KR20040044168A - Thermoplastic polyurethane, and method and apparatus for producing the same - Google Patents

Abstract

PURPOSE: A thermoplastic polyurethane, its preparation method and its preparation apparatus are provided, to reduce the using amount of a catalyst, to inhibit the sticky adhesion of gelled product and to prevent the deterioration of physical properties or storage stability of a thermoplastic polyurethane. CONSTITUTION: The thermoplastic polyurethane is prepared by passing a reaction source comprising a pre-mix of at least polyisocyanate and macropolyol and a chain extender through a static mixer(17) to react them. Preferably polyisocyanate and macropolyol are pre-mixed and a chain extender is added to the obtained pre-mix to prepare the reaction source; or polyisocyanate, macropolyol and a chain extender are mixed simultaneously to prepare the reaction source. Preferably the static mixer for mixing the mixture comprises a plurality of static mixers connected in serial whose internal temperature can be controlled independently.

Description

Thermoplastic polyurethane, its manufacturing method, and manufacturing apparatus {THERMOPLASTIC POLYURETHANE, AND METHOD AND APPARATUS FOR PRODUCING THE SAME}

The present invention relates to a thermoplastic polyurethane, a method for producing the same, and a device for producing the same. Specifically, the present invention provides a method for producing a thermoplastic polyurethane for producing a thermoplastic polyurethane by a reaction extrusion molding method, an apparatus for producing a thermoplastic polyurethane for carrying out the method for producing the thermoplastic polyurethane, and a production of the thermoplastic polyurethane. It relates to a thermoplastic polyurethane obtained by the method.

Background Art Conventionally, various methods for producing a thermoplastic polyurethane continuously by the reaction extrusion molding method have been proposed.

For example, JP-A-5-214062, JP-A-6-192368, etc. mix polyisocyanate, macropolyol, and a chain extender, and continuously manufacture a thermoplastic polyurethane using a twin screw extruder. A method is proposed.

For example, in JP-A-5-271370 and JP-A-10-81725, first, after mixing polyisocyanate and macropolyol, the prepolymerization is promoted by passing through a static mixer, and then, And a method of blending a chain extender, and then continuously producing a thermoplastic polyurethane using a twin screw extruder.

For example, Japanese Patent Application Laid-open No. Hei 8-337630 or Japanese Patent Application Laid-Open No. 2000-344855 connect two static mixers to mix polyisocyanate, macropolyol and chain extender with a first static mixer, and a second static mixer. A method of continuously producing a thermoplastic polyurethane has been proposed by reacting the mixture with a mixer.

However, in the method described in JP-A-5-271370 or JP-A-10-81725, or in JP-A-5-271370 and JP-A-10-81725, both polyisocyanate and macro After blending the chain extender to the polyol, the reaction is carried out using a twin screw extruder, and the reaction and mixing proceed simultaneously and are pressed by mechanical shearing of the extruder screw, or gelled by retention in the groove of the screw. There is a problem that child) is easy to occur.

In addition, since these methods require a large amount of catalyst for promoting the reaction, when extrusion or injection molding the produced polyurethane, due to the catalyst contained in such a large amount, deterioration of physical properties such as decomposition deterioration is caused, and Deterioration with time is inevitable also in the obtained molded article.

On the other hand, in the method described in JP-A-8-337630 or JP-A-2000-344855, it is possible to press the gel by mechanical shearing of the extruder screw or to generate gelation due to retention in the groove of the screw. On the other hand, since polyisocyanate, macropolyol and chain extender are directly introduced into the static mixer, the stirring is insufficient to cause gelation. Particularly, a high melting point macropolyol or a high melting point chain extender is used. When used, there is a problem that a reactant with polyisocyanate is precipitated and gelation is more likely to occur.

Moreover, also in this method, a large amount of catalyst for accelerating the reaction is required, and as described above, physical properties such as degradation degradation due to the catalyst contained in such a large amount, and deterioration with time of the obtained molded article are inevitable. .

The present invention has been made in view of the above problems, and an object thereof can be prepared by reducing the amount of catalyst using a macropolyol having a high melting point, a chain extender having a high melting point, and a polyisocyanate having a slow reaction. Thermoplastic polyurethane for carrying out the manufacturing method of the thermoplastic polyurethane which can produce the thermoplastic polyurethane which is hardly pressed, and which has little physical property fall and deterioration with time, and low hardness thermoplastic polyurethane, and the manufacturing method of the thermoplastic polyurethane It is providing the thermoplastic polyurethane obtained by the manufacturing apparatus of a urethane, and the manufacturing method of this thermoplastic polyurethane.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram which shows the 1st specific example of the manufacturing apparatus of the thermoplastic polyurethane to which the manufacturing method of the thermoplastic polyurethane of this invention is applied.

It is a schematic block diagram which shows the 2nd specific example of the manufacturing apparatus of the thermoplastic polyurethane to which the manufacturing method of the thermoplastic polyurethane of this invention is applied.

It is a schematic block diagram which shows the 3rd specific example of the manufacturing apparatus of the thermoplastic polyurethane to which the manufacturing method of the thermoplastic polyurethane of this invention is applied.

It is a schematic block diagram which shows the 4th specific example of the manufacturing apparatus of the thermoplastic polyurethane to which the manufacturing method of the thermoplastic polyurethane of this invention is applied.

<Description of the symbols for the main parts of the drawings>

1a, 1b, 1c and 1d: manufacturing apparatus

4: static mixer

9 (9a, 9b): high speed stirrer

15: chain extender supply line

17: static mixer

In order to achieve the above object, the method for producing a thermoplastic polyurethane of the present invention is characterized by reacting a reaction raw material including a mixture of at least polyisocyanate and macropolyol previously mixed with a chain extender while passing through a static mixer.

According to this method, since polyisocyanate and macropolyol are introduce | transduced into the static mixer in the state mixed previously, it can make it react uniformly by stirring in a static mixer. Therefore, generation | occurrence | production of gelling can be prevented effectively, and a thermoplastic polyurethane can be manufactured continuously using a high melting | fusing macropolyol, a high melting point chain extender, and a slow reaction polyisocyanate. In addition, since the twin screw extruder is not used, the mechanical shearing of the screw does not cause pressing or gelling due to the retention of the screw in the groove of the twin screw extruder. Can be. As a result, a thermoplastic polyurethane with little physical property degradation and deterioration with time can be manufactured.

Moreover, in the manufacturing method of the thermoplastic polyurethane of this invention, it is preferable to mix a polyisocyanate and macropolyol at least by a high speed stirrer.

By mixing at least the polyisocyanate and the macropolyol by a high speed stirrer, the reaction can be made more uniformly in the static mixer, and the occurrence of gelation can be prevented more reliably.

In the method for producing a thermoplastic polyurethane of the present invention, the reaction raw material may be prepared by simultaneously mixing polyisocyanate, macropolyol and chain extender, or, first, polyisocyanate and macropolyol are mixed and then obtained The reaction raw material may be prepared by blending a chain extender with the mixture.

In the latter case, after the polyisocyanate and the macropolyol are mixed, the obtained mixture and the chain extender are then mixed with a high speed stirrer, and the polyisocyanate and the macropolyol are mixed, and then the obtained mixture is It includes the form which reacts by passing through a static mixer, and then mix | blends a chain extender with the mixture from the supply line connected so that it may join the said static mixer.

Moreover, in the manufacturing method of the thermoplastic polyurethane of this invention, it is preferable that the contact part of the static mixer which contacts the said reaction raw material is formed with the material which consists of a substantially nonmetallic material.

If the contact part of the static mixer which contacts a reaction raw material is formed with the material which consists of a substantially nonmetallic material, it can further prevent sticking.

Moreover, in the manufacturing method of the thermoplastic polyurethane of this invention, it is preferable that the said static mixer is comprised by connecting several static mixers which can control the temperature in a pipe independently.

By constructing the static mixer in this manner, the thermoplastic polyurethane can be produced under optimum reaction conditions while reducing the amount of catalyst by changing the in-tube temperature of each static mixer connected in series according to the composition of the reaction raw material.

The present invention also provides mixing means for mixing at least polyisocyanate and macropolyol, chain extender compounding means for blending a chain extender with the mixture mixed by the mixing means; And an apparatus for producing a thermoplastic polyurethane, comprising a static mixer for reacting a reaction raw material in which a chain extender is added to the mixture.

When the thermoplastic polyurethane is produced by such a device, at least the polyisocyanate and the macropolyol are mixed by the mixing means, and the chain extender is blended into the mixture mixed by the mixing means by the chain extender blending means. Since the reaction raw material manufactured by this is reacted in a static mixer, it can make it react uniformly by stirring in a static mixer. Therefore, generation | occurrence | production of gelling can be prevented effectively, and a thermoplastic polyurethane can be manufactured continuously using a high melting | fusing macropolyol, a high melting point chain extender, and a slow reaction polyisocyanate. In addition, since the twin screw extruder is not used, the mechanical shear of the twin screw extruder screw does not press or gelate due to retention in the groove of the screw, and the amount of catalyst is reduced to produce thermoplastic polyurethane. can do. As a result, a thermoplastic polyurethane with little physical property degradation and deterioration with time can be manufactured.

The present invention also encompasses thermoplastic polyurethanes obtained by reacting a reaction raw material comprising a mixture of at least polyisocyanate and macropolyol pre-mixed with a chain extender while passing through a static mixer.

Since such thermoplastic polyurethane is obtained by reacting uniformly by stirring in a static mixer, there is little sticking and gelation, and there is little physical property degradation and deterioration with time, and tensile strength, breaking elongation, tear strength, compression In addition to excellent mechanical properties such as permanent strain, and at the same hardness, the flow initiation temperature is low and the melting point range is wide, so that the molding processability is excellent. In addition, there are few gelled products (fish eyes) associated with the pressed particles and granules, and since the so-called non-yellowing polyisocyanate is used, the amount of catalyst can be reduced at the time of manufacture, and thus has excellent properties of not being yellowed.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram which shows the 1st specific example of the manufacturing apparatus of the thermoplastic polyurethane to which the manufacturing method of the thermoplastic polyurethane of this invention is applied. EMBODIMENT OF THE INVENTION Hereinafter, with reference to FIG. 1, the 1st specific example of the manufacturing method of the thermoplastic polyurethane of this invention is demonstrated.

In FIG. 1, this manufacturing apparatus 1a is an apparatus for continuously manufacturing thermoplastic polyurethane by the reaction extrusion molding method, The raw material tank part 2, the mixing part 3, the static mixer part 4, and a pellet The fire part 5 is provided.

The raw material tank part 2 is provided with the polyisocyanate storage tank 6, the polyol storage tank 7, and the chain extender storage tank 8.

In the polyisocyanate storage tank 6, polyisocyanate is stored as a raw material of the thermoplastic polyurethane.

The polyisocyanate is an organic compound such as an aromatic, aliphatic, alicyclic or the like having two or more isocyanate groups in one molecule. For example, as the aromatic polyisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, these 80:20 weight ratio of tolylene diisocyanate (TDI-80 / 20), isomeric mixture of 65:35 weight ratio (TDI-65 / 35), 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane Diisocyanate, 2,2'-diphenylmethane diisocyanate, any isomeric mixture of these diphenylmethane diisocyanates, toluylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, paraphenylenedi isocyanate, naphthalenedi Isocyanate etc. are mentioned.

Examples of the aliphatic polyisocyanates include ethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2, 4-trimethylhexanediisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecamethylene Triisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanatemethyloctane, bis ( Isocyanate ethyl) carbonate, bis (isocyanate ethyl) ether, 1,4-butylene glycol dipropyl ether-ω, ω'-diisocyanate Nate, lysine isocyanate methyl ester, lysine triisocyanate, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, 2-isocyanate propyl-2,6-diisocyanate hexanoate, bis (4-isocyanate-n-part Thylidene) pentaerythritol, etc. are mentioned.

As alicyclic polyisocyanate, isophorone diisocyanate, bis (isocyanate methyl) cyclohexane, dicyclohexyl methane diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, 2,2'- dimethyl dicyclohexyl methane di, for example. Isocyanate, dimer diisocyanate, 2,5-diisocyanatemethyl-bicyclo [2,2,1] -heptane, isomer of 2,6-diisocyanatemethyl-bicyclo [2,2,1] -heptane, 2 -Isocyanatemethyl-2- (3-isocyanatepropyl) -5-isocyanatemethyl-bicyclo- [2,2,1] -heptane, 2-isocyanatemethyl-2- (3-isocyanatepropyl) -6-isocyanatemethyl- Bicyclo- [2,2,1] -heptane, 2-isocyanatemethyl-3- (3-isocyanatepropyl) -5- (2-isocyanateethyl) -bicyclo- [2,2,1] -heptane, 2 Isocyanatemethyl-3- (3-isocyanatepropyl) -6- (2-isocy Nateethyl) -bicyclo- [2,2,1] -heptane, 2-isocyanatemethyl-2- (3-isocyanatepropyl) -5- (2-isocyanateethyl) -bicyclo- [2,2,1] -Heptane, 2-isocyanate methyl-2- (3-isocyanatepropyl) -6- (2-isocyanate ethyl) -bicyclo- [2,2,1] -heptane, etc. are mentioned.

Moreover, as polyisocyanate, modified isocyanate, such as urethane modified body, carbodiimide modified body, uretimine modified body, biuret modified body, allophanate modified body, isocyanurate modified body, etc. of polyisocyanate are mentioned, for example. .

Among the polyisocyanates described above, preferably 4,4'-diphenylmethane diisocyanate (hereinafter referred to as MDI), hydrogenated MDI (dicyclohexylmethane diisocyanate, hereinafter referred to as HMDI), paraphenylene 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-diisocyanate methyl -Bicyclo [2,2,1] -heptane, an isomer thereof 2,6-diisocyanatemethyl-bicyclo [2,2,1] -heptane (hereinafter referred to as NBDI), and more preferably Examples include MDI, HDI, HMDI, PPDI, NBDI, and urethane-modified products, carbodiimide-modified products, uretimine-modified products, and isocyanurate-modified products of these diisocyanates.

In addition, these polyisocyanates may be used independently or may be used together 2 or more types. When using together 2 or more types, you may mix and store in one polyisocyanate storage tank 6, or may store each polyisocyanate in the some polyisocyanate storage tank 6, respectively.

In the polyol storage tank 7, macropolyol is stored as a raw material of the thermoplastic polyurethane.

As a macropolyol, as a polymer which has 2 or more hydroxyl groups in 1 molecule, polyoxyalkylene polyol, polyester polyol, polycarbonate diol, etc. are mentioned, for example.

Examples of the polyoxyalkylene polyol include polyoxyalkylene glycol (styrene) by addition polymerization of alkylene oxides such as propylene oxide, ethylene oxide and butylene oxide to one or two or more compounds of a relatively low molecular weight dihydric alcohol. And polyoxyallylene glycol obtained by addition polymerization of an oxide or the like). In particular, propylene oxide and ethylene oxide are preferably used as the alkylene oxide. Examples of such polyoxyalkylene glycols include polypropylene glycol, polyethylene glycol and propylene oxide, copolymerized polyols of ethylene oxide, and the like.

As for the number average molecular weight of the polyoxyalkylene polyol used for the manufacturing method of the thermoplastic polyurethane of this invention, 200-10000 are preferable, More preferably, it is 500-8000.

Moreover, in the manufacturing method of the thermoplastic polyurethane of this invention, in order to reduce the glass transition temperature of a thermoplastic polyurethane, and to improve a flow characteristic, it uses together 2 or more types of polyoxyalkylene polyol from which molecular weight and concentration of an oxyalkylene group differ. It is preferable. Moreover, in such polyoxyalkylene polyol, it is preferable that there are few monools which have an unsaturated group in the terminal of a molecule | numerator produced | generated by the side reaction of propylene oxide. The monool content in the polyoxyalkylene polyol can be measured by the index of total unsaturation described in JIS K-1557. The total unsaturation in the polyoxyalkylene polyol is preferably 0.03 meq./g or less. More preferably, it is 0.02 meq./g or less. If the total unsaturated is greater than 0.03 meq./g, the heat resistance and durability of the thermoplastic polyurethane tend to be lowered. Moreover, it is preferable that the minimum of total unsaturated degree is about 0.01 meq./g from a viewpoint of industrial manufacture of polyoxyalkylene polyol.

Moreover, as a polymerization catalyst of the alkylene oxide in manufacture of such polyoxyalkylene polyol, alkali metal compounds, such as a cesium hydroxide and rubidium hydroxide, and the compound which has P = N bond (for example, a phosphazeneium compound and a phosphine oxide) Compounds, phosphazene compounds, and the like). By using such a polymerization catalyst of alkylene oxide, a polyoxyalkylene polyol having a low total unsaturated can be produced.

Moreover, as polyoxyalkylene polyol, the polytetramethylene ether glycol (henceforth PTMEG) obtained by ring-opening-polymerizing tetrahydrofuran is mentioned. As for the number average molecular weight of PTMEG used for the manufacturing method of the thermoplastic polyurethane of this invention, about 250-4000 are preferable. More preferably, it is about 250-2000. Moreover, polyoxyalkylene polyol which addition-polymerized the above-mentioned alkylene oxide to PTMEG can also be used.

Examples of the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, trimethylolpropane, neopentyl glycol, One kind or two or more kinds of low molecular polyols, such as 3-methyl-1,5-pentanediol, hydrogenated bisphenol A, hydrogenated bisphenol F, and the like, for example, glutaric acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid And polyester polyols obtained by condensation polymerization with one or two or more of other low molecular dicarboxylic acids and oligodimer acids, such as dimer acid and the like. Moreover, the polycaprolactone diol obtained by ring-opening-polymerizing (epsilon) -caprolactone as a polyester polyol can also be mentioned. It is preferable that the number average molecular weight of the polyester polyol used for the manufacturing method of the thermoplastic polyurethane of this invention is about 500-3000. More preferably, it is about 800-2000.

As polycarbonate diol, polycarbonate diol obtained by condensation reaction, such as dihydric alcohol, such as 1, 4- butanediol and 1, 6- hexanediol, and dimethyl carbonate, diethyl carbonate, is mentioned, for example. As a number average molecular weight of the polycarbonate diol used for the manufacturing method of the thermoplastic polyurethane of this invention, about 500-3000 are preferable. More preferably, it is about 800-2000.

Moreover, these macropolyols may be used independently and may be used together 2 or more types. When using together 2 or more types, you may mix and store in one polyol storage tank 7, and may store each macropolyol in the some polyol storage tank 7, respectively.

The chain extender storage tank 8 stores a chain extender as a raw material of the thermoplastic polyurethane.

The chain extender is an aliphatic, aromatic ring, heterocyclic or alicyclic ring low molecular compound having two or more hydroxyl groups in one molecule, and is an aliphatic polyol such as ethylene glycol, propylene glycol, 1,3-propanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, trimethylolpropane, etc. are mentioned.

Moreover, as an aromatic ring, a heterocyclic ring, or an alicyclic polyol, for example, paraxylene glycol, bis (2-hydroxyethyl) terephthalate, bis (2-hydroxyethyl) isophthalate, 1, 4-bis (2- Hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, resorcin, hydroquinone, 2,2'-bis (4-hydroxycyclohexyl) propane, 3,9-bis (1 , 1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol and the like Can be.

Moreover, these chain extenders may be used independently and may be used together 2 or more types. When using together 2 or more types, you may mix and store in one chain extender storage tank 8, and may store each chain extender in the some chain extender storage tank 8, respectively.

In addition, in the manufacturing method of the thermoplastic polyurethane of this invention, you may mix | blend a catalyst, an adjuvant, etc. with each component mentioned above according to the objective, a use, etc., and in that case, it carries out the catalyst to each storage tank 6, 7, and 8 Auxiliary agents and the like may be stored together with the above-mentioned components, or may be supplied by providing a separate storage tank although not shown. The auxiliary agent may be kneaded after production of the thermoplastic polyurethane.

As a catalyst, the well-known catalyst which produces polyurethane, such as an amine compound and an organometallic compound, is mentioned, for example, Preferably an organometallic compound is used. Examples of the organometallic compound include tin acetate, tin octylate, tin oleate, tin lauryl acid, dibutyl tin diacetate, dibutyl tin dilaurate, dibutyl tin dichloride, lead octanoate, lead naphthenate and naph. Nickel tenate, cobalt naphthenate, etc. are mentioned. These catalysts may be used alone or in combination of two or more thereof.

In addition, the catalyst is usually stored in a polyol storage tank 7 and / or a chain extender storage tank 8 other than the polyisocyanate storage tank 6, preferably in the polyol storage tank 7. In addition, the amount of the catalyst blended is 90 ppm or less, preferably 30 ppm or less, based on the weight of the macropolyol.

Examples of the auxiliary agent include known release agents, coupling agents, colorants, lubricants, weathering stabilizers, antioxidants, ultraviolet absorbers, foaming agents, rust preventive agents, milk whitening agents, fillers, and the like, and usually, other than the polyisocyanate storage tank 6. It is stored in the polyol storage tank 7 and / or the chain extender storage tank 8, preferably in the polyol storage tank 7.

In addition, each of these storage tanks 6, 7 and 8 is provided with a heater (or jacket), a temperature sensor, and a stirring blade which are not shown in figure, and the raw material (polyisocyanate, Polyol, chain extender, etc.) is configured to be stirred while maintaining at a predetermined set temperature. For example, the polyisocyanate storage tank 6 is set to, for example, 30 to 70 ° C, the polyol storage tank 7 is set to, for example, 60 to 140 ° C, and the chain extender storage tank 8 is, for example, , 30 to 130 ° C.

Moreover, each of these storage tanks 6, 7, and 8 is comprised so that connection of an inert gas line, such as a nitrogen line which is not shown in figure, can replace the inside of storage tanks 6, 7, and 8 with an inert gas atmosphere. It is configured to.

The mixing section 3 is provided with a high speed stirrer 9 as mixing means. The high speed stirrer 9 is not particularly limited as long as it can stir and mix the above-described raw materials at high speed. For example, in the case of a stirring blade 10a, for example, a stirring blade diameter of 4 cm phi and a circumferential length of 12 cm 300-5000 revolutions / minute (circumferential speed 100-600 m / min), Preferably it is provided with the stirring blade 10b which can be stirred at 1000-3500 revolutions / minute (120-420 m / min.) Is used. In addition, the high speed agitator 9 is provided with a heater (or jacket) and a temperature sensor (not shown), and is configured to control the temperature of the agitator tank 10a by controlling the heater based on the temperature detected by the temperature sensor. have.

In addition, as shown by an imaginary line, the mixing section 3 is provided with a reaction port 16 for temporarily holding the reaction raw materials (to be described later) mixed in the high-speed stirrer 9 to promote the reaction as necessary. You may. It is preferable that such a reaction port 16 is comprised so that temperature adjustment is possible, and when it installs, the 1st static mixer 17a of the most upstream in the high speed stirrer 9 and the static mixer part 4 mentioned later. ) Is connected between.

And the polyisocyanate storage tank 6 is connected with the high speed stirrer 9 via the polyisocyanate supply line 11, The gear pump 12a and the gear pump 12a in the middle of the polyisocyanate supply line 11 are carried out. The flowmeter 13a is interposed in the downstream of ().

In addition, the polyol storage tank 7 is connected to the high speed stirrer 9 via the polyol supply line 14, and in the middle of the polyol supply line 14, the gear pump 12b and the downstream of the gear pump 12b. The flowmeter 13b is interposed in the side.

Further, the chain extender storage tank 8 is connected to the high speed stirrer 9 via the chain extender supply line 15 as the chain extender compounding means, and in the middle of the chain extender supply line 15, a gear pump ( 12c) and the flowmeter 13c is interposed in the downstream of the gear pump 12c.

The static mixer part 4 is comprised by connecting some static mixer (still mixer) 17 in series.

In the case of distinguishing each static mixer 17 (hereinafter, each static mixer 17), the first static mixer 17a and the second from the upstream side in the flow direction of the reaction raw material (to be described later) to the downstream side. The static mixer 17b (... n-th static mixer 17n) is not particularly limited in the shape of the mixer member in the pipe, for example, "Advanced 24th Agitating and Mixing of Chemical Engineering" (the Society of Chemical Engineering, Japan) The number of branches, such as Company-N type, Company-T type, Company-S type, and Company-T type, described in Fig. 10.1.1 on page 155 of the October 20, 1990 issue of Makishoten). The shape can be used, Preferably the right element and the left element are alternately arrange | positioned, The straight pipe | tube may be provided between each static mixer 17 as needed.

In addition, each static mixer 17 has a tube length of, for example, 0.13 to 3.6 m, preferably 0.3 to 2.0 m, more preferably 0.5 to 1.0 m, and its inner diameter is, for example, 10 to 300 mmφ, preferably Is 13-150 mm (phi), More preferably, it is 15-50 mm (phi), Tube length / inner diameter ratio (it describes as L / D hereafter) is 3-25, Preferably the thing of 5-15 is used.

In addition, each static mixer 17 is formed of substantially non-metallic material such as fiber-reinforced plastics (FRP), or the surface of the contact portion with the reaction raw material (described later) in the tube is, for example, polytetrafluoroethylene or the like. It is preferable to use what is covered by the fluorine resin. By forming the contact portion with the reaction raw material (described later) substantially as a non-metallic material, it is possible to effectively prevent the thermoplastic polyurethane from sticking. Preferably, what coat | covered the contact part of the static mixer 17 with fluororesins, such as polytetrafluoroethylene, is used. As such a static mixer 17, More specifically, the tube which consists of fluorine-type resins, such as polytetrafluoroethylene, was inserted in the static mixer 17 which consists of metals, the MX series by a commercially available Noritake company, etc. are mentioned. This is used.

In addition, each static mixer 17 is provided with a heater (or jacket) and a temperature sensor (not shown), and is configured to independently control the temperature in the tube by controlling the heater based on the detected temperature in the temperature sensor. have. Thereby, since the in-tube temperature of each static mixer 17 can be changed according to the composition of reaction raw material (after-mentioned), thermoplastic polyurethane can be manufactured on optimal reaction conditions, reducing a catalyst amount.

And the 1st static mixer 17a of the most upstream in the static mixer part 4 is connected to the high speed stirrer 9 (or reaction port 16) in the mixing part 3, and is static The most downstream n-th static mixer 17n in the mixer part 4 is connected to the strand die 19 (or the single screw extruder 18 mentioned later) in the pelletizing part 5 later.

In addition, the number of connected static mixers 17 can be suitably determined by the purpose and use, raw material composition, etc., and the total length which connected each static mixer 17 is 3-25 m, for example, Preferably it is For example, 10 to 50, preferably 15 to 35 static mixers are continuously connected so as to be 5 to 20 m, and a gear pump (not shown) is appropriately interposed between the static mixers 17. It is configured to adjust the flow rate.

The pelletizing unit 5 includes a strand die 19 and a cutter 20. In addition, the pelletizing part 5 is not limited to the strand die 19 and the cutter 20 in particular, You may comprise in the form of a well-known pelletizer (including an underwater cutting device etc.).

In addition, as shown in the phantom between the static mixer section 4 and the pelletizing section 5, a single screw extruder 18 is provided as necessary to further knead the reactant flowing out of the static mixer section 4. good.

In the case where the single screw extruder 18 is provided, a filtration device may be provided at the tip of the single screw extruder 18 to remove granules and gels from the reactants. As the filtration device, for example, a polymer filter or the like is used.

Next, a method for producing a thermoplastic polyurethane by the manufacturing apparatus 1a shown in FIG. 1 will be described.

In this method, first, the polyisocyanate, macropolyol and chain extender stored in the polyisocyanate storage tank 6, the polyol storage tank 7 and the chain extender storage tank 8 are supplied to the high speed stirrer 9, Reaction raw materials are manufactured by mixing them simultaneously in the high speed stirrer 9.

In order to supply the polyisocyanate from the polyisocyanate storage tank 6, the gear pump 12a is controlled based on the flow rate detected by the flow meter 13a, for example, 2 to 100 kg / h, preferably 2.5 to 60 The polyisocyanate is fed from the polyisocyanate feed line 11 to the high speed stirrer 9 at a flow rate of kg / h.

Further, in order to supply the macropolyol from the polyol storage tank 7, the gear pump 12b is controlled based on the flow rate detected by the flow meter 13b, for example, 10 to 200 kg / h, preferably 15 to 100. The macropolyol is fed from the polyol supply line 14 to the high speed stirrer 9 at a flow rate of kg / h.

Further, in order to supply the chain extender from the chain extender storage tank 8, the gear pump 12c is controlled based on the flow rate sensed by the flow meter 13c, for example, 0.2 to 50 kg / h, preferably The chain extender is fed from the chain extender supply line 15 to the high speed stirrer 9 at a flow rate of 0.3 to 30 kg / h.

Thereby, in the high speed stirrer 9, the equivalence ratio (NCO / OH) of the macropolyol to the isocyanate group of the polyisocyanate and the hydroxyl group of the chain extender in the steady state is, for example, 0.9 to 1.2, preferably 0.95 to 1.05. Is set. In addition, the weight ratio of the macropolyol to the chain extender is set to, for example, 2 to 90 times, preferably 3 to 50 times.

In the high-speed stirrer 9, these polyisocyanates, macropolyols and chain extenders are kept in the stirring tank 10a for a residence time of 0.05 to 0.5 minutes, preferably 0.1 to 0.4 minutes, and a temperature of 70 to 130 ° C, preferably Is 500-4000 revolutions / minute (60-480 m / min circumference speed) of the stirring blade 10b in the case of 80-120 degreeC, stirring blade diameter 4cmφ, and circumference 12cm, Preferably it is 2000-3000 The reaction raw material is manufactured by high speed stirring at rotation / min (circumferential speed 240-360 m / min).

Thereafter, if necessary, the reaction raw material obtained after the reaction port 16 is held at 70 to 140 ° C., preferably 80 to 120 ° C. at 0.1 to 15 minutes, preferably 0.5 to 10 minutes, is static. It supplies to the mixer part 4, and makes it react, passing through each static mixer 17. As shown in FIG.

The in-tube temperature in each static mixer 17 may be suitably selected at, for example, 100 to 300 ° C, preferably 140 to 250 ° C, and the passage speed is, for example, 20 to 300 kg / h, preferably 30. -150 kg / h.

Then, the reactant flowing out of the static mixer section 4 is further kneaded by the single screw extruder 18 as necessary, and then extruded from the strand die 19 in the pelletizing section 5, and then cooled by a known method. The thermoplastic polyurethane is obtained by cutting this with the cutter 20 and shaping it into pellets.

According to this method, since the reaction raw material in which the polyisocyanate, the macropolyol, and the chain extender are mixed in advance by the high speed stirrer 9 is introduced into the static mixer section 4, the stirring in each static mixer 17 is uniform. Can react. Therefore, generation | occurrence | production of a gelatinizer can be prevented effectively, and the macropolyol of a high melting point (the polyester polyol which consists of aromatic carboxylic acids, such as terephthalic acid and isophthalic acid, and low molecular polyol, polycarbonate diol in the above-mentioned polyester polyol) Etc.) or a high melting point chain extender (the polyols of the above-mentioned aromatic ring, heterocyclic ring or alicyclic ring are exemplified, and more specifically, paraxylene glycol, bis (2-hydroxyethyl) terephthalate, Bis (2-hydroxyethyl) isophthalate, 1,4-bis (2-hydroxyethoxy) benzene, 1,3-bis (2-hydroxyethoxy) benzene, resorcin, hydroquinone, 2,2 ' -Bis (4-hydroxycyclohexyl) propane, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1, 4- cyclohexane dimethanol, 1, 4- cyclohexanediol, etc. are illustrated.) Moreover, a slow reaction polyiso Oh carbonate by using a (for example, so-called non-yellowing (NY-based) a polyisocyanate, such as the aforementioned aliphatic polyisocyanate or alicyclic polyisocyanate) may be prepared by a continuous thermoplastic polyurethane. In addition, since the twin screw extruder is not used, the mechanical shearing of the screw does not cause the sticking, and the gelation does not occur due to the retention of the screw in the groove. It can reduce and manufacture. As a result, a thermoplastic polyurethane with little physical property degradation and deterioration with time can be manufactured.

It is a schematic block diagram which shows the 2nd specific example of the manufacturing apparatus of the thermoplastic polyurethane to which the manufacturing method of the thermoplastic polyurethane of this invention is applied. Hereinafter, with reference to FIG. 2, the 2nd specific example of the manufacturing method of the thermoplastic polyurethane of this invention is demonstrated. 2, the same code | symbol is attached | subjected to the member same as FIG. 1, and the detailed description is abbreviate | omitted.

In FIG. 2, this manufacturing apparatus 1b is equipped with the raw material tank part 2, the mixing part 3, the static mixer part 4, and the pelletizing part 5 like the manufacturing apparatus 1a shown in FIG. Doing.

The raw material tank part 2 is equipped with the polyisocyanate storage tank 6 like the manufacturing apparatus 1a shown in FIG. 1, the polyol storage tank 7, and the chain extender storage tank 8. As shown in FIG.

The polyisocyanate storage tank 6 stores the above-mentioned polyisocyanate, the polyol storage tank 7 stores the above-mentioned macropolyol, and the chain extender storage tank 8 stores the above-mentioned chain extender. .

The mixing section 3 is provided with two high speed stirrers 9a and 9b. Each of the high speed stirrers 9a and 9b has the same configuration as the high speed stirrer 9 shown in FIG. 1 described above, and these are connected in series.

In addition, in the mixing part 3, as shown by an imaginary line, between the upstream high speed stirrer 9a and the downstream high speed stirrer 9b, and downstream of the downstream high speed stirrer 9b as needed. Reaction ports 16a and 16b may be provided on the side to temporarily hold the reaction raw materials mixed in the high speed stirrers 9a and 9b to promote the reaction. Such reaction ports 16a and 16b are preferably configured to be temperature-adjustable as described above, and any one or both of the reaction ports 16a and 16b may be provided as necessary.

And the polyisocyanate storage tank 6 is connected with the high speed stirrer 9a upstream through the polyisocyanate supply line 11, The gear pump 12a and the gear in the middle of the polyisocyanate supply line 11 are carried out. The flowmeter 13a is interposed in the downstream of the pump 12a.

In addition, the polyol storage tank 7 is connected to the high speed stirrer 9a on the upstream side through the polyol supply line 14, and the gear pump 12b and the gear pump 12b in the middle of the polyol supply line 14. The flowmeter 13b is interposed in the downstream of ().

In addition, the chain extender storage tank 8 is connected to the downstream high speed stirrer 9b via the chain extender supply line 15, and in the middle of the chain extender supply line 15, the gear pump 12c, And a flow meter 13c on the downstream side of the gear pump 12c.

Moreover, the static mixer part 4 is comprised by connecting several static mixer 17 as mentioned above in series, and the 1st static mixer 17a of the most upstream is downstream in the mixing part 3 Strand die 19 (or short axis) which is connected to the high-speed stirrer 9b (or reaction port 16b) on the side, and which the n-th static mixer 17n on the downstream side is described later in the pelletizing unit 5. Extruder 18).

In addition, the number of connected static mixers 17 can be suitably determined according to the purpose, use, raw material composition, etc. as mentioned above, and the total length which connected each static mixer 17 is 3-25 m, for example. 10-50, preferably 15-35 static mixers are continuously connected so that it may become 5-20 m preferably, and the gear pump (illustration shown) suitably is between each static mixer 17. Flow rate control is possible.

The pelletization part 5 is equipped with the strand die 19 and the cutter 20 as mentioned above. In addition, a single screw extruder 18 may be provided between the static mixer section 4 and the pelletizing section 5 as necessary in order to further knead the reactant flowing out of the static mixer section 4 as shown by a virtual line. . In addition, when installing the single screw extruder 18, you may install a filtration apparatus in the front-end | tip of the single screw extruder 18, and may remove the granule and gel in a reaction material. As a filtration apparatus, a polymer filter etc. are used, for example.

Next, a method for producing the thermoplastic polyurethane by the manufacturing apparatus 1b shown in FIG. 2 will be described.

In this method, first, the polyisocyanate and macropolyol stored in the polyisocyanate storage tank 6 and the polyol storage tank 7 are supplied to the high speed stirrer 9a on the upstream side and mixed with the high speed stirrer 9a on the upstream side. After that, the resulting mixture and the chain extender stored in the chain extender storage tank 8 are then supplied to the high speed stirrer 9b on the downstream side and reacted by mixing them in the high speed stirrer 9b on the downstream side. Manufacture raw materials.

The flow rate for supplying the polyisocyanate from the polyisocyanate storage tank 6 to the high speed stirrer 9a on the upstream side is, for example, 2 to 100 kg / h, preferably 5 to 60 kg / h, and the polyol storage tank 7 The flow rate at which the macropolyol is supplied to the high speed stirrer 9a on the upstream side is, for example, 10 to 200 kg / h, preferably 15 to 100 kg / h.

Thereby, in the upstream high speed stirrer 9a, the equivalence ratio (NCO / OH) of the hydroxyl group of the macropolyol to the isocyanate group of the polyisocyanate in the steady state is set to, for example, 1.05 to 6, preferably 1.1 to 5 do.

In the upstream high speed stirrer 9a, these polyisocyanates and macropolyols are kept in the stirring tank 10a for a residence time of 0.05 to 0.5 minutes, preferably 0.1 to 0.4 minutes, and a temperature of 60 to 150 ° C, preferably 80. Speed of the stirring blade 10b in the case of -130 degreeC, stirring blade diameter 4cmφ, and circumference length 12cm 500-4000 rotations / minute (60-480 m / min of circumference), Preferably 2000-3000 rotations / The mixture is prepared by high speed stirring at minutes (240-360 m / min.).

Thereafter, if necessary, the resulting mixture is allowed to remain at the reaction port 16a at, for example, 0.1 to 60 minutes, preferably 1 to 30 minutes at 80 to 150 ° C, preferably 90 to 140 ° C, and then the resulting mixture is downstream. It is supplied to the high speed stirrer 9b. The flow rate for supplying the mixture from the upstream high speed stirrer 9a to the downstream high speed stirrer 9b is, for example, 10 to 200 kg / h, preferably 20 to 100 kg / h, and the high speed stirrer 9a ( Alternatively, the flow rate may be adjusted by a gear pump (not shown) provided downstream of the reaction port 16a.

Further, the flow rate for supplying the chain extender from the chain extender storage tank 8 to the high speed stirrer 9b downstream is, for example, 0.2 to 50 kg / h, preferably 0.3 to 30 kg / h.

Thus, in the downstream high speed stirrer 9b, the equivalent ratio (NCO / OH) of the macropolyol to the isocyanate group of the polyisocyanate and the hydroxyl group of the chain extender in the steady state is, for example, 0.9 to 1.2, preferably 0.95. It is set to -1.05. In addition, the weight ratio of the macropolyol to the chain extender is set to, for example, 2 to 90 times, preferably 3 to 50 times.

In the downstream high speed stirrer 9b, these polyisocyanates, macropolyols and chain extenders are kept in a stirring tank 10a for a residence time of 0.05 to 0.5 minutes, preferably 0.1 to 0.4 minutes, a temperature of 60 to 150 ° C, Preferably, the speed | rate 500-4000 rotations / minute (60-480 m / min of circumferential speeds) of the stirring blade 10b in the case of 80-140 degreeC, stirring blade diameter 4cmφ, and circumference length 12cm, Preferably The reaction raw material is manufactured by high speed stirring at 2000-3000 revolutions / minute (circumferential speed 240-360 m / min).

Thereafter, if necessary, the resulting reaction raw material is statically retained at, for example, 0.1 to 15 minutes, preferably 0.5 to 10 minutes, at 70 to 140 ° C, preferably 80 to 120 ° C in the reaction port 16b. It supplies to the mixer part 4, and makes it react, passing through each static mixer 17. As shown in FIG.

The in-tube temperature in each static mixer 17 may be suitably selected at, for example, 100 to 300 ° C, preferably 140 to 250 ° C, and the passage speed is, for example, 20 to 300 kg / h, preferably 30. -150 kg / h.

Then, the reactant flowing out of the static mixer section 4 is further kneaded by the single screw extruder 18 as necessary, and then extruded from the strand die 19 in the pelletizing section 5, and cooled by a known method. Then, this is cut by the cutter 20 and molded into pellets to obtain a thermoplastic polyurethane.

According to this method, polyisocyanate and macropolyol are mixed by the high speed stirrer 9a on the upstream side, and the obtained mixture and the chain extender are mixed by the high speed stirrer 9b on the downstream side, thereby producing Since a reaction raw material is introduce | transduced into the static mixer part 4, it can make it react uniformly by stirring in each static mixer 17. As shown in FIG. Therefore, it is possible to effectively prevent the generation of gelling, and as described above, the thermoplastic polyurethane can be continuously produced using a high melting point macropolyol, a high melting point chain extender, and a slow reaction polyisocyanate. Can be. In addition, since a twin screw extruder is not used, the mechanical shearing of the screw does not cause the sticking or gelation due to the retention of the screw in the groove, and no catalyst is used or the amount of catalyst is greatly increased. It can reduce and manufacture. As a result, a thermoplastic polyurethane with little physical property degradation and deterioration with time can be manufactured.

It is a schematic block diagram which shows the 3rd specific example of the manufacturing apparatus of the thermoplastic polyurethane to which the manufacturing method of the thermoplastic polyurethane of this invention is applied. Hereinafter, with reference to FIG. 3, the 3rd specific example of the manufacturing method of the thermoplastic polyurethane of this invention is demonstrated. 3, the same code | symbol is attached | subjected to the member same as FIG. 1, and the detailed description is abbreviate | omitted.

In FIG. 3, this manufacturing apparatus 1c uses the raw material tank part 2, the mixing part 3, the static mixer part 4, and the pelletizing part 5 like the manufacturing apparatus 1a shown in FIG. Equipped.

The raw material tank part 2 is equipped with the polyisocyanate storage tank 6 like the manufacturing apparatus 1a shown in FIG. 1, the polyol storage tank 7, and the chain extender storage tank 8. As shown in FIG.

The polyisocyanate storage tank 6 stores the above-mentioned polyisocyanate, the polyol storage tank 7 stores the above-mentioned macropolyol, and the chain extender storage tank 8 stores the above-mentioned chain extender. .

The mixing part 3 is equipped with the high speed stirrer 9 like the manufacturing apparatus 1a shown in FIG.

In addition, the mixing section 3 may be provided with a reaction port 16 for temporarily holding the mixture mixed in the high-speed stirrer 9 to promote the reaction, as shown by the phantom line. It is preferable that such a reaction port 16 is comprised so that temperature adjustment is possible, and when it installs, the 1st static mixer 17a of the most upstream in the high speed stirrer 9 and the static mixer part 4 mentioned later. ) Is connected between.

And the polyisocyanate storage tank 6 is connected with the high speed stirrer 9 via the polyisocyanate supply line 11, The gear pump 12a and the gear pump 12a in the middle of the polyisocyanate supply line 11 are carried out. The flowmeter 13a is interposed in the downstream of ().

In addition, the polyol storage tank 7 is connected to the high speed stirrer 9 via the polyol supply line 14, and in the middle of the polyol supply line 14, the gear pump 12b and the downstream of the gear pump 12b. The flowmeter 13b is interposed in the side.

In addition, the chain extender storage tank 8 is connected between the static mixers 17 in the static mixer section 4 as described below through the chain extender supply line 15 (the first static mixer in FIG. 3). It is connected to the T-shaped connecting pipe 21 provided between the 17a and the 2nd static mixer 17b, The gear pump 12c and the gear pump (in the middle of the chain extender supply line 15) The flowmeter 13c is interposed in the downstream of 12c).

Moreover, the static mixer part 4 is comprised by connecting several static mixer 17 as mentioned above in series, and the 1st static mixer 17a of the most upstream is the high speed in the mixing part 3, It is connected to the stirrer 9 (or the reaction port 16), and the most downstream n-th static mixer 17n is the strand die 19 (or single screw extruder 18) mentioned later in the pelletization part 5. Is connected to)).

In addition, the number of connected static mixers 17 can be suitably determined according to the purpose, use, raw material composition, etc. as mentioned above, and the total length which connected each static mixer 17 is 3-25 m, for example. 10-50, preferably 15-35 static mixers are continuously connected so that it may become 5-20 m preferably, and the gear pump (illustration shown) suitably is between each static mixer 17. It is configured to be able to adjust the flow rate through). In addition, in this static mixer part 4, the T-shaped connecting pipe 21 connected so that the chain extender supply line 15 may join between arbitrary in the middle of each static mixer 17 as mentioned above is provided. It is installed.

The pelletization part 5 is equipped with the strand die 19 and the cutter 20 as mentioned above. Moreover, as shown by a virtual line between the static mixer part 4 and the pelletizing part 5, the single screw extruder 18 is provided as needed, and the kneading | mixing material which flows out from the static mixer part 4 is further kneaded. You may. In addition, when installing the single screw extruder 18, you may provide a filtration apparatus in the front-end | tip of the single screw extruder 18, and may remove the granule and gel in a reaction material. As the filtration device, for example, a polymer filter or the like is used.

Next, a method for producing the thermoplastic polyurethane by the manufacturing apparatus 1c shown in FIG. 3 will be described.

In this method, first, polyisocyanate and macropolyol stored in the polyisocyanate storage tank 6 and the polyol storage tank 7 are supplied to the high speed stirrer 9, and then mixed in the high speed stirrer 9, and then The obtained mixture is allowed to react by passing through each of the static mixers 17 (first static mixer 17a in FIG. 3) upstream from the T-shaped connecting tube 21 in the static mixer section 4 thereafter. A chain feeder is supplied from the chain extender supply line 15 to the T-shaped connecting tube 21, and the chain extending agent is blended and mixed in the mixture in the T-shaped connecting tube 21 to produce a reaction raw material.

The flow rate for supplying the polyisocyanate from the polyisocyanate storage tank 6 to the high speed stirrer 9 is, for example, 2 to 100 kg / h, preferably 5 to 60 kg / h, and from the polyol storage tank 7 to the high speed stirrer. The rate at which the macropolyol is supplied to (9) is, for example, 10 to 200 kg / h, preferably 15 to 100 kg / h.

Thereby, in the high speed stirrer 9, the equivalence ratio (NCO / OH) of the hydroxyl group of the macropolyol with respect to the isocyanate group of polyisocyanate in a steady state is set to 1.05-6, Preferably it is 1.1-5.

In the high-speed stirrer 9, these polyisocyanates and macropolyols are kept in a stirring tank 10a for a residence time of 0.05 to 0.5 minutes, preferably 0.1 to 0.4 minutes, and a temperature of 60 to 150 ° C, preferably 80 to 130. 500-4000 rotations / minute (60-480 m / min of circumferential speed) of stirring blade 10b in the case of (degreeC), stirring blade diameter 4cm (phi), and circumference length 12cm, Preferably 2000-3000 rotations / minute ( The mixture is prepared by high speed agitation at 240 to 360 m / min.

Thereafter, if necessary, the resulting mixture is allowed to remain in the reaction pot 16 at, for example, 0.1 to 60 minutes, preferably 1 to 30 minutes at 80 to 150 ° C, preferably 90 to 140 ° C, and then the resulting mixture is static. It supplies to the mixer part 4, and makes it react, passing through each static mixer 17 (1st static mixer 17a in FIG. 3). Moreover, in each static mixer 17 (1st static mixer 17a in FIG. 3) upstream rather than the T-shaped connection pipe 21 in the static mixer part 4, the internal temperature of the tube is 100-300, for example. At 캜, preferably 150 to 280 캜, the passage speed is set to, for example, 10 to 200 kg / h, preferably 30 to 150 kg / h.

Further, the flow rate for supplying the chain extender from the chain extender storage tank 8 to the T-shaped tube 21 is, for example, 1 to 50 kg / h, preferably 3 to 30 kg / h. In the T-shaped connecting tube 21, the equivalence ratio (NCO / OH) of the macropolyol to the isocyanate group of the polyisocyanate and the hydroxyl group of the chain extender in the steady state is, for example, 0.9 to 1.2, preferably 0.95 to 1.05. do. In addition, the weight ratio of the macropolyol to the chain extender is set to, for example, 2 to 90 times, preferably 3 to 50 times.

In this method, the reaction raw materials produced in the T-shaped tube 21 are each static mixer 17 on the downstream side of the T-shaped tube 21 in the static mixer section 4 ( The reaction is carried out while passing through the two static mixers 17b to n-th static mixer 17n.

In the pipe in each static mixer 17 (second static mixer 17b to n-th static mixer 17n in the downstream side) of T-shaped tube 21 in static mixer part 4 downstream. The temperature may be appropriately selected from, for example, 100 to 300 ° C, preferably 150 to 280 ° C, and the passage speed is, for example, 20 to 300 kg / h, preferably 30 to 150 kg / h.

And after knead | mixing the reactant which flowed out from the static mixer part 4 by the single screw extruder 18 as needed, it extrudes from the strand die 19 in the pelletizing part 5, and after cooling, this cutter It cuts as (20) and shape | molds as a pellet and by this, a thermoplastic polyurethane is obtained.

According to this method, the polyisocyanate and macropolyol are mixed by the high speed stirrer 9, and the obtained mixture is mixed with each static mixer upstream of the T-shaped connecting tube 21 in the static mixer section 4 ( 17) (the first static mixer 17a in FIG. 3) reacts to synthesize the prepolymer, and then the chain extender supplied in the T-shaped tube 21 is blended to produce a reaction The raw material is introduced into each of the static mixers 17 (second static mixers 17b to nth static mixers 17n in the downstream side) in the downstream side of the T-shaped connecting pipe 21 in the static mixer section 4. Since it reacts, it can react uniformly by stirring in each static mixer 17. As shown in FIG. Therefore, it is possible to effectively prevent the generation of gelling, and as described above, the thermoplastic polyurethane can be continuously produced using a high melting point macropolyol, a high melting point chain extender, and a slow reaction polyisocyanate. Can be. In addition, since a twin screw extruder is not used, the mechanical shearing of the screw does not cause the sticking or gelation due to the retention of the screw in the groove, and no catalyst is used or the amount of catalyst is greatly increased. It can reduce and manufacture. As a result, a thermoplastic polyurethane with little physical property degradation and deterioration with time can be manufactured.

In addition, the thermoplastic polyurethane obtained by the above-described method is less pressed and gelled as described above, less physical property deterioration and deterioration with time, and also tensile strength, breaking elongation, tear strength, compression set and strain rate. In addition to excellent mechanical properties, even when the hardness is the same, the flow initiation temperature is low and the melting point range is wide, thereby excellent molding processability. In addition, there are few gellings (fisheyes) related to the pressed and granules, and even when non-yellowing polyisocyanate is used, the amount of catalyst can be reduced at the time of manufacture, which has excellent properties of not being yellowed further.

Therefore, such thermoplastic polyurethanes can be effectively used in various fields such as, for example, shoe soles, insoles, ski shoes, automotive exterior parts, interior parts, electrical parts or castors, hoses, tubes, sheets, films, fibers, and the like. Can be.

In this process, any known additive (preferably a masterbatch additive), which possesses properties which are insoluble to the abovementioned raw materials or which itself possesses non-hot melt properties, can be added, for example inorganic pigments, Inorganic antibacterial agents, inorganic deodorants and flame retardants.

Although there is no particular limitation on the method of adding the additive, the additive may be added using the apparatus 1d of the fourth embodiment shown in FIG. As shown in FIG. 4, an injection tee 22 is connected to any intermediate portion between adjacent static mixers 17 of the static mixer section 4. In FIG. 4, similar reference numerals are used for parts corresponding to those of FIG. 1, and a detailed description of corresponding members is omitted.

The additive is filled into the single screw extruder 23 and supplied from the injection tee 22 to an intermediate portion between adjacent static mixers 17 of the static mixer section 4. Therefore, the additive supplied from the infusion tee 22 is combined with the reaction raw material which passes through each static mixer 17 located upstream of the infusion tee 22 in the static mixer part 4, and the static mixer part 4 The mixture is uniformly mixed with the reaction raw materials in each static mixer 17 located downstream of the injection tee 22). The additive is continuously filled from the single screw extruder 23 at a filling rate of, for example, 0.1 to 80 kg / h, preferably 0.5 to 30 kg / h.

Moreover, reactive hot melt can also be manufactured using the manufacturing apparatus 1a-1c shown to FIG. 1 thru | or FIG. That is, the reactive hot melt is composed of a polyurethane prepolymer having an isocyanate group at its molecular end as a main component, and a thermoplastic polymer, a tackifier, a plasticizer, and the like are blended for the purpose of imparting adhesion to a substrate, heat resistance of the adhesive itself, and the like. . In order to obtain this, the polyurethane prepolymer which mainly uses macropolyol and polyisocyanate as a main raw material is manufactured by the manufacturing apparatus 1a-1c shown to FIG.

Usually, polyester polyol is mainly used as a macropolyol. Examples of the polyester polyols include low-molecular polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentylglycol and trimethylolpropane, and the like, for example, adipic acid, sebacic acid, and azela. And polyester polyols produced by esterification with aliphatic carboxylic acids such as acids or aromatic carboxylic acids such as terephthalic acid and isophthalic acid.

In order to express the function as a hot-melt adhesive agent, the liquid or crystallized polyester polyol near room temperature is used individually or in mixture of 2 or more types. About 500-10000 are preferable, and, as for the number average molecular weight of polyester polyol, about 1000-9000 are more preferable.

As polyisocyanate, said MDI, TDI, HMDI, HDI, IPDI, XDI, NBDI, etc. are used suitably. The equivalent ratio (NCO / OH) of the hydroxyl group of the macropolyol to the isocyanate group of the polyisocyanate is set to, for example, 1.1 to 8, preferably 1.3 to 5.

The following method is illustrated as a method of manufacturing the polyurethane prepolymer which is a main component of the reactive hot melt. That is, the above-mentioned polyisocyanate is first put into the polyisocyanate storage tank 6 of the manufacturing apparatus 1a shown in FIG. 1 in the atmosphere of an inert gas, and is stored at the temperature used as liquid phase. Although it depends on the property of the polyisocyanate to be used, it stores normally, stirring at about 40-60 degreeC in nitrogen atmosphere.

Subsequently, the above-mentioned polyester polyol is put into the polyol storage tank 7 of the manufacturing apparatus 1a shown in FIG. 1, and it stores at the temperature used as liquid phase. Although it depends also on the property of the polyester polyol to be used, it adjusts to about 40-150 degreeC under nitrogen atmosphere, and stores normally, stirring.

Then, through the polyisocyanate supply line 11 and the polyol supply line 14 by the gear pumps 12a and 12b, respectively, from the polyisocyanate storage tank 6 and the polyol storage tank 7 by the above-described method. Polyisocyanate and polyester polyol are supplied to the high speed stirrer 9, and the liquid is passed through to the first static mixer 17a.

In addition, the number of connected static mixers 17 may vary depending on the amount of polyurethane prepolymer produced, but is configured such that, for example, 3 to 80, preferably 5 to 60, static mixers are continuously connected, It is possible to adjust the flow rate between each static mixer 17 via a gear pump (not shown) as appropriate. Although the temperature of the static mixer 17 depends on the raw material composition to be used, about 40-260 degreeC is preferable, More preferably, it is about 60-230 degreeC.

Then, the polyurethane prepolymer polymerized in the static mixer 17 under the above conditions is passed through the single screw extruder 18 shown in FIG. 1, and the thermoplastic polymer, the tackifier, the plasticizer, and the like are fed using the single screw extruder 18. A reactive hot melt is prepared by adding and kneading the polyurethane prepolymer. Although the content (NCO%) of the free isocyanate group of the reactive hot melt obtained in this way varies with the use, 1-5% is preferable and about 1.2-3% is more preferable.

EXAMPLES

The invention will be further described by the examples and comparative examples which follow, but it should be understood that the scope of the invention is not limited to any of the examples presented.

Example 1

In the manufacturing apparatus 1a shown in FIG. 1, the reaction port 16 and the single screw extruder 18 were connected, and each static mixer 17 of the static mixer part 4 was connected 15 times, using the following By operation, a thermoplastic polyurethane (hereinafter referred to as TPU) was produced.

Moreover, the static mixer part 4 is the 1st-3rd static mixers 17a-17c (the state which connected three static mixers with a pipe length of 0.5 m and an internal diameter of 20 mmφ, the internal temperature of 240 degreeC), 4th-agent 5 static mixers 17e to 17f (tube length 1.0 m, two stack mixers with an inner diameter of 20 mmφ connected, pipe temperature 200 ° C), 6th to 12th static mixers (17 g to 17j) (tube length 1.0 m, 7 static mixers with an internal diameter of 38 mmφ are connected, the internal temperature of the tube is 200 ° C., and the 13th to 15th static mixers (17k to 17m) (with a pipe length of 0.5 m and 3 static mixers with an internal diameter of 38 mmφ). State, the internal temperature of the tube was 200 ° C).

12.4 parts by weight of 4,4'-diphenylmethane diisocyanate (manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Cosmonate PH, hereinafter referred to as MDI) was placed in a polyisocyanate storage tank 6 and adjusted to 40 ° C.

195 parts by weight of polyethylene glycol having a number average molecular weight of 8300 (Sanyo Kasei Co., Ltd. trade name: Ekipeg 6000, melt at 100 ° C), and 30 ppm of dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.) based on the weight of the macropolyol. (Hereinafter, these components are called polyol solution) was put into the polyol storage tank 7, and it adjusted to 90 degreeC.

2.33 parts by weight of 1,4-butanediol (made by BASF, melted at 50 ° C, hereinafter referred to as BG) was placed in a chain extender storage tank 8, and adjusted to 40 ° C. In addition, these operations were performed in nitrogen atmosphere.

Subsequently, MDI was used at a flow rate of 2.86 kg / h, polyol solution at a flow rate of 45 kg / h, and BG at a flow rate of 0.54 kg / h. After passing through and stirring each raw material sufficiently, after making it hold | maintain for 1 to 7 minutes in reaction port 16 (10L), it passed through the 1st static mixer 17a of the static mixer part 4.

Thereafter, the reactant flowing out of the fifteenth static mixer 17m is press-fitted into a single screw extruder (GM Engineering, Inc., 65 mmφ, press-fitted portion 150 ° C), and then extruded from the strand die 19 to a chilled roll / cooling belt. After cooling, the pellet-shaped TPU was obtained by cutting with a pelletizer (Ishinaka Tekkojo Co., PPL-130 type).

Example 2

In the manufacturing apparatus 1a shown in FIG. 1, without connecting the reaction port 16, the single screw extruder 18 was connected, and each static mixer 17 of the static mixer part 4 connected 16 stations was used. Thus, the TPU was manufactured by the following operation.

Moreover, the static mixer part 4 is the 1st-7th static mixers 17a-17g (the state which connected 7 static mixers with a pipe length of 0.5 m and an internal diameter of 20 mmφ, internal temperature of 190 degreeC), 8th-agent 9 static mixers 17h to 17i (tube length 1.0 m, two static mixers with an inner diameter of 20 mmφ connected, pipe temperature 180 ° C), 10th to 14th static mixers (17j to 17n) (tube length 1.0 m 5 static mixers with an internal diameter of 38 mmφ are connected, the internal temperature of 170 ° C, and the 15th to 16th static mixers 17o to 17p (with a 0.5 m tube length and 2 static mixers with an internal diameter of 38 mmφ) And a tube temperature of 170 ° C.).

1623 parts by weight of dicyclohexyl methane diisocyanate (manufactured by Sumica Bayer Urethane Co., Ltd., melting at 50 ° C, hereinafter referred to as HMDI) was placed in a polyisocyanate storage tank 6 and adjusted to 40 ° C.

3048 parts by weight of a polyester polyol having a number average molecular weight of 200 (manufactured by Hokoku Seyou Co., Ltd., trade name: HT-12, melt at 95 ° C), and 50 ppm of first tin octoate (yoshitomi pine) by weight based on macropolyol Chemicals Co., Ltd., trade name: Stannock), 1.0 part by weight of bis (2,6-diisopropylphenyl) carbodiimide (Rasig GmbH, trade name: Stabilizer 7000), 0.34 based on 100 parts by weight of macropolyol Parts by weight of hindered phenolic antioxidants (Shiba Kaigi Co., Ltd., trade name: Irganox 1010), 0.34 parts by weight of benzotriazole-based UV absorber (manufactured by Johoku Chemical Co., Ltd., trade name: JF-83), 0.16 parts by weight of hinderamine A light stabilizer (manufactured by Asahi Denka Co., Ltd., trade name: LA-52) (hereinafter, these components are referred to as a polyol solution) was placed in a polyol storage tank 7 and adjusted to 90 ° C.

400 weight part (made by BASF Corporation, melting | fusing point: 50 degreeC) was put into the chain extender storage tank 8, and it adjusted to 50 degreeC. In addition, these operations were performed in nitrogen atmosphere.

Subsequently, a high speed stirrer 9 (SM40 manufactured by Sakura Plant Co., Ltd., SM40 at a set temperature of 120 ° C) at a flow rate of 16.8 kg / h, a polyol solution at a flow rate of 30.5 kg / h, and BG at a flow rate of 4.0 kg / h After passing through and stirring and mixing each raw material sufficiently, it passed through to the 1st static mixer 17a of the static mixer part 4.

Thereafter, the reactant flowing out of the sixteenth static mixer 17p is press-fitted into a single screw extruder (GM Engineering Co., Ltd., 65 mmφ, press-fitted portion 140 ° C.), and then extruded from the strand die 19, and an underwater cut device ( Pellet-shaped TPU was obtained by cutting in water by GaLa).

Example 3

In the manufacturing apparatus 1a shown in FIG. 1, without connecting the reaction port 16, the single screw extruder 18 was connected, and each static mixer 17 of the static mixer part 4 connected 16 stations was used. And TPU was manufactured by the following operation.

Moreover, the static mixer part 4 is the 1st-7th static mixers 17a-17g (a state which connected 7 static mixers with a pipe length of 0.5 m and an internal diameter of 20 mmφ, pipe | tube temperature 180 degreeC), 8th-agent 9 static mixers 17h to 17i (tube length 1.0 m, two static mixers with an inner diameter of 20 mmφ connected, pipe temperature 170 ° C), 10th to 14th static mixers (17j to 17n) (tube length 1.0 m , 5 static mixers with an internal diameter of 38 mmφ are connected to each other, the internal temperature of the tube is 180 ° C, and the 15th to 16th static mixers 17o to 17p (with a pipe length of 0.5 m and 2 static mixers with an internal diameter of 38 mmφ) , The internal temperature of the tube was 180 ° C).

1676 parts by weight of HMDI (manufactured by Sumica Bayer Urethane Co., Ltd., melt at 50 ° C) was placed in a polyisocyanate storage tank 6 and adjusted to 40 ° C.

2408 parts by weight of polycarbonate diol having a number average molecular weight of 2000 (manufactured by Ube Kyossan, trade name: UH-CARB 200 at 110 ° C), and dibutyltin dilaurate of 30 ppm by weight relative to macropolyol (Nitto Kase Manufacture of director, brand name: Neostan U-100,), 0.4 parts by weight of bis (2,6-diisopropylphenyl) carbodiimide (manufactured by BASF, trade name: Luplagen-9119), based on 100 parts by weight of polyol, 0.1 parts by weight of hindered phenolic antioxidant (manufactured by Ciba-Geigy Corporation, trade name: Irganox 1010), 0.34 parts by weight of benzotriazole ultraviolet absorber (manufactured by Johoku Chemical Co., Ltd., brand name: JF-83), 0.16 parts by weight of hinder An amine light stabilizer (manufactured by Asahi Denka Co., Ltd., trade name: LA-52) (hereinafter, these components were referred to as a polyol solution) was placed in a polyol storage tank 7 and adjusted to 110 ° C.

452 parts by weight of BG (manufactured by BASF Corporation, melt at 50 ° C) was placed in a chain extender storage tank 8 and adjusted to 50 ° C. In addition, these operations were performed in nitrogen atmosphere.

Subsequently, a high speed stirrer 9 (SM40 manufactured by Sakura Plant Co., Ltd., SM40 at a set temperature of 120 ° C) at a flow rate of 16.8 kg / h, a polyol solution at a flow rate of 24.1 kg / h, and a BG at a flow rate of 4.55 kg / h. After passing through and stirring and mixing each raw material sufficiently, it passed through to the 1st static mixer 17a of the static mixer part 4.

Thereafter, the reactant flowed out of the sixteenth static mixer 17p was press-fitted into a single screw extruder (GM Engineering, Inc., 65 mmφ, press-fitting part 140 ° C.), and then extruded from the strand die 19 and cooled in a water bath. Pellet-type TPU was obtained by cutting with a pelletizer (PPL-130 type, manufactured by Ishinaka Tekkojo Co., Ltd.).

Example 4

In the manufacturing apparatus 1b shown in FIG. 2, the reaction port 16a is connected only between two high speed stirrers 9a and 9b, and the single screw extruder 18 is connected and each static of the static mixer part 4 is carried out. Using the 16 connection of the mixer 17, the TPU was manufactured by the following operation.

Moreover, the static mixer part 4 is the 1st-7th static mixers 17a-17g (a state which connected 7 static mixers with a pipe length of 0.5 m and an internal diameter of 20 mmφ, internal temperature of 240 degreeC), 8th-agent 9 static mixers 17h to 17i (tube length 1.0 m, two static mixers with an inner diameter of 20 mm phi connected, pipe temperature 200 ° C), 10th to 14th static mixers (17j to 17n) (tube length 1.0 m 5 static mixers with an internal diameter of 38 mmφ are connected, the internal temperature of 170 ° C, and the 15th to 16th static mixers 17o to 17p (with a pipe length of 0.5 m and two static mixers with an internal diameter of 38 mmφ) , The internal temperature of the tube was 150 ° C).

MDI 1003 parts by weight (Mitsui Takeda Chemical Co., Ltd., trade name: Cosmonate PH) was placed in a polyisocyanate storage tank 6 and adjusted to 40 ° C.

3833 parts by weight of polyester polyol having a number average molecular weight of 2000 (manufactured by Mitsui Takeda Chemical, trade name: U-2001, melt at 120 ° C), and 0.3 part by weight of bis (2,6-diisopropyl) based on 100 parts by weight of macropolyol Phenyl) carbodiimide (RASCHIG GmbH, trade name: Stabilizer 7000) (hereinafter, these components are called polyol solution) was put into the polyol storage tank 7, and it adjusted to 120 degreeC.

17.6 parts by weight of BG (melted at 50 ° C by BASF Corporation) was placed in a chain extender storage tank 8 and adjusted to 50 ° C. In addition, these operations were performed in nitrogen atmosphere.

Subsequently, MDI was passed through the high-speed stirrer 9a (SM40 manufactured by Sakura Plant Co., Ltd., set temperature 120 ° C.) at a flow rate of 16.8 kg / h and a polyol solution at a flow rate of 38.3 kg / h. After stirring and mixing a raw material, the prepolymer (mixture) was synthesize | combined by hold | maintaining in reaction port 16a (10 L) for 10 minutes.

The prepolymer is passed through a high speed stirrer 9b (SM40 manufactured by Sakura Plant Co., Ltd., SM40, set temperature of 120 ° C) downstream at a flow rate of 55.1 kg / h and BG at a flow rate of 1.76 kg / h. After that, the liquid was passed through to the first static mixer 17a of the static mixer section 4.

Thereafter, the reactant flowing out of the sixteenth static mixer 17p was press-fitted into a single screw extruder (GM Engineering Co., Ltd., 65 mmφ, press-fitted portion 140 ° C), and then extruded from the strand die 19, and an underwater cut device (GaLa) Pellet-shaped TPU was obtained by cutting in water under the present invention.

Example 5

In the manufacturing apparatus 1c shown in FIG. 3, without connecting the reaction port 16 and the single screw extruder 18, each static mixer 17 of the static mixer part 4 is connected with 24 stations, The 1st TPU was manufactured by the following operation using the thing which connected the T-shaped connection pipe 21 between 4th static mixers 17a-17d and 5th-8th static mixers 17e-17h.

Moreover, the static mixer part 4 is the 1st-4th static mixers 17a-17d (the state which connected four static mixers with a pipe length of 0.5 m and an internal diameter of 38 mmφ, pipe | tube temperature 200-260 degreeC), 5th To 8th static mixers 17e to 17h (tube length 0.5 m, 4 static mixers with an inner diameter of 13 mm phi connected, pipe temperature 280 ° C), ninth to twelfth static mixers 17i to 17l (tube length Four static mixers with a diameter of 0.5 m and an internal diameter of 20 mmφ connected to each other, the internal temperature of 250 to 280 ° C, the thirteenth to sixteenth static mixers (17m to 17p) (0.5 m of pipe length and four internal diameters of 20 mmφ) In the state of connection, pipe | tube temperature 220-230 degreeC), the 17th-20th static mixers (17q-17t) pipe length 0.5m, the state which connected four static mixers of 20 mm diameter inside, pipe | tube temperature 210-220 degreeC) And the twenty-first to twenty-fourth static mixers (17u to 17x) (in a state in which four static mixers having a pipe length of 0.5 m and an inner diameter of 20 mmφ were connected, the internal temperature of the tube was 210 ° C).

MDI 326 weight part (Mitsui Takeda Chemical Co., Ltd. make, brand name: Cosmonate PH) was put into the polyisocyanate storage tank 6, and it adjusted to 45 degreeC.

510 parts by weight of polytetramethylene ether glycol having a number average molecular weight of 1000 (manufactured by Hodogaya Chemical Co., Ltd., trade name: PTG-1000), and 0.965 parts by weight of a hindered phenolic antioxidant (Ciba Specialty Chemical Co., Ltd.) based on 100 parts by weight of macropolyol. Manufacture, brand name: Irganox 1010 (Hereinafter, these components are called polyol solution) was put into the polyol storage tank 7, and it adjusted to 60 degreeC.

158 parts by weight of 1,4-bis (2-hydroxyethoxy) benzene (manufactured by Sun Techno Chemical Co., Ltd., trade name: BHEB, hereinafter referred to as BHEB) was placed in a chain extender storage tank 8, and adjusted to 125 ° C. did. In addition, these operations were performed in nitrogen atmosphere.

Subsequently, after passing MDI at a flow rate of 16.32 kg / h and a polyol solution at a flow rate of 25.76 kg / h, the mixture was passed through a high speed stirrer (SM40 manufactured by Sakura Plant Co., Ltd., set temperature 120 ° C.), and each raw material was sufficiently stirred and mixed. The liquid was passed through the first static mixer 17a of the static mixer section 4 to synthesize prepolymers having terminal groups in isocyanate groups in the first to fourth static mixers 17a to 17d.

The reaction rate of the isocyanate group was 99% when the free isocyanate group concentration (NCO%) of this prepolymer was measured and calculated.

Subsequently, the BHEB is continuously fed from the chain extender storage tank 8 at a flow rate of 7.92 kg / h, and the first to fourth static mixers 17a to 17d and the fifth to fifth agents in the static mixer section 4. 8 was passed through the T-shaped tube 21 between the static mixers 17e to 17h.

The reactant which flowed out in the 24th static mixer 17x was extruded from the strand die 19, and this was cut by the pelletizer 20, and it dried at 100 degreeC for 24 hours, and obtained the pellet-shaped TPU.

Example 6

In the manufacturing apparatus 1c shown in FIG. 3, without connecting the reaction port 16 and connecting the single screw extruder 18, each static mixer 17 of the static mixer part 4 is made into 24 connection, TPU connecting tube 21 is connected between the first to fourth static mixers 17a to 17d and the fifth to eighth static mixers 17e to 17h. Prepared.

Moreover, the static mixer part 4 is the 1st-4th static mixers 17a-17d (the state which connected four static mixers with a pipe length of 0.5 m and an internal diameter of 38 mmφ, pipe | tube temperature 200-250 degreeC), 5th To 8th static mixers 17e to 17h (tube length 0.5 m, 4 static mixers with an inner diameter of 13 mmφ connected, internal temperature 250C), 9th to 12th static mixers 17i to 17l (tube length) Four static mixers with a diameter of 0.5 m and an internal diameter of 20 mmφ connected to each other, the internal temperature of 230 to 250 ° C, the thirteenth to sixteenth static mixers (17 m to 17p) (four static mixers with a pipe length of 0.5 m and an internal diameter of 20 mmφ) In the state of connection, pipe | tube temperature 210-220 degreeC, the 17th-20th static mixers 17q-17t (pipe length 0.5m, 4 static mixers with an internal diameter of 20 mm phi), the inside temperature of 200-210 degreeC ) And the twenty-first to twenty-fourth static mixers (17u to 17x) (a pipe length of 0.5 m, a state in which four static mixers having an inner diameter of 20 mm phi were connected, and an internal temperature of the tube was 190 ° C).

Mixture of isomers of 2,5-, 2,6-diisocyanatemethyl-bicyclo [2,2,1] -heptane (manufactured by Mitsui Takeda Chemical, trade name: Cosmonate NBDI, hereinafter referred to as NBDI) It put in the polyisocyanate storage tank 6, and adjusted to 55 degreeC.

484 parts by weight of polycaprolactonediol having a number average molecular weight of 1000 (manufactured by Daicel Chemical Co., Ltd., Plaque Cell 210), and 20 ppm of dilauryl acid di-n-butyltin (manufactured by Tokyo Kasei Co., Ltd.) by weight based on macropolyol. ) And 1.2 parts by weight of a liquid light stabilizer (manufactured by Chiba Specialty Chemical Co., Ltd., trade name: Tinuvin B75) (hereinafter, these components are referred to as polyol solution) in a polyol storage tank 7 It adjusted to ° C.

185 parts by weight of BHEB (manufactured by Sun Techno Chemical Co., Ltd., trade name: BHEB) was placed in a chain extender storage tank 8, and adjusted to 125 ° C. In addition, these operations were performed in nitrogen atmosphere.

Subsequently, NBDI was passed through a high-speed stirrer (SM40 manufactured by Sakura Plant, set temperature 120 ° C) at a flow rate of 16.28 kg / h and a polyol solution at a flow rate of 24.49 kg / h. The liquid was passed through the first static mixer 17a of the static mixer section 4 to synthesize prepolymers having terminal groups in isocyanate groups in the first to fourth static mixers 17a to 17d.

In addition, the BHEB is continuously fed from the chain extender storage tank 8 at a flow rate of 9.23 kg / h and the first to fourth static mixers 17a to 17d and the fifth to fifth agents of the static mixer section 4. 8 was passed through to the T-shaped connecting pipe 21 between the static mixers 17e to 17h.

The reactant which flowed out in the 24th static mixer 17x was extruded from the strand die 19, this was cut by the pelletizer 20, and it dried at 100 degreeC for 24 hours, and obtained the pellet-shaped TPU.

Example 7

The TPU has twenty static mixers 17 continuously connected to the static mixer unit 4, and includes a single screw extruder 18 but no reaction port 16, and includes a first to twentieth static mixer ( 17a to 17l) and the thirteenth to twentieth static mixers 17m to 17t, which were manufactured by the following operation using the apparatus 1d shown in FIG. 4, including an injection tee 22 connected to the static mixer. .

The said static mixer part 4 is the 1st-7th static mixers 17a-17g (the state which connected 7 static mixers with a pipe length of 0.5 m and an inner diameter of 20 mmΦ, the internal temperature of 190 degreeC), 8th-9th Static mixers 17h to 17i (tube length 1.0 m and internal diameter 20 mm Φ two static mixers connected, pipe temperature 180 ° C), 10th to 12th static mixers 17j to 17l (tube length 1.0 m and inner diameter In the state which connected three static mixers with 38mm Φ, the internal temperature of 170 degreeC, the 13th-14th static mixers 17m-17n (the pipe length 0.5m, and two static mixers with an internal diameter of 20mmΦ), the inside of a pipe Temperature 170 ° C) and the fifteenth to twentieth static mixers 17o to 17t (a state in which six static mixers having a pipe length of 0.5 m and an internal diameter of 38 mm Φ are connected, and the inside temperature of the pipe is 170 ° C). A 30 mmφ single screw extruder 23 (manufactured by GM Engineering, 160-180 ° C.) is connected to the infusion tee 22.

1623 parts by weight of HMDI (manufactured by Sumika Bayer Urethane Co., Ltd., melting point 50 ° C.) was charged in a polyisocyanate storage tank 6, and the temperature was adjusted to 40 ° C.

3048 parts by weight of a polyester polyol having a number average molecular weight of 200 (trade name: HT-12, manufactured by Hokoku Corporation, melting point of 95 ° C), 1 st tin octoate (trade name: Stan Oct, manufactured by API Corporation) 25 ppm (macro) Based on the weight of the polyol), 1.0 parts by weight of bis (2,6-diisopropylphenyl) carbodiimide (trade name: Stabilizer 7000, manufactured by Rasig GmbH), impaired phenolic antioxidant (trade name: Irganox) 1010, manufactured by Ciba-Geigy Co., Ltd., 0.34 parts by weight, benzotriazole ultraviolet absorber (trade name: JF-83, manufactured by Johoku Chemical Co., Ltd.), and 0.34 parts by weight of the impaired amine light stabilizer (trade name: LA-52, Asaki Denka High School) 0.16 weight part (These compounds are called "polyol solution" hereafter.) To the polyol storage tank 7, and the temperature was adjusted to 90 degreeC.

400 weight part of BG (made by BASF Corporation, melting | fusing point 50 degreeC) was charged to the chain extender storage tank 8, and the temperature was adjusted to 50 degreeC. These operations were performed under a nitrogen atmosphere.

Subsequently, HMDI, polyol solution and BG were fed to the high speed stirrer 9 (SM40 manufactured by Sakura Plant Company Limited, preset temperature 120 ° C) at flow rates of 11.76 kg / h, 21.35 kg / h and 2.8 kg / h, respectively. It was. After fully stirring and mixing these raw materials, the mixture was supplied to the first static mixer 17 of the static mixer part 4.

In the continuous operation, the masterbatch pellet containing 40 wt% of a deodorant (trade name: Kesumon, manufactured by Toagosei Co., Ltd.) (same composition as the TPU obtained in Example 7) was shortened to a flow rate of 6 kg / h. Continuous filling into the extruder 23, from which the injection tee 22 positioned between the first to twentieth static mixers 17a to 17l and the thirteenth to twentieth static mixers 17m to 17t of the static mixer section 4. Supplied to.

Then, the reaction raw material discharged | emitted from the 20th static mixer 17t was compressed into the single screw extruder (65 mm (phi), 140 degreeC by a compression fixed part, GM engineering company limited company make). After extruding from the strand die 19, the reaction raw material was cut | disconnected in water by the underwater pelletizer (made by Gara Corporation), and the pellet form containing the deodorant added to the TPU was produced.

Comparative Example 1

Using the same raw material as Example 1 (but adding 40 ppm of catalyst in terms of weight based on the macropolyol), the mixture was mixed using the same high speed stirrer (SM40 manufactured by Sakura Plant Co., Ltd., set temperature of 120 ° C) as in Example 1. After passing through a 46 mmφ twin screw extruder (Ikegai Machinery, PCM46, L / D = 41.5, 200 to 250 ° C), mixing and reacting, a static mixer (tube length 0.5 m, inner diameter 38 mmφ, It pressed in in-tube temperature 200 degreeC).

Thereafter, pelletization was attempted in the same manner as in Example 1, but the melt viscosity did not rise at the tip of the die, and cut by the pelletizer was not possible.

Comparative Example 2

Using the same raw material as in Example 1 (however, the amount of the catalyst added at 1000 ppm based on the weight of the macropolyol), a pellet-type TPU was obtained by the same operation as in Comparative Example 1.

Comparative Example 3

Using the same raw material as in Example 2, each component was reacted by mixing in the reaction vessel. In this reaction, the reaction of HMDI was slow, even though about 1 hour had elapsed, fluidity was exhibited in the reaction vessel, and it was necessary for 5 hours or more until it completely solidified. Then, after annealing at 100 degreeC, TPU was obtained by the batch method by making a flake type with a cutter and a grinder.

Comparative Example 4

2408 parts by weight of polycarbonate diol having a number average molecular weight of 2000 containing 1599 parts by weight of MDI and an additive (0.34 parts by weight of a blocked phenolic antioxidant against 100 parts by weight of polyol) (manufactured by Ube Kyossan, trade name: UH-CARB 2000 After mixing each component using 452 weight part of BG, it annealed at 120 degreeC for 16 hours, Then, TPU was obtained by the batch method by making a flake type with a cutter and a grinder.

Comparative Example 5

A pellet-shaped TPU was obtained under the same apparatus and conditions as those of Comparative Example 1 using the same raw material as in Example 4 except that 20 ppm of first tin octoate was added based on the weight of the macropolyol. Moreover, although it manufactured without adding a catalyst like Example 4, it could not thicken until it could pelletize. On the other hand, when the melt viscosity of the TPU obtained in Example 4 was measured, it became 500 Pa.s or more, and the residual isocyanate reacted with time and it was 2000 Pa.s or more after 3 days.

Comparative Example 6

In the manufacturing apparatus 1a shown in FIG. 1, macropolyol, a polyisocyanate, and a chain extender were introduce | transduced directly into the static mixer, without connecting the mixing part 3, the reaction port 16, and the single screw extruder 18. FIG. Each static mixer 17 of the static mixer part 4 was comprised so that it may be connected continuously. The raw material adjusted like this was passed through this and the TPU was manufactured by the following operation.

Moreover, the static mixer part 4 is the 1st-4th static mixers 17a-17d (the state which connected four static mixers with a pipe length of 0.5 m and an internal diameter of 38 mmφ, pipe | tube temperature 200-260 degreeC), 5th To 8th static mixers 17e to 17h (tube length 0.5 m, 4 static mixers with an inner diameter of 13 mm phi connected, pipe temperature 280 ° C), ninth to twelfth static mixers 17i to 17l (tube length Four static mixers with a diameter of 0.5 m and an internal diameter of 20 mmφ connected to each other, the internal temperature of 250 to 280 ° C, the thirteenth to sixteenth static mixers (17m to 17p) (0.5 m of pipe length and four internal diameters of 20 mmφ) In the state of connection, pipe | tube temperature 220-230 degreeC, the 17th-20th static mixers 17q-17t (pipe length 0.5m, 4 static mixers with an internal diameter of 20 mm phi), pipe | tube temperature 210-220 degreeC ) And the twenty-first to twenty-fourth static mixers (17u to 17x) (a pipe length of 0.5 m, a state in which four static mixers having an inner diameter of 20 mmφ are connected, and an inside temperature of a tube is 210 ° C).

The polyol solution was passed through at a flow rate of 25.76 kg / h, MDI 16.32 kg / h, and BHEB at 7.92 kg / h.

The reactant which flowed out in the 24th static mixer 17x was extruded from the strand die 19, and this was cut by the pelletizer 20, and it dried at 100 degreeC for 24 hours, and obtained the pellet-shaped TPU.

Comparative Example 7

In the manufacturing apparatus 1a shown in FIG. 1, macropolyol, a polyisocyanate, and a chain extender were introduce | transduced directly into the static mixer, without connecting the mixing part 3, the reaction port 16, and the single screw extruder 18. FIG. Each static mixer 17 of the static mixer part 4 was comprised so that it may be connected continuously. The raw material adjusted to this was carried out similarly to Example 6 (however, the addition amount of di-n-butyltin dilauryl acid in the weight basis with respect to a macropolyol is 600 ppm). The TPU was manufactured by the following operation.

Moreover, the static mixer part 4 is the 1st-4th static mixers 17a-17d (the state which connected four static mixers with a pipe length of 0.5 m and an internal diameter of 38 mmφ, pipe | tube temperature 200-250 degreeC), 5th To 8th static mixers 17e to 17h (tube length 0.5 m, 4 static mixers with an inner diameter of 13 mmφ connected, internal temperature 250C), 9th to 12th static mixers 17i to 17l (tube length) Four static mixers with a diameter of 0.5 m and an internal diameter of 20 mmφ connected to each other, the internal temperature of 230 to 250 ° C, the thirteenth to sixteenth static mixers (17 m to 17p) (four static mixers with a pipe length of 0.5 m and an internal diameter of 20 mmφ) In the state of connection, pipe | tube temperature 210-220 degreeC, the 17th-20th static mixers 17q-17t (pipe length 0.5m, 4 static mixers with an internal diameter of 20 mm phi), the inside temperature of 200-210 degreeC ) And the twenty-first to twenty-fourth static mixers (17u to 17x) (a pipe length of 0.5 m, a state in which four static mixers having an inner diameter of 20 mm phi were connected, and an internal temperature of the tube was 190 ° C).

The polyol solution was passed at a flow rate of 24.49 kg / h, NBDI 16.28 kg / h, and BHEB at 7.92 kg / h.

The reactant which flowed out in the 24th static mixer 17x was extruded from the strand die 19, it was cut by the pelletizer 20, and it dried at 100 degreeC for 24 hours, and obtained the pellet-shaped TPU.

evaluation

Test Example 1

The melt viscosity after one day of the TPU obtained in Example 1 and Comparative Example 2 was measured using a high-priced flow tester (manufactured by Shimadzu Seisakusho Co., Ltd., model: CFT-500D, and measurement conditions are the same as those of the following item (3).) did. As a result, both TPUs were 10000 Pa.s or more.

When these TPUs were stored at room temperature in a cool dark place and the melt viscosity was measured after 2 months, the TPU of Example 1 had a reaction of the remaining isocyanate and had reached 15000 Pa.s or more, whereas the TPU of Comparative Example 2 was It became 7000 Pa.s or less and when it measured continuously, it was confirmed that melt viscosity fell further. It was estimated that the decrease in the melt viscosity of the TPU of Comparative Example 2 was due to decomposition by a catalyst.

Test Example 2

The TPU obtained by Example 3 (HMDI type) and Comparative Example 4 (MDI type) was produced by using an injection molding machine (75 MSII manufactured by Mitsubishi Juko Co., Ltd., set at 210 ° C) of a plate of 100 × 100 mm having a thickness of 3 mm. Each plate obtained was left to stand outdoors for one week in sunlight, and the light resistance test was carried out. One week later, as a result of comparing the plates, it was confirmed that the plate made of the TPU of Example 3 did not discolor, whereas the plate made of the TPU of Comparative Example 4 was clearly yellowed.

Test Example 3

The TPU obtained in Example 1 and Comparative Example 5 was molded into a sheet shape having a width of 80 mm and a thickness of 0.1 mm using a bra fender (manufactured by Brafender Co., Ltd.), and the fish eye (gelled) under the same conditions as in the following Item (4) ) Was measured.

As a result, the fish eye was confirmed in the initial stage of operation in the TPU of Comparative Example 5. On the other hand, in the TPU of Example 4, the fish eye could not be confirmed when 24 hours passed from the operation.

Test Example 4

The test piece was produced by shape | molding the TPU obtained by each Example 5 and 6 and each comparative example 6 and 7, by injection molding or the film, and measured about the item of following (1)-(5). Moreover, the test piece was heat-processed at 100 degreeC for 24 hours, and then used for various tests. The results are shown in Table 1.

(1) hardness

Shore hardness was measured by the method of JISK-7311 at 23 degreeC and 50% relative humidity. In addition, the durometer used A type.

(2) Tensile strength (unit: MPa), elongation at break (unit:%), tear strength (unit: kN / m), amount of taper wear (unit: mg), compression set (unit:%)

Tensile strength, elongation at break, tear strength and taper wear were measured at 23 ° C. and 50% relative humidity by the method described in JIS K-7311. The compression set was measured under the conditions of 20 hours at 70 ° C. by the method described in JIS K-6251.

(3) Flow start temperature (unit: ° C) and melting point range (unit: ° C)

2 g of pellets (or flakes) of the TPU obtained in Examples 5 and 6 and Comparative Examples 6 and 7, were charged into an expensive flow tester (manufactured by Shimadzu Corporation, model: CFT-500D), and 1 mm (diameter). The flow start temperature was measured on the conditions of a temperature increase rate of 2.5 degree-C / min, and a load of 196 N using the nozzle of 10 mm (length). The melting point range was measured as the difference between the temperature at which 2 g of pellets (or flakes) started melting and the temperature at which the outflow from the nozzle was completed.

(4) fish child (unit: dog / 300cm ² )

After molding the TPU obtained in Examples 5 and 6 and Comparative Examples 6 and 7, to a film having a thickness of 100 µm, the film having a length of 200 mm and a width of 150 mm was cut out and small granules having a diameter of 80 µm or more. ) Was measured with a polarizing microscope, and the number was measured.

(5) yellowing (ΔYI)

It measured based on JISK-7350-2A method using the injection molding sheet of TPU obtained by the comparative examples 6 and 7. Using a xenon irradiation tester (Super Xenon Weather Meter SX75: manufactured by Suga Tester Co., Ltd.) and irradiating under conditions of a black panel temperature of 63 ° C., a relative humidity of 50%, and an illuminance of 0.35 w / m ² , the test piece was extracted at 1000 hours, and yellow. Evaluated by the growth rate of the index.

Example and Comparative Example Example 5 Comparative Example 6 Example 6 Comparative Example 7 Hardness (Shore Hardness ・ A Type) 96 96 87 86 Tensile Strength (MPa) 51.2 44.5 41.1 38.2 Elongation at Break (%) 565 615 623 655 Tear strength (kN / m) 157.1 142.1 121.1 113.4 Teva wear (mg) 19 23 21 25 Compression set (%) 25.2 31.3 34.3 38.5 Flow start temperature (℃) 195 212 175 181 Melting Point Range (℃) 26 11 35 28 Fish Eyes (pcs / cm ² ) 21 387 15 245 Yellowing (ΔYI) Not rated Not rated 7.4 16.7

While exemplary embodiments of the present invention have been presented as described above, these are merely for illustrative purposes and should not be construed as limiting. Modifications of the invention will be apparent to those skilled in the art, which are also within the scope of the following claims.

As mentioned above, according to the manufacturing method and manufacturing apparatus of the thermoplastic polyurethane of this invention, generation | occurrence | production of a gelled product can be effectively prevented, and a macropolyol of a high melting point, a chain extender of a high melting point, and slow reaction Polyisocyanates can be used to continuously produce thermoplastic polyurethanes. Moreover, since a twin screw extruder is not used, it does not press by a mechanical shear of a screw, and does not produce gelation by retention in a groove | channel of a screw, and can manufacture by reducing a catalyst amount. As a result, a thermoplastic polyurethane with little physical property degradation and deterioration with time can be manufactured.

As a result, the thermoplastic polyurethane obtained as described above is less squeezed or gelled, there is less physical degradation and deterioration with time, and also has excellent mechanical properties such as tensile strength, elongation at break, tear strength, and compression set. Even if the hardness is the same, the flow start temperature is low and the melting point range is wide, thereby excellent molding processability. In addition, there are few gels associated with the pressed and granules, and even if so-called unyellowed polyisocyanate is used, the amount of catalyst can be reduced during production, and thus has excellent properties of not being yellowed further.

Claims (10)

A process for producing a thermoplastic polyurethane, wherein the reaction raw material comprising a mixture of at least polyisocyanate and macropolyol premixed and a chain extender is reacted while passing through a static mixer. The method for producing a thermoplastic polyurethane according to claim 1, wherein at least the polyisocyanate and the macropolyol are mixed by a high speed stirrer. The method according to claim 1, wherein the reaction raw material is prepared by mixing polyisocyanate, macropolyol and chain extender at the same time. The method for producing a thermoplastic polyurethane according to claim 1, wherein the reaction raw material is prepared by first mixing a polyisocyanate and a macropolyol, and then blending a chain extender with the obtained mixture. The method for producing a thermoplastic polyurethane according to claim 4, wherein after mixing the polyisocyanate and the macropolyol, the obtained mixture and the chain extender are mixed with a high speed stirrer. 5. The chain extender of claim 4, wherein after mixing the polyisocyanate and macropolyol, the obtained mixture is reacted by passing through the static mixer, and then chain extender is added to the mixture from a supply line connected to join the static mixer. A method for producing a thermoplastic polyurethane, which is blended. The method for producing a thermoplastic polyurethane according to claim 1, wherein the contact portion of the static mixer in contact with the reaction raw material is formed of a material substantially made of a nonmetallic material. The method of claim 1, wherein the static mixer includes a plurality of static mixers connected in series, each of which can independently control a temperature inside the static mixer. Mixing means for mixing at least polyisocyanate and macropolyol; And Chain extender blending means for blending a chain extender with at least a mixture of the polyisocyanate and macropolyol mixed by the mixing means; Static mixer for reacting the reaction raw material in which the chain extender is added to the mixture Apparatus for producing a thermoplastic polyurethane, comprising a. A thermoplastic polyurethane obtained by reacting a reaction raw material comprising a mixture of at least polyisocyanate and macropolyol pre-mixed with a chain extender while passing through a static mixer.