are omitted and the detailed description of the corresponding elements is omitted. In Fig. 3, the device] 3 'static mixer part 4 In the case of the device 1 a. The raw material tank member 2, the mixing portion and the granular member 5 are included, as shown in Fig. 1 315225 30 1338698. The raw material tank member 2 includes a multi-reservoir 7 and a chain extender storage tank. 6, polyol storage 8, as shown in Figure 1, the device La Ding in the polyisocyanic storage tank 6 'on the majority read system stored in the polyol storage tank above the chain growth of the material in the chain growth (four) in mind Towels. 'The mixing unit 3 is equipped with a high-speed mixer 9 with the device shown in the figure, and the page is constructed. If necessary, the 'mixing part 3 can be borrowed from the ancient JX # 8# p- ^ as shown by the dotted line. The reaction kettle 16 is provided in the presence of a temporary sheller, and the reactor 6 is mixed in the speed mixer 9. It is preferably designed to adjust the π heart at the high speed search machine 9 also: degree. The reaction provided by the father] 6 series ', After Yang "the uppermost side of the joint part 4 is connected between the first meditation and the machine I 7 a. Storage tank 6 Y Li Li Shi Xi s & ^ ^ 糸 'From the oxime phthalate supply line 1 1 connected with the high speed crawler 9. Tooth # $ 〇 斗 斗 w ^ W wheel pump 123 with the gear pump 2a The downstream stream is connected to the intermediate portion of the polyisocyanate supply line 1 extending between the tank 6 and the mixer 9. ^ το alcohol storage tank 7 is via a polyol supply line and a high-frequency mixer #轮果I2b and The flow meter located downstream of the gear train I2b] is connected to the intermediate portion of the polyol supply line between the tank 7 and the picker 9. The chain center* agent storage tank 8 is connected via a key growth agent supply line. ^ with the connection between::: the adjacent static mixer 丨7 of the assembly part 4 (in the third picture in the month? > between the Kunming machine 1 7a and the second static mixer 1 7b) D-shaped 31 315225 1338698 The connecting pipe 21 is connected. The gear pump 12c and the flow rate 131cc located downstream of the gear pump 12c are on the middle portion of the chain extender supply line 15 extending between the groove 8 and the butt-shaped connecting pipe 21 The static "mechanical component 4" includes a plurality of static mixers connected in series t. The device is located at the uppermost side of the static mixer component 4, and is quiet. The machine 1 7 a is connected to the high-speed search machine 9 (or the reaction kettle 16) of the mixing unit 3, and is located at the lowermost side of the static mixer part 4, and is connected to the 第1 7η The cotton mold in the granular member 5] 9 (or a single screw extruder 18) (described later). The number of connected static mixers 17 can be suitably determined depending on the intended purpose and the application and composition of the raw materials, as described above. The static mixer 17 is connected in a row, such as a horizontal 1 to 5 (M solid static mixer or preferably a 5 to 35 static mixer, which is connected by a static mixer) The entire length is ... 5m ' or preferably 5 to -. In the vicinity: Static, a gear pump designed to adjust the flow rate is inserted between the machines 1 7 . In the static mixing machine part 4, the τ-shaped connecting pipe 2 which can be joined to the chain extender supply line 15 is connected between the adjacent static mixers 17. The intergranular granule 5 is provided with a wire strand mold 19 and a cutter 2, such as =. If required*, a single screw extruder 18 can be provided between the static mixer component 4 and the granulation section: 5, as indicated by the dashed line, to react the effluent from the static mixer component 4 . Configured::: The rod extruder 18 can be equipped with a filtering device at its front end to move from the reactive material: particles and granules. The passing device #:r g h人 ', the over-the-device used contains 'for example, polymer filtration 315225 32 1338698

Next, a method of producing a thermoplastic 1 aminocarboxylic acid by the manufacturing apparatus u shown in Fig. 3 will be described. In this method, the polyisocyanate and the large polyhydric alcohol are separately stored in the polyisocyanate 6 and the polyol storage tank 7 and then supplied to the core f-mixer 9 by the high-speed compounding machine 9 Mixing, then, forcing: the selected mixture is passed through an individual static mixer 17 (the first static mixer in Figure 3) located in the static mixer part 4 and upstream of the τ-shaped connection to react the mixture. From the chain extender supply line. Supply the bond...-form the connecting tube 21 and mix it with the mixture and mix it with the splicer 2 1 to prepare the reaction material. The polyisocyanate is, for example, 21 to A flow rate of 1 〇〇 kg/h, or preferably 5 to 6 〇 kg/h, is supplied from the polyisocyanate storage tank 6 to the high-speed feeder 9. The large polyol is, for example, 1 Torr to 2 Torr. Kg/h, or preferably ???$ to 9 g/h U speed is supplied from the multi-presence storage tank 7 to the high-speed search machine. This result 'in the steady state high-speed mixer 9, large polyol r< The equivalent ratio (nc〇/〇h) of the isocyanic acid g group is set to, for example, K05 to 6, or preferably $] to 5. After the 'return speed mixing 胄9 In the transfer container &&&&" cyanide from the "曰 and most sterols to prepare the mixture: residence time: 〇 to 5 knives ~ ' or 杈 good for 〇 · · to 〇 · 4 minutes , temperature: 60 to 150 I: or preferably 8 〇 to l3 〇 ° C, and with a purple diameter of 4c - and 2cm, the length of the stirring paddle 〇 b stirring: 4 minutes to 4, cut 33 315225 1338698 number (peripheral speed: 60 to 48 〇 m / min), or preferably 2, (9) 〇 to 3, 〇〇 0 revolutions per minute (peripheral speed: 240 to 360 m / min). If necessary, then ' The resulting mixture may be maintained at a temperature of from 8 Torr to 15 Torr, or preferably from 90 to 4 〇 in the reactor 6 for example 〇1 to 6 :: 'or preferably 丨 to 3 〇 minutes Then, the mixture is supplied to a static mixer. The crucible 4 is forced to pass through a separate static mixer 1 7 (the third static mixer 1 7a) to react the mixture. In the individual static mixer 1 7 (the first static mixer 17a in Fig. 3) downstream of the component 4 t T-shaped connecting pipe 21, the pipe temperature is set to, for example, 1 〇 0 to 13 〇〇 ° C. Or preferably from 150 to 28 (TC, and the speed system is set to, for example, 10 to 2 〇〇 kg/h, or preferably 3 〇 to i5 〇 kg/h. The chain extender is, for example, i to 50 kg/h. , or preferably a flow rate of 3 to 3 Torr, is supplied from the chain extender storage tank 8 to the τ•-shaped connecting pipe η. As a result, in the Τ-shaped connecting pipe 21 in a stable state, the large polyol and the chain The equivalent ratio (NCO/OH) of the hydroxyl group of the growth agent to the isocyanate group of the polyisocyanate is set to, for example, 〇9 to 12, or preferably ^ to w, and the weight ratio of the large polyol to the chain extender is It is set to, for example, 2 to column times, or preferably 3 to 50 times. In this method, the wide material prepared in the butt-shaped connecting pipe 21 is forced to pass through the individual static mixer 17 located downstream of the τ_shaped y reversed official 2 1 in the static mixer part 4 (the third in the third figure) The two static mixers are connected to the nth static mixer 1 7 η) to react the reaction materials. In the individual static mixer 17 (the second static mixing _ ^ to the η 315225 34 1338698 static mixer 1 7 η in the third figure) located in the static mixer part 4 The temperature is suitably selected from a temperature range of, for example, 1 Torr to 3 Torr, or preferably 150 to 2801, and the passage speed is, for example, 20 to 300 kg/h, or preferably 30 to 150 kg/h. The reaction material discharged from the static mixer part 4 can then be further kneaded by a single screw extruder 18 if needed. Then, the strand mold 19 from the granulation member 5 is pressed and the reaction material is cooled. Thereafter, the thermoplastic polyurethane vinegar is obtained by cutting by a cutter 20 to form granules. According to this method, first, a mixture of 8 hydrazine polyisocyanate and a large amount of 7 L of alcohol is mixed by a high-speed mixer 9 to prepare a mixture, and then the obtained mixture is allowed to flow downstream of the τ-shaped connecting pipe 2 1 located in the static mixer part 4. The individual static mixers 17 (the first static mixer 17a in Fig. 3) react to synthesize the prepolymer therein. Thereafter, a chain extender is supplied and blended in the prepolymer in the T-shaped connecting tube 21 to prepare a reaction material. Then, the reaction material thus prepared is introduced into an individual static mixer 7 downstream of the butt-shaped connecting tube 2 1 in the static mixer part 4 (the second static mixer 1 7b to the 11th static in Fig. 3) The mixer is reacted in and reacted therein. Therefore, the components of the reaction material can be uniformly reacted with each other in the individual static mixers 17, which can effectively prevent the generation of the gelled matter. This can be accomplished by continuously using a high melting point polyol, a high melting chain extender, and a slow reacting polyisocyanate S. Moreover, since the method of the present invention does not use a twin-screw extruder, the burning deposit caused by the mechanical J-cut of the screw cup of the twin-screw extruder is not generated and remains after the twin-screw extruder. A gelled substance caused by a mixture in the trench. Furthermore, the manufacture of heat 315225 35 1338698 plastic polyamine phthalate requires no catalyst or requires a significant reduction in the amount of catalyst. This makes it possible to produce a thermoplastic polyurethane which is less deteriorated in nature and which has less deterioration over time and a low hardness. The thermoplastic polyurethanes prepared by the above methods provide less cautery deposits and gelled materials and are less degraded in nature and less prone to deterioration over time. Moreover, it has excellent mechanical properties such as tensile strength, elongation after fracture, tear resistance, and compression set, and has the advantage of being manufactured so that it has such a wide melting temperature range that it is for the same hardness. It begins to fluidize at a lower temperature. Furthermore, it provides very little gelatinous material (fish eyes) on the charred and granular structure. Moreover, since the amount of the catalyst can be reduced in manufacturing, even in the case of using a non-tanning multi-tano-acid Kus, the enamel has an excellent tendency to yellow. Therefore, the thermoplastic polyamino phthalate having these properties can be effectively applied to various fields, including, for example, the sole and the insole of shoes and ski boots, the exterior and interior of the automobile, the gas components, the casters, and the long water pipes. , tube 'plates, membranes, and fibers. In the method described, any known additive (preferably = described, masterbatch) having insoluble properties to the above-listed raw materials may be added, including, for example, Inorganic inorganic antibacterial antimony, inorganic deodorant, and flame retardant. : ', ', there is no special restriction on the method of adding additives, but it is added. It is added by using the apparatus 1d of the fourth embodiment shown in Fig. 4. As shown in Figure 4, + & one into ', left-handed two-way tube (injecU〇n tee) 22 series connected to the next month f resent mixer parts 4 φ to post L jing state mixer 1 7 Any of the three (3) 315225 36 丄 869 8869: P injury in Figure 4 'The same reference value refers to the relative deer parts of the i-th figure and the detailed description of the corresponding elements is omitted. The additive is placed in a single screw extruder 23 and supplied from the injection tee U to the static cokeite component 4 in the vicinity of the static mixer 17 "injured + ® Λ 'self & shot tee The additive supplied by the tube 22 is doped in the downstream of the injection tee 22 located in the static joint unit 4: in the reaction material of the static machine i 7 and in the static mixer part 4: injection three The individual static mixers 17 downstream of the tubes 22 are uniformly mixed in the reaction material. The additives are continuously fed from the single screw extruder u at a rate of, for example, 〇丨i(7)(iv), or preferably '〇5 to 30 kg/h. The reactive heat smelt can also be produced by using the apparatus 丨3 to 〖c shown in Figures 1 to 3. The reactive hot melt is a polyamine having a (10) isocyanate group at the terminal of the ruthenium molecule. The base sl prepolymer is used as a main component and is coated with a thermoplastic polymer, a tackifier, an elasticizer, etc. for the purpose of imparting heat resistance to the base material and the heat resistance of the adhesive itself. This reactive hot melt, first, by using the apparatus shown in Figures 1-3 a to U manufacture a polyurethane prepolymer containing a large polyol and a polyisocyanate as a main raw material. A polyacetate polyol is generally used as a large polyol. The polyglycol which can be used contains, for example, at a low Molecular weight polyols such as ethylene glycol, propylene glycol, =4-butanediol, hydrazine, 6-hexanediol, neopentyl glycol, and trimethylolpropane, and = aliphatic carboxylic acids such as adipic acid, Azelaic acid and sebacic acid' or an aromatic carboxylic acid, such as a polyester polyol prepared by esterification of adipic acid and isophthalic acid. 315225 37 1338698 In order to develop a thermal melt adhesive The function, which is used alone and with two or more polyester liquefied or crystallized at room temperature, preferably, the number average molecular weight of the polyester polyol used is on the order of 丨〇,000. Or more preferably from 1 〇〇〇 to 9 。. It is preferred to use the above-listed Mm, TDI, HMDI, Hdi, IpDI, (10) and sin as the polyisocyanate. The equivalent ratio (NC〇/〇H) of the isocyanate S group of polyisocyanate is set to, for example, five to eight' Or preferably from 1 · 3 to 5. The following method is exemplified as a method of producing a polyurethane prepolymer which is a main component of the reactive hot melt. First, the acid vinegar is placed in an isocyanate storage tank 6 of the apparatus 丨3 shown in Fig. 1 in an inert gas atmosphere, and stored in a temperature at which the polyisocyanate becomes a liquid. The polycyanate is usually stored in a nitrogen atmosphere at a temperature below the H 6 generation, although it depends on its nature. Then, the above polyester polyol was placed in a multi-read storage tank 7 of the apparatus la shown in Fig. 1 and stored therein at a temperature at which the polyisocyanate sl became a liquid. Multi-S poly-S alcohols are usually in the 4th to 4th to (9). The adjusted temperature of C is stored in a nitrogen atmosphere, although it depends on its nature. Thereafter, through the above method, the individual gears l2a, m are supplied to the polyisocyanate and the polyhydric alcohol supply line 14 via the polyisocyanic supply line U and the polyol supply line 14 from the poly(4) (4) storage tank 6 and the polyol storage. It is supplied to the idle mixer 9 and then fed into the first static mixer i7a. The number of connected static mixers 17 can be suitably determined depending on the amount of the polyamino 曱I S 曰 prepolymer produced. Static mixer 1 7 series horizontal 315225 38 1338698 column connection '3 to 8 静态 static mixers, such as rows 5 to 6 static mixers. Between the sound of the adjacent static encounter machine 17 W designed to adjust the flow rate, the number of turtles used for the raw materials used is inserted into the 忐 — — 静 静 静 静 静 静 静 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 17 60 to 230. (: the temperature. 6〇C ' or better ^ under the above conditions in the static mixer formic acid vinegar prepolymer feed into the water amine base shown in Figure 1 ^ ^ ω Η» 早 early screw extrusion In machine 18, then, .,,, earthy poly & substance, tackifier e, J Pinggang added to polyamine

The vinegar prepolymer was further subjected to a single-screw extruder, and the reactive cerium melt was obtained. The δ amount (NCO%) of the free isocyanate group of the reaction prepared by the reaction is preferably! Up to 5 〇 / Example ' is preferably 1.2 to 3%. Examples and comparative examples are given to illustrate the examples. Although in the following, the invention will be implemented with reference to

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS However, the present invention is not limited to any of the embodiment I using fifteen static mixers 17 having a package a reactor 16 and a single screw extruder 8 connected in a static mixer section 4. (The apparatus la shown in the drawing produces a thermoplastic polyamine (4) (hereinafter referred to as "TPU") by the following operation. The static mixer part 4 includes the first to third static mixers na to 17c (horizontal) The three static mixers connected each have a tube length of 〇5m and an inner diameter of 2Omm0 and are preset to 24〇t), and the fourth to fifth static machine 1 7d纟1 7e (the row is connected Two static mixers each having a tube length of 1.0 m and an inner diameter of 20 mm (/» tubular and preset at 2〇〇t:), 315225 39 1338698 six to twelfth static mixer i 7f to Π1 (Seven static mixers connected in a row) each having a tube length of l.〇m and an inner diameter of 38 mm0 and preset at 200 ° C) and the thirteenth to fifteenth static mixers 1 7m to 17〇 (three static mixers connected in series, each having a tube length of 〇5m and an inner diameter of 38mm 0 and preset at 2〇〇. (: 12.4 parts by weight of 4,4,-diphenylmethane diisocyanate (hereinafter referred to as MDI)/brand: Cosmonate PH (produced by Mitsui Takeda Chemical Co., Ltd.) was placed in a polyisocyanate storage tank 6 and adjusted to 40 tons. 195 parts by weight of polyglycol having an average molecular weight of 8,300 (brand: Ekipeg 6,000' Sanyang Chemical Industry Co., Ltd., melting point: 100. (:) and 3 〇ppm of two laurels by weight of the large polyol) Dibutyltin acid (produced by NITIO KASEI Co., Ltd.) (these components are hereinafter referred to as ''polyol solutions'') are placed in the polyol storage tank 7 and adjusted to t. 2.33 parts by weight of l, 4-butyl The diol (hereinafter referred to as "BG", produced by Basf, melting point: 5 (TC) is placed in the chain extender storage tank 8 and adjusted at 4 ° C. These operations are carried out in a nitrogen atmosphere. 2.86kg/h, 45kg/h, and 〇'54kg/h flow rate MDI, polyol solution and BG are fed to the high-speed mixer 9 (SM40, SakuraP丨ant company, preset temperature · · 12〇.〇 After these materials are thoroughly stirred and mixed, The compound is held in the reaction ΐ6 (ι〇) for 1 to 7 minutes' and then fed to the first static mixer 17a in the static mixer part 4. After that, 'will be from the fifteenth static mixer 17〇 The discharged reaction material 315225 40 1338698 is pressed into a single screw extruder (65mm0&15〇, manufactured by GM Engineering Co., Ltd.). After being extruded from the strand mold 19, the chill roll is used. The cooling belt is cooled, and then the reaction material is cut by a granulator (ppL_) 3, ishinaka IRON WORKS 3) to obtain a granular TPU. Example 2 A device as shown in Fig. 1 using sixteen static mixers 17 connected in a row in a static mixer section 4 comprising a single screw extruder 18 but not containing a reactor 16 was used! a Manufacture of τρυ by the following operation. The static mixer part 4 includes first to seventh static mixers 7a to 17g (seven static mixers connected in series, each having a tube length of 〇5m and an inner diameter of a tubular shape and preset to 19 (Γ( :), eighth to ninth static 'Ken 5 machine 1 7 h to 1 7 i (two static mixers connected in series, each having a tube length of 1. 〇m and an inner diameter of 2〇mm 0 And preset to 18〇.匸), tenth to fourteenth static mixers 17j to 17n (five static mixers connected in series, each having a tube length of 1_〇„1 and an inner diameter of 38 mm0 And preset at 170. 〇, and fifteenth to sixteenth static mixers 17〇 to i7p (two static mixers connected in series, each having a tube length of 〇5m and an inner diameter of 38mm0 tubular and pre- Set at 170. 〇. Word, 23 cc of one ring, hexyl sulphuric acid diisocyanate (hereinafter referred to as HMDI 'Sumika Bayer Urethane, Hyun: 5 〇 °c) placed into the oxime isocyanate storage tank 6 And adjusted to 40. It will be 3,048 parts by weight of polyester polyol with 2〇〇 number average molecular weight (brand: HT-12, produced by HOKOKU, melting point: 9 5. 〇, 315225 4] 1338698 50 ppm of stannous octoate (brand: STANDOC, API company) based on the weight of the large polyol' 10 parts by weight per 100 parts by weight of the polyol (2·6·diisopropyl) Phenyl phenyl) carbodiimide (brand: STABILIZER 7000 'RASCHIG company), 0.34 parts by weight of hindered phenol antioxidant (brand: IRGANOX 1 010 'Ciba-Geigy), 0.34 parts by weight of benzoic acid. Raw UV absorber (Brand: SF - 8 3, J 〇h 〇ku C hemica 1), and 〇, 16 parts by weight of hindered amine light stabilizer (brand: lA_52, produced by Asaki Denka K〇gy〇) (these ingredients are later called For example, the polyol solution ") is placed in the polyol storage tank 7 and adjusted to 9 〇t. 400 parts by weight of BG (BASF product, melting point: 5 〇. (:) is placed in the chain extender storage tank 8 And adjusted to 50 °c. These operations were carried out in a nitrogen atmosphere. Then 'HMDI, polyol solution and BG were fed to the flow rate of I 6.8kg / h, 30.5kg / h ' and 4_0kg / h respectively High-speed mixer 9 (SM40, produced by Sakura Plant, preset temperature: 12 (:). After these materials are thoroughly mixed and mixed, the mixture is fed into the first static mixer 7a in the static mixer part 4. After that, 'from the sixteenth static mixer 1 7p The discharged reaction material was pressed into a single screw extruder (in a press-fit part 65 mrn0, i40 ° C, produced by GM Engineering). After being extruded from the strand mold 丨9, the reaction material was cut underwater by an underwater granulator (produced by GaLa) to obtain a pelletized TPU.贯方fe 歹1j 3 Using the sixteen static mixers 17 with a single screw extruder 18 but not including the reactor 164,225 of 4 Here, < mourning 1 a to manufacture TPIJ by the following operation. 17j The core assembly part 4 includes a first to seventh static mixer 1 7 a to seven static mixers connected in series, each having a tubular length of 〇5 m and an inner diameter of λ λ mm 0 and Preset to j 8〇〇c 8th to 9th static 1 7 to 71 (two static mixers connected in series, each with a tube. Good and 〇Γη with an inner diameter of 20mm 0 tubular and preset In ι7〇ι ), tenth to fourteenth static mixers 17j to 17n (static mixing of the horizontal connection), /, a length of 1. 〇m and an inner diameter of 38 mm 0 is preset to 1 8 Π °P \ , ), and fifteenth to sixteenth static mixers 1 7〇 to 17p (two static mixers connected in series, each with a tube length of 0.5m and an inner diameter of 38mm Tubular and preset at 180. (:). 1,676 parts by weight of HMDi (Sumika Bayer Urethane: 50 ° C) was placed in the polyisocyanate storage tank 6 and adjusted to 40 t. 2,408 parts by weight Polycarbonate diol having a number of 2,000 average molecular weights (Brand: UH-CARB200, produced by Ube Industries, melting point: u〇C) '3 〇ppm based on the weight of the large polyol Dibutyltin laurate (brand: NEOSTANN U-100, produced by NITTO KASEI), 0.4 parts by weight of bis(2,6-diisopropylphenyl)carbodiimide per part by weight of polyol (brand: LUPRAGEN-9119, produced by BASF, 0.1 parts by weight of hindered phenol antioxidant (brand: IRGANOX 1010, produced by Ciba-Geigy) '0.34 parts by weight of benzotriazole ultraviolet absorber (brand: "-83'" 〇11 〇1<11〇^171 丨 丨 )), and 0.16 parts by weight of hindered amine chloramphenicol 43 315225 1338698 疋 ( (brand: LA-52, Asaki Denka Gongzhang Gongshan σ,, a division produced) Hereinafter, the polyol solution ") is placed in the polyol storage tank 7 and adjusted to 110 ° C. 452 parts by weight of BG (BASF product, melting point: 5 〇. 〇 placed in the bond growth agent storage tank) 8 and adjusted to 5 (TC. These operations were carried out in a nitrogen atmosphere and then fed HMDI, polyol solution and BG to high speed at a flow rate of 6.8 kg/h, 24. Ikg/h and 4.55 kg/h, respectively. Mixer 9 (SM40, produced by Sakura Plant, preset temperature: 12〇〇c). In these After the mixture is completely stirred and mixed, the mixture is fed to the first static mixer 17a in the static mixer section 4. Thereafter, the reaction material discharged from the sixteenth static mixer 1 7 p is pressed into the single sheet. Screw extruder (in press-fit parts, produced by gm Engineering). The pellet was cut by a pelletizer (PPL-130' ISHINAKAIRONWORKS Co. Example 4 A sixteen static mixer 1 7 having a row of static mixer components 4 comprising a reaction crucible 16a interposed between two high speed mixers 9a, 9b and a single screw extruder 18 was used. The device 1b shown in Fig. 2 is manufactured by the following operation. The static mixer part 4 comprises first to seventh static mixers 17a to 17g (seven static mixers connected in series, each having a tubular length of 〇5 mm and an inner diameter of 20 mm 0 and preset At 24°°c), the eighth to the ninth static 44 315225 h to 17l (two static mixers connected in k columns, each having a tube, such as a tube having an inner diameter of 2G_4 and preset to 2G (TC), Tenth to fourteenth static mixers 17...7n (five static mixers connected in series) each having an official length of i 0m and an inner diameter of tubular shape and preset to (10), and fifteenth to tenth Six static mixers 170 to 17p (two static mixers connected in series) each having a tube length of 05 m and an inner diameter of 38 mm0 and preset to 15 〇. 字. Word 〇〇 3 heavy injury MDI ( Brand: c〇smonate PH, Mitsui Takeshi, Division A. σ) Placed in polyisocyanate storage tank & and adjusted to Τ: 3,833 parts by weight of polyester polyol with 2,000 number average molecular weight (brand :U-20(H 'Mitsui Takeda Chemical Co., Ltd., melting point: 12〇C) and 3 parts by weight of each of the large polyols (2,6 diiso) Carbonyl diimide (brand: STABILIZER 7000, manufactured by RASCHIG) (these ingredients are referred to hereinafter, polyol solution,), placed in the polyol storage tank 7 and adjusted to 120 ° C. 17_6 parts by weight of BG (produced by BASF, melting point: 50. The crucible is placed in the chain extender storage tank 8 and adjusted to 50 ° C. These operations are carried out in a nitrogen atmosphere. Then, respectively, 16.8 kg / h and 38.3 kg /h flow rate The MDI and polyol solution are fed to the upper high-speed mixer 9a (SM40, Sakura P1 ant's 'preset temperature · · 1 20 ° C). After these materials are completely stirred and mixed, The mixture was kept in the reactor 16a (10 liters) for ten minutes to synthesize the prepolymer (mixture). 45 315225 1338698 The knife was obtained at a flow rate of S5.ikg/h and i.76 kg/h. The prepolymer and BG are fed to the lower high speed mixer 9b (SM40, Sakura P "A s. Q, preset temperature: 1 2 01:). After these materials are completely stirred and mixed, they are fed. To the first static mixer 17a in the static mixer part 4. After 'will be from the sixteenth The reaction timber mixer Shu 7p state of being discharged

The material was pressed into an early screw extruder (in a press-fit part 65mm 0, 140X: produced by GM Industrial and Trading Company). After being extruded from the strand mold 19, the reaction material was cut underwater by an underwater pelletizer (produced by GaLa) to obtain a pelletized TPU. Example 5 Using a T_shaped connecting tube 2 1 having a static mixer connected between first to fourth static mixers 17a to 17d and fifth to eighth static mixers 17e to 17h The apparatus 1 c shown in Fig. 3 of the twenty-four static mixers 17 of the static mixer unit 4 of the single-screw extruder 1 and the single-screw extruder 18 is manufactured without the following operation. . The static mixer part 4 includes first to fourth static mixers 17a to I7d (four static mixers connected in a row, each having a tube length of 〇5 m and an inner diameter of 38 mm0 and preset to 200 to 260. (:) 'The fifth to eighth static blame mixers 1 7e to 1 7h (four static mixers connected in series) each have a tube length of 〇.5m and an inner diameter of i3mm0 and are preset 280 °C), ninth to twelfth static mixers 丨7i to I 7丨 (four static mixers connected in series, each having a tube length of 0.5m and an inner diameter of 2〇mm0 tubular and preset From 250 to 28 〇r), thirteenth to sixteenth static mixer 46 315225 1338698 1 7m to 17P (four static mixers connected in series, each having a tube length of 〇.5m and an inner diameter of 2 〇mm 0 is tubular and preset at 22〇 to 23(rc), and the seventeenth to twentyth static mixers 丨7q to 丨7t (four static mixers connected in series) each have a tube length of 0.5m and The inner diameter is 2Omm0 and is preset to 210 to 220. 〇, and the 21st to 24th static mixers i7u to 1 7x (four static mixers connected in series, each having a tube The degree is 〇5m and the inner diameter is 2〇mm and the tube is preset to 21〇〇c). 3 26 parts by weight of MDI (brand: Cosmonate PH, manufactured by Mitsui Takeda Chemical Co., Ltd.) is placed in the polyisocyanate storage tank 6 And adjusted to 45 V. 510 parts by weight of polytetramethylene ether glycol (brand: PTG-1000, produced by Hodogaya Chemical Co., Ltd.) having a number average molecular weight of !, and 00 parts by weight of a large polyol 0.965 parts by weight of a hindered phenol antioxidant (branded by IRGANOX 1〇1〇' ciba Specialty Chemicals) (these ingredients are hereinafter referred to as, polyol solution,), placed in a polyol storage tank 7 and adjusted to 60 °C. 158 parts by weight of bis-hydroxypropoxy benzene (brand: BHEB, produced by SUN TECHN〇CHEMicals, referred to as ''BHEB') was placed in the bond growth agent storage tank 8 and adjusted To ι25χ: These operations are carried out in a nitrogen atmosphere. Then 'MDI and scorpion alcohol are fed to the high-speed mixer at a flow rate of 16.32 kg/h and 25.76 kg/h, respectively. Lu Wei (4) PUnt Produced, preset temperature] machine). In these materials completely After mixing: 3⁄4, the mixture is fed to a static mixer 1 7a in the static mixer part 4 to synthesize isocyanate in the first to fourth static mixers 17a to 17d. Prepolymer of the base terminal When the concentration (NCO%) of the free isocyanate group of the prepolymer thus obtained was measured and calculated, the reaction rate of the isocyanate group was 99%. The BHEB is then fed from the chain extender storage tank 8 to the first to fourth static mixers 1 7a to 17d and the fifth to the eighth set in the static mixer part 4 at a flow rate of 7.92 kg/h. The butt-shaped connecting tube 2 1 between the static mixtures of the static mixers I 7e to 17h. The reaction material discharged from the strand mold 19 from the twenty-fourth static mixer 1 7X was cut by a granulator 20 and then dried at 100 Torr for 24 hours to obtain a granular τρυ. Example 6 using a reactor comprising a reaction vessel 16 but not including a single screw extruder 1 8 but comprising a first to fourth static mixers 17a to 17d and a fifth to eighth static mixer 1 7e The device lc shown in Fig. 3 of the twenty-four static mixers 17 of the static mixer component 4 in the static mixer section of the 7h static mixer is manufactured by the following operation. The static mixer part 4 comprises four static mixers of the first to fourth static mixers 1 7 a to the row, each having a tube length of 〇5〇1 and an inner diameter of 38 mm φ and preset at 200 To 250. (:), 5th to 8th static mixers 1 7e to 丨7h (four static mixtures connected in a row, each having a tube length of 0.5 m and an inner diameter of 3 mm must be tubular and preset at 250 C) 'Ninth to Twelfth Static Mixers 1 7i to I 7】 (four months of cross-linking 'mixer' each having a tube length of 0.5 m and an inner diameter of 20 mm </> tube 48 315225 1338698 shape and preset at 230 to 250 °C), the twelfth 黾 丄丄 丄丄 主 a brother 16 static mixer 1 7m to 1 7p (four static mixers connected, a length of 0.5m and an inner diameter of 20mm 0 tubular and preset at 21〇 to 22〇), a seventeenth to twentyth static mixer 17q to 17t (four static mixers connected to each other, each having The tube has a length of 〇5m and an inner diameter of 2〇mm0 and is preset to 2〇〇 to 210. 〇, and 21st to 24th static mixing to 17x (four static mixing of the horizontal connection) The machines 'each have a tubular length of 〇5m and an inner diameter of 2〇mm 0 and are preset to i9(rc). 2,5-, 2,6-diisocyanurylmethyl-bicyclo[m] -heptane (Brand: C〇Sm〇nate NBDI, Mitsui Takeda Chemical Co., Ltd. produced a mixture of its isomers called NBDD, which was placed in a polyisocyanate storage tank 6 and adjusted to have 484 parts by weight of polycaprolactone diol (the number average molecular weight). :P]acce]21〇, produced by DAICEL Chemical Industry Co., Ltd., based on the weight of the large polyol, 2 0nr>m --B 4 soil μ T 2Uppm, one of di-n-butyl laurate (Toky«

Kasei Kogyo Co., Ltd., and liquid light stabilizers per 100 parts by weight of polyol (brand _· Tinuvin b75, Ciba Speciahy

Produced by Chemica^i) (these ingredients are hereinafter referred to as "polyol solutions,") placed in the polyol storage tank 7 and adjusted to 9 〇. 185 parts by weight of the egg (brand: bheb, sun TECHNOCHEMICALS) The product was placed in the chain extender storage tank 8 and adjusted to 1251. These operations were carried out in an i atmosphere. Then, the NBDI and the 7C alcohol solution were fed to the flow rate of 16.28 kg/h and 24.49 kg/h, respectively. High speed mixer 9 (sM4(), 49 315225 1338698

Plant produced 'preset temperature: 120. (:)in. After the raw materials are completely stirred and mixed, the mixture is fed into the first static mixer 17a in the static mixer part 4 to synthesize the isocyanate group terminal in the first to fourth static mixers i7a to 1 Polymer. Then continue to feed the BHEB from the chain extender storage tank 8 to the first to fourth static mixers 173 to 17d and the fifth to eighth statics disposed in the static mixer part 4 at a flow rate of 9.23 kg/h. In the D-shaped connecting tube 2 between the static mixers of the mixers i7e to 17h. The reaction material discharged from the wire strand mold 丨9 from the twenty-fourth static mixer 17 is then cut by the granulator 20 and then placed in a crucible (: drying for 24 hours to produce a granular τ Ρυ) Example 7 uses a static mixer comprising a single screw extruder 1 8 but not containing a reaction dad 6, but comprising a connection between the first to twelfth static mixers 17 & to 17 and the twelfth to twentieth static mixing Machine] between the static mixers of 7m to 7t, the injection manifold of the static mixer 2, the static static mixer part 4, the twenty static connections, the device id shown in Fig. 4 of the machine 17 is operated as follows The dynamometer mixer component 4 includes first to seventh static mixers 17a to 17g (seven static mixers connected in series) each having a tubular length of 〇5ηι and an inner diameter of 20 mm 0 and Preset at 19〇〇c), 8th to 9th static mixers 1 7h to 1 7i (two static mixers connected in series, each having a tube length of 1.0m and an inner diameter of 20mm 0) Set at 18〇. (:), tenth to twelfth static mixers I 7 i to 1 71 (three static mixes of horizontal connections) 'Each tube having a tube length of 1 〇m and an inner diameter of 30 and pre-50 3) 5225 1338698 6 again at 170 C), thirteenth to fourteenth static mixers 17m to 17n (two of the rows a static blame mixer, each having a tube length of 20 mm and having a diameter of 20 mm and preset at 7 〇. 〇), and a fifteenth to twentieth static machine 1 7 〇 to 17 ft (row) The six static mixers connected each have a tube length of 0.5 m and an inner diameter of 38 mm and are preset to n (rc). Make a 30 mm </> single screw extruder 23 (gm engineering The company produces 16 〇 to 1 ° C) and is connected to the injection tee 22. The 1,623 parts by weight of HMDI (Sumika Bayer Urethane 'melting point: 50 ° C) is placed in the polyisocyanate storage tank 6 and adjusted to 4〇〇C. 3.048 parts by weight of a polyester polyol having a 200-number average molecular weight (brand: HT-12 'HOKOKU Co., melting point: 95 ° C), 25 ppm of octanoic acid by weight of the large polyol Tin (Brand: STANOCT 'API company) 'Every 1 〇〇 by weight of large polyol 〗 〇 Heavy i (2,6-diisopropylphenyl) carbodiimide Brand: STABILIZER 7000, produced by RASCHIG), 〇, 34 parts by weight of hindered phenol antioxidant (brand: IRGANOX 1〇1〇, produced by Ciba_Geigy), 0.3 4 parts by weight of benzotriene. Sitting UV absorber (brand: jF_ 83, produced by Johoku Chemical), and 0. 16 parts by weight of hindered amine light stabilizer (brand: LA-52, produced by Asaki Denka Kogyo Co., Ltd.) (these ingredients are referred to as "polyol solutions" hereinafter). The alcohol storage tank 7 was adjusted to 90 〇C 400 400 parts by weight of BG (BASF product, · melting point: 5 〇. 〇) Insert the bond in the growth agent storage tank 8 and adjust to 50 °C. These operations were carried out in a nitrogen atmosphere 5) 315225 1338698. Then, 'the HMDI 'polyol solution and BG were fed to the high-speed picker 9 at a flow rate of 11.76 kg/h, 2 1.35 kg/h, and 2_8 kg/h, respectively. (SM40, produced by Sakura Plant, preset temperature: 12〇.〇). After the materials were thoroughly stirred and mixed, the mixture was fed into the first static mixer 17a in the static mixer section 4. Subsequently, the masterbatch pellets containing 40% by weight of a deodorant (brand: KESUMON, TOAGOSEI Co., Ltd.) (the composition of the TPU obtained in Example 7) were continuously placed at a flow rate of 6 kg/h. The screw extruder 23 is then supplied to the first to twelfth static mixers 17a to 1 71 and the thirteenth to twentieth static mixers 1 7m to 1 7t provided in the static mixer part 4 Injection tee between static mixers 22 〇

After that, the reaction cake discharged from the twentieth static mixer 丨7t was pressed into a single-screw extruder (in a press-fit part, M (rc, gM engineering company)' in the strand mold 1 9 After extrusion, the reaction material was cut underwater by an underwater granulator (produced by GaLa) to obtain a granular TPU containing the added deodorant. Comparative Example 1 The same raw materials as in Example 1 were used ( However, 40 ppm of the catalyst was added by weight of the large polyol, and the same high-speed mixer (SM40, Sakura Plant Co., Ltd., manufactured by Sakura Plant Co., Ltd., preset temperature: 12 (Γ:) was applied. After that, the mixture was mixed. Feed to a 4 6 mm 0 twin-screw press (PCM46'L/D = 41.5'200 to 25 (TC, 1KEGAI), 52 315225 1338698 for mixing and reaction. Then 'by gear pump The obtained reaction material was pressed into a static mixer (tube length of 〇5 m, inner diameter of 38 mm0 and preset temperature of 200 ° C). Then, the reaction materials were tried in the same manner as in Example 1. Granulation, but it cannot be borrowed because its melt viscosity at the top of the mold is not strong enough It was cut and granulated by a granulator. Comparative Example 2 The same raw materials as in the above examples were used (but 1,000 ppm of the catalyst was added by weight of the large polyol) and the same operation as in Comparative Example 1 was also carried out to obtain Granular TPU. Comparative Example 3 The same materials as in Example 2 were used and mixed in a reaction vessel to react their components with each other. In this reaction, the HMDI reaction was so slow that after about one hour passed' The reaction material in the reaction vessel is still liquid. The reaction costs for five hours or more to completely cure the reaction material. Then 'react the reaction material at 1 〇〇. (: Annealing and then slicing by a cutter and a powder machine The sheet was prepared by batch method to obtain TPU. Comparative Example 4 Using 1.599 parts by weight of MDI ' 2.408 parts by weight of the additive (per 100 parts by weight of the polyol oxime, 34 parts by weight of the hindered phenol antioxidant) A polycarbonate diol having a number average molecular weight of 2,000 (brand UH-CARB2000, available from Ube), and 452 parts by weight of BG are mixed to react their components with each other. 20 (3) Annealing for 16 hours and then slicing into tablets by a cutter and a powder machine, 53 315225 I338698 to obtain tpu by a batch method. The same material as in Example 4 was used. However, 20 Ppm of octanoic acid octanoate is added as a large polyol, and α 稽田兴Comparative Example I is the same as #罟* A device for producing granules of τρυ η from the same conditions and fJ π Τηττ 仕 'Add any catalyst Under: and illusion: as in the case of Example 4, but the viscosity cannot be thick enough to the full size. In contrast, the 2 viscosity of the TPU obtained in Example 4 was a or greater when it was just produced. Furthermore, due to the residual = isocyanate reaction over time, the TPU (four) (four) degree increased to 2,000 Pa or more after three days. iLl ό ό 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 大 ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό ό in. In the apparatus 1a, twenty-four static mixers 17 are connected in the static mixer section 4. The raw materials prepared in the same manner as in the embodiment 5 were forced through a static mixer to produce a TPU by the following operation. The static mixer part 4 includes first to fourth static mixers 7a to 17d (four static mixers connected in a row, each having a tube length of 〇5 mm and an inner diameter of 38 mm 0 and preset at 200) Up to 2 60 ° C), 5th to 8th static mixers 1 7e to 17h (four static mixers connected in series, each having a tube length of 〇.5m and an inner diameter of 13mm0) and preset 280 °C) 'Ninth to Twelfth Static Mixer】7i to 1 71 (four static mixers connected in a row, each having a tube length of 〇.5m and an inner diameter of 20mm 0) 54 315225 1338698 It is preset to 250 to 280. 〇, the thirteenth to sixteenth static mixers 17m to l7p (four static mixers connected in each row have a tube length of 〇_5m and an internal 杈 of 2〇mm. Tubular and preset to 23 )), seventeenth to tenth static mixers 1 7q to 17t (four static mixers connected in series, each with a tube length of 〇5m and an internal diameter of 2 〇 0 tubular and pre-a between 210 and 220.)' and the twenty-first to twenty-fourth static mixer i7u to 17x (four static mixers connected in series, each with a tube length The tube is 0.5 m and has an inner diameter of 2Omm0 and is preset to 21 〇. 刀 The knife is forced to pass the polyol solution at a flow rate of 25_76 kg/h, 16.32 kg/h and 7.92 kg/h,] V1DI and BHEB. From the strand stock fixture] 9 extruded from the 24th static mixer 1 7x discharged reaction material and then cut by the granulator 2 然后 then at 1 〇〇χ: drying for 24 hours 'to obtain granules Τρτυ. Comparative Example 7 Directly introduces the big oxime alcohol, the polyisocyanate, and the bond growth agent without the buckle. The yak 3 reaction dad 1 6 and the single screw extruder 1 8 are shown in the figure. In the static mixer of the apparatus 1 a. Twenty-four static mixers 17 were connected in the static mixer section 4 in the apparatus 1 & The raw materials prepared in the same manner as in Example 6 were forced ( However, 600 ppm of di-n-butyltin dilaurate was added by weight of the large polyol. The TPU was produced by a static mixer's operation as follows. The static mixer component 4 includes the first to fourth static mixers 1 7a to 1 7 d (four static mixers connected in series, each having a tube length of 〇. 5 m and an inner diameter of j8 mm 0 Preset at 200 to 250X), fifth to 55th 315225 1338698 Eight static mixers 1 7 e to 1 7 h (four static mixers for π, * only connected, each with a tube length of 〇.5m And the inner main μ, the horse 13mm must be tubular and preset at 25 0 °C) 'The ninth to twelfth static mixing machine 1 71 to 1 71 (the four U ports connected to the page page) The length is 〇5m and the inner diameter is 2〇_ must-tubular and preset to 230 to 25〇t) 'thirteenth to sixteenth static mixers 17m to 17P: four static mixers connected in series, each It has a tubular shape with a tube length of 0.5 m and an inner diameter of 2 〇 mm 0 and is preset to 21 〇 to 22 〇. 〇, the seventeenth to twentieth static mixers l7q to i7t (four static mixers connected in a row) each having a tube length of 〇5m and an inner diameter of 2〇-the tubular and pre-square, 200 to 210.)' and the twenty-first to twenty-fourth static mixers 17u to 17x (four static mixers connected in series, each having a tube length of 0.5m and an inner diameter of 2〇mm0 tubular and preset At 19〇〇c). The polyol solutions 'NBDI and BHEB were forced to pass at flow rates of 24.49 kg/h, 16.28 kg/h and 7.92 kg/h, respectively. From the strand mold] 9 extruded from the 24th static mixer] 7 χ discharged reaction material and then cut by the granulator 2 然后 and then!艺 0 art drying for 24 hours' to obtain a granular diced PU. Evaluation Test Example 1 The melt viscosity of the TPU obtained in Example 1 was measured by using a flow tester (Model: CFT-5 00D'Shimadzu Co., Ltd., measurement conditions: see item (3) below) after one day of manufacture. The melt viscosity of the TPU obtained in Comparative Example 2. As a result, both the melt viscosity of the TPU of Example 1 and the melt viscosity of the TPU of Comparative Example 2 were both 10,000 Pa or more. 56 315225 1338698 Afterwards, these TPUs were kept at room temperature for two months in a dark room. When the measurement was carried out two months after the first measurement, it was found that in the TPU of the example, the residual isocyanate reaction continued, and the melt viscosity of the TPU of Example i was increased to not less than 15, 〇〇〇Pa, and the melt viscosity of the TPU of Comparative Example 2 was lowered to not more than 7, 〇〇〇Pa. From the continuous measurement, it was found that the melt viscosity of the TPU of Comparative Example 2 was further lowered. It is presumed that the decrease in the viscous viscosity of the TPU of Comparative Example 2 is due to the sputum due to the catalyst. break down. Test Example 2 The TPU (HMDI-type) obtained in Example 3 and the TPU (MDI-type) obtained in Comparative Example 4 were molded by an injection molding machine (75MSII, manufactured by Mitsubishi Heavy Industries, Inc., preset at 21 CTC). It is 3mm thick, i〇〇mm wide, and 1 〇〇mm long. The obtained sheet was allowed to stand outside for seven days and exposed to sunlight for light resistance test. After one week of injection molding, it was found from the comparison of the two sheets that the sheet formed by the TPU of Example 3 did not yellowish and the sheet formed by the TPU of Comparative Example 4 was noticeably yellowed. In the case of Test Example 3, the TPU obtained in Example 1 and the TPU obtained in Comparative Example 5 were formed into a long sheet of 1 mm thick and 8 mm wide by using Brabender (produced by Brabender OHG). Then, the measurement of the presence of the fisheye (gelatinized matter) in the obtained sheet was carried out under the same conditions as the following item (4). It was found by measurement that no fisheye was observed from the initial stage of the operation, that is, in the sheet formed of the TPU of Comparative Example 5, and was not observed in the sheet formed of the TPU of Example 4 after 24 hours of operation. Fisheye. 315225 57 丄338698

The τρυ obtained in Examples 5 and 6 and the U obtained in the comparative example were formed into a film material or molded by an injection molding method to prepare a test piece = after 'for those tests>; the following item (1) was carried out (5) The nature of the shape = test. Make the test piece before testing! 〇〇β (: heat treatment Μ hours. The results are shown in Table 1. (1) Hardness The Shore hardness of each test piece was measured according to JIS K-7311 at 50% relative humidity at 23. Type hardness tester (2) Tensile strength (unit: MPa), elongation after fracture (unit: %), tear resistance (unit: kN/m) ' Taber wear (unit: mg), compression set (Unit: %) The tensile strength, elongation after fracture, tear resistance, and butyl enthalpy of each test piece were measured at 50% relative humidity at 23 ° C according to JIS K-73 1 1 . The compression set of each test piece was measured at 70t for 20 hours according to JIS K-625 1. (3) Initial fluidization temperature (unit: 乞) and melting temperature range (unit: 艽) 2g of the example 5 6 and the τρu particles (or flakes) obtained in Comparative Examples 6 and 7 were packaged in a flow tester (model: CFT-500D, Shimadzu) and then loaded at a temperature rise rate of 25 t:/min and 196 N. Under the conditions, the initial fluidization temperature was measured by using a mouth of 1 mm (diameter) χ 1 〇 mm (length). 2 g of measurement was measured. The difference between the temperature at which melting (or sheet) begins to melt and the temperature at which the molten material completely flows out of the nozzle is taken as the melting temperature range. 58 315225 1338698 (4) Fisheye (unit: number per 300 cm2) In Examples 5, 6 and comparison After the TPU obtained in Examples 6 and 7 was formed into a film of 100 #m thick, the film was cut into pieces of 200 mm in length and 150 mm in width. The fine particles having a diameter of not less than 80 μm were observed by a polarizing microscope. The number of the fine particles was measured. (5) Yellowing (ΔYI) The injection molded sheet formed of the TPU obtained in Comparative Examples 6 and 7 was used and measured in accordance with JIS K-73 50-2A. At a blackboard temperature of 63 ° C, a relative humidity of 50%, and an illumination intensity of 〇 35 w/m 2 'by using a helium irradiation tester (Super Xenon Weather Meter SX 75 . Suga Test Instruments) The test piece was subjected to a yellowing test for 100 hours. After the irradiation, the test piece was taken out and the yellowing was evaluated by the increase rate of the yellowness index. (Table 1) Example / Comparative Example Example 5 Comparative Example 6 Example 6 _ , Comparative Example 7 Hardness (Shore Hard /A type) 96 96 8 7 86 Tensile strength (MPa) 51.2 44.5 41.1 3872 Elongation after fracture (%) 565 615 623 655 Tear resistance (kN/m) 157.1 142.1 121.1 Π3:4~ Taber wear ( Mg) 19 23 21 21 Compressive deformation characteristics. (%) 25.2 3 1.3 34.3 38.5 Flow initial temperature (°C) 195 212 175 181 Melting temperature range CC ) 26 11 35 28 Fish eyes (number of sheets per 300 cm 2 ) 21 387 Not evaluated 15 1 245 Yellowing (Δ YI) Not evaluated ---- 7.4 ---- ' •-------- 16.7 59 315225 1338698 Although an illustrative example of the invention is provided in the above description It is for illustrative purposes only and is not intended to be limiting. Modifications and variations of the present invention will be apparent to those skilled in the art. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram showing the production of a thermoplastic polyurethane mold using the method of the present invention; and Fig. 2 is a view showing the production of a thermoplastic polyamine based thermoplastic resin by the method of the present invention. A configuration example of a second example of a device for producing a thermoplastic polyurethane having a first example of a device of a phthalate ester ester; and FIG. 3 is a view showing the production of a thermoplastic polyurethane using the present invention A structural example of a third example of a device for producing a thermoplastic polyurethane using the method of the present invention; and FIG. 4 is a view showing the production of a thermoplastic polyurethane using the method for producing a thermoplastic polyurethane according to the present invention. A structural diagram of a fourth example of a brewed device. 1 a, 1 b, 1 c 2 Raw material tank parts 4 Static mixer parts Polyisocyanate storage tank 8 Chain extender storage tank 9 , 9a , 9b Installation Mixing parts Granulation parts Polyol storage tank High speed mixer 60 315225 1338698

1 Oa Stirring vessel 10b Stirring paddle 11 Polyisocyanate supply line 12a, 12b, 12c Gear fruit 13a, 13b, 13c Flow meter 14 Polyol supply line 1 5 Chain extender supply line 16, 16a, 16b Reactor 17a First static mixing Machine 17b second static mixer 17n η static mixer 18 single screw extruder 19 strand mold 20 cutter/cutting machine 21 Τ-shaped connecting tube 22 injection tee 23 single screw extruder 315225

Claims (1)

Patent Application No. 92131461 (May 19, 1999) Axis Wang Ben_ Scope of Application: A method for producing a thermoplastic polyurethane, which comprises pre-mixing at least polyisocyanuric acid and a large polyol The reaction material of the mixture and the chain extender reacts while passing through a static mixer. For example, the method of producing thermoplastic polyurethane urethane according to claim 1 is a method in which at least a polyisoacid vinegar and a large polyhydric alcohol are mixed by a high speed mixer. A method of producing a thermoplastic polyurethane according to the first aspect of the invention, wherein the reaction material is prepared by simultaneously mixing a polyisocyanate, a large polyol and a chain extender. The method for producing a thermoplastic polyurethane according to claim 1, wherein the reaction material is prepared by first mixing polyisocyanate with a large polyol and then blending a chain extender in the obtained mixture. The method for producing a thermoplastic polyurethane vinegar according to claim 4 of the patent application is to mix the obtained mixture with a chain extender after mixing the octadecanoic acid with the large polyol. t Manufacture of thermoplastic polyurethane urethane according to item 4 of the patent application: after mixing the oxime isocyanate with the large polyol, the obtained mixture is reacted and then combined by the (4) machine The 4&E type is connected to the supply line of the static mixer to blend the chain extender in the mixture. = Please refer to paragraph 1 of the patent scope for the manufacture of thermoplastic polyamine-based vinegar vinegar's part of the contact between the medium and the reaction material by the substance 315225 revision 62 1338698 Patent Application No. 92131461 (May 19, 1999)曰) Formed from materials of non-metallic materials. 8. The method of making a thermoplastic polyurethane according to claim 1 wherein the static mixer comprises a plurality of static mixers each capable of independently performing a series of connections within the temperature control of the static mixer. 63 315225 revision