KR20150101087A - Heterogeneous polyurethane prepolymer for nonpneumatic-type tire and method for manufacturing the same - Google Patents

Abstract

One aspect of the present invention provides a polyurethane prepolymer, regarding a polyurethane prepolymer, which is configured to react a polyisocyanate compound with a polyol mixture mixed with the weight ratio of 1 : 0.11-9 of polytetramethylene ether polyol and polycaprolactone polyol, respectively.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a polyurethane prepolymer for a non-pneumatic tire member mixed with a heterogeneous polyol, and a process for producing the polyurethane prepolymer. BACKGROUND ART < RTI ID = 0.0 >

TECHNICAL FIELD The present invention relates to a polyurethane prepolymer and a process for producing the same, and more particularly, to a polyurethane prepolymer containing a heterogeneous polyol at a certain ratio and a process for producing the same.

As oil prices rise and environmental pollution problems become global challenges, environmental regulations are tightening in China, which has recently emerged as the world 's second largest automobile market, as well as the US, EU, and Japan. It is clear that these environmental regulations will be strengthened in the future, and companies and organizations in each country are accelerating the development of technologies related to environmentally friendly tires. In addition, nitrosoamine-based additives and poly-Aromatic Hydrocarbons (PAHs) ) -Based oil in the tire industry, and is making various efforts to improve the environment of the tire industry.

Recently, advanced companies such as Michelin have been developing non-pneumatic tires utilizing new elastic materials, developing new processes to reduce energy and improve durability and recyclability of tires, and improve performance of other parts of tires To reduce the rolling resistance and to prepare for such environmental regulations.

The non-pneumatic tire is a tire having a structure in which a spoke portion having a shape similar to the spokes of a wagon is formed on a tire wheel and a tread portion of a tire contacting the ground surface is coupled to an outer surface of the spoke portion. The frictional resistance characteristic is important because the tread portion is in contact with and friction with the ground surface. On the other hand, in the spoke portion, the glass transition temperature and the tensile characteristic are set so as to prevent the tire from being compressed, It is important to adjust.

Recently, as the trade barriers in the automobile industry have been lifted and the climate variability of each country has become larger, studies on tire spoke members capable of exhibiting the same physical characteristics under different climatic conditions are underway. Among them, poly Urethane elastomers have attracted attention.

Korean Patent Laid-Open No. 10-2012-0096132 discloses a polycaprolactone polyol, a polycarbonate polyol or a mixture thereof as a polyurethane prepolymer for a non-pneumatic tire member. However, such a prepolymer has a high tensile strength, There is a problem in that it is difficult to secure the cold resistance required under the conditions. In response thereto, there is a growing demand for a polyurethane prepolymer for a tire member that can simultaneously realize physical properties as well as heat resistance and cold resistance.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a polyurethane prepolymer for a tire member which can be applied regardless of region and climate by simultaneously realizing heat resistance and cold resistance as well as physical properties, To provide a manufactured non-pneumatic tire member.

In order to achieve the above object, one aspect of the present invention is a polyurethane prepolymer, wherein a polyol mixture in which a polytetramethylene ether polyol and a polycaprolactone polyol are mixed at a weight ratio of 1: 0.11 to 9, A polyisocyanate compound, and an isocyanate compound.

In one embodiment, the polytetramethylene ether polyol may be polytetramethylene ether glycol.

In one embodiment, the polycaprolactone polyol may be polycaprolactone glycol.

In one embodiment, the number average molecular weight of the polytetramethylene ether polyol and the polycaprolactone polyol may be 250 to 10,000, respectively.

In one embodiment, the polyisocyanate compound may be diphenylmethane diisocyanate.

In one embodiment, the NCO% of the polyurethane prepolymer may range from 8.0 to 12.0%.

In order to achieve the above object, another aspect of the present invention provides a non-pneumatic tire member characterized by comprising a polyurethane elastomer cast by adding a chain extender to a polyurethane prepolymer.

In one embodiment, the reaction index of the polyurethane prepolymer and the chain extender may range from 80 to 120%.

In one embodiment, the chain extender is selected from the group consisting of 1,4-butanediol, hydroquinone-bis-hydroxyethyl ether, 1,4-cyclohexanedimethanol, trimethylolpropane, ethylenediamine, 1,2- 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine and 1,4-cyclohexanediamine And the like.

In order to achieve the above object, another aspect of the present invention is a method for producing a polyurethane prepolymer, which comprises mixing polytetramethylene ether glycol and polycaprolactone glycol at a weight ratio of 1: 0.11 to 9, Preparing a polyol mixture; And polymerizing the polyurethane prepolymer by stirring the polyol mixture and the polyisocyanate compound. The present invention also provides a method for producing a polyurethane prepolymer.

In one embodiment, the number average molecular weight of the polytetramethylene ether glycol and the polycaprolactone glycol may be 250 to 10,000, respectively.

In one embodiment, the polyisocyanate compound may be diphenylmethane diisocyanate.

In one embodiment, the NCO% of the polyurethane prepolymer may range from 8.0 to 12.0%.

In order to achieve the above object, another aspect of the present invention provides a method for producing a polyurethane prepolymer, comprising: adding a chain extender to a polyurethane prepolymer and then stirring to prepare a melt; And introducing the melt into a preheated mold to produce a polyurethane elastomer. The present invention also provides a method of manufacturing a non-pneumatic tire member.

In one embodiment, the reaction index of the polyurethane prepolymer and the chain extender may range from 80 to 120%.

In one embodiment, the chain extender is selected from the group consisting of 1,4-butanediol, hydroquinone-bis-hydroxyethyl ether, 1,4-cyclohexanedimethanol, trimethylolpropane, ethylenediamine, 1,2- 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine and 1,4-cyclohexanediamine And the like.

According to one aspect of the present invention, by using a polyol mixture in which a polytetramethylene ether polyol and a polycaprolactone polyol are mixed as a raw material of a polyurethane prepolymer and an elastomer in a certain ratio, The physical and mechanical characteristics required to achieve the desired characteristics can be harmonized.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

1 is a graphical representation of the relationship between elongation and tensile strength of a polyurethane elastomer according to an embodiment of the present invention.
FIG. 2 is a graphical representation of the correlation between temperature and loss factor (tan delta) of a polyurethane elastomer according to an embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" to another part, it includes not only "directly connected" but also "indirectly connected" . Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Polyurethane prepolymer ( prepolymer )

In order to achieve the above object, one aspect of the present invention is a polyurethane prepolymer, wherein a polyol mixture in which a polytetramethylene ether polyol and a polycaprolactone polyol are mixed at a weight ratio of 1: 0.11 to 9, A polyisocyanate compound, and an isocyanate compound.

As used herein, the term "prepolymer" refers to a polymer having a relatively low degree of polymerization, in which the polymerization reaction is terminated in the middle stage to facilitate molding of the final polymer. The synthesis route through such a prepolymer may be advantageous in that a part of the reaction heat is already generated in the synthesis of the prepolymer to reduce the exothermicity of the substantial polymer synthesis.

The polyol mixture may be a mixture of the polytetramethylene ether polyol and the polycaprolactone polyol, or a mixture of a known polyol such as a polyester polyol or an acrylic polyol.

The polyol mixture may be prepared by mixing the polytetramethylene ether polyol and the polycaprolactone polyol at a weight ratio of 1: 0.11 to 9, respectively, in order to prevent the physical properties of the polyurethane prepolymer and the tire member produced therefrom from deteriorating .

In the polyol mixture, when the content of the polycaprolactone polyol relative to 1 part by weight of the polytetramethylene ether polyol is less than 0.11 parts by weight, heat resistance and tensile strength may be lowered. When the content is more than 9 parts by weight, Can be degraded.

The polytetramethylene ether polyol may be a polytetramethylene ether glycol prepared by ring-opening polymerization with a tetrahydrofuran monomer and an acid catalyst, and the polycaprolactone polyol may be a polycaprolactone polymer produced by ring-opening polymerization with a caprolactone monomer and a catalyst, Lactone glycol, and other commercially available polytetramethylene ether glycols and polycaprolactone glycols.

The number-average molecular weight of the polycaprolactone polyol and / or the polytetramethylene ether polyol is preferably in the range of from 0.01 to 10 parts by weight, more preferably from 0.1 to 10 parts by weight, Can be from 250 to 10,000, preferably from 500 to 6,000, and more preferably from 650 to 3,000.

The polyisocyanate compound may be a diisocyanate compound so that the prepared polyurethane prepolymer may cause an additional crosslinking reaction, and may preferably be diphenylmethane diisocyanate.

The diphenylmethane diisocyanate is superior in physical properties and processability to aliphatic diisocyanates such as hexamethylene diisocyanate or isophorone diisocyanate, has a lower vapor pressure than toluene diisocyanate, The storage stability can be improved as compared with a polyurethane prepolymer prepared from paraffin diisocyanate or naphthalene diisocyanate having a high melting point.

The polyurethane prepolymer may be a NCO term prepolymer suitable for the production of an elastomer. In the case of the prepolymer at the OH end, the molecular weight is more than twice that of the prepolymer at the NCO end, so that it may not be suitable for the production of a high viscosity casting elastomer.

The NCO% of the polyurethane prepolymer may be in the range of 8.0 to 12.0%, preferably in the range of 9.2 to 11.5%, and more preferably in the range of 9.6 to 10.2%. If the NCO% value is less than 8.0%, the physical properties such as hardness, tensile strength, repulsive elastic modulus and abrasion resistance may be lowered due to a low hard phase content. If the NCO% value is more than 12.0%, hardness of the urethane group The size of the phase is increased and the strain rate may be greatly increased due to the rearrangement of the hard phase during tension and compression.

As used herein, the term "NCO%" is the percentage of the unreacted remaining NCO groups in the polyurethane prepolymer, expressed as a percentage, and can be calculated by the following equation.

[Equation 1]

NCO% = [100 * 2 * (NCO chemical formula) * (capping ratio -1)] / [{(diisocyanate molecular weight) * (capping ratio)} +

In the above formula (1), the capping ratio is the molar ratio of the diisocyanate to the molar ratio of the polyol.

The polyurethane prepolymer may be used to prepare a polyurethane elastomer by reacting with a chain extender immediately after preparation, and may be cooled at a low temperature for later use.

Non-pneumatic  The tire member

In order to achieve the above object, another aspect of the present invention provides a non-pneumatic tire member characterized by comprising a polyurethane elastomer cast by adding a chain extender to a polyurethane prepolymer.

As used herein, the term "elastomer" means a polymeric material having rubber elasticity such as vulcanized rubber at room temperature, which is melted and plasticized when heated to a high temperature and molded by a conventional plastic molding machine.

The polyurethane elastomer can be cast by stirring the polyurethane prepolymer decompressed and deaerated at room temperature or at a temperature elevated temperature with a chain extender, and the cast polyurethane elastomer can be used as a non-pneumatic tire member as an elastic molding.

As used herein, the term "chain extender" refers to a material that extends the backbone of the polymer and is commonly referred to as a cross-linker.

The chain extender may be an organic diamine compound or a polyol compound depending on the reactivity, applicability, process conditions, or casting time, but is not limited thereto. Preferably, the chain extender is a low melting point solid or liquid, May be an alcohol-based material or a mixture thereof.

On the other hand, the reaction index of the polyurethane prepolymer and the chain extender may range from 80 to 120%, preferably from 95 to 110%.

As used herein, the term "reaction index" refers to the number of moles of isocyanate-reactive hydrogen atoms present in the chain extender (number of moles) contained in the polyurethane prepolymer The ratio of the number of moles of NCO functional groups expressed as a percentage, which may be expressed by the following formula (2), is also referred to as "isocyanate index" or "NCO index".

&Quot; (2) "

Reaction index (%) = 100 * [number of moles of NCO functional groups contained in the polyurethane prepolymer] / [number of moles of isocyanate-reactive hydrogen atoms present in the chain extender]

If the reaction index is less than 80%, the physical properties such as hardness and tensile strength may be lowered due to a low hard phase content in the polyurethane elastomer. If the reaction index is more than 120%, the hard phase size in the casting elastomer increases, The strain rate can be greatly increased due to the rearrangement of the hard phase.

In one embodiment, the chain extender is selected from the group consisting of 1,4-butanediol, hydroquinone-bis-hydroxyethyl ether, 1,4-cyclohexanedimethanol, trimethylolpropane, ethylenediamine, 1,2- 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine and 1,4-cyclohexanediamine But is not limited thereto. Preferably, aliphatic diol such as 1,4-butanediol, hydroquinone-bis-hydroxyethyl ether, 1,4-cyclohexanedimethanol and trimethylolpropane .

Polyurethane Prepolymer ( prepolymer ) And Non-pneumatic  Manufacturing Method of Tire Member

In order to achieve the above object, another aspect of the present invention is a method for producing a polyurethane prepolymer, which comprises mixing polytetramethylene ether glycol and polycaprolactone glycol at a weight ratio of 1: 0.11 to 9, Preparing a polyol mixture; And polymerizing the polyurethane prepolymer by stirring the polyol mixture and the polyisocyanate. The present invention also provides a method for producing a polyurethane prepolymer.

The polytetramethylene ether glycol and the polycaprolactone glycol are completely defoamed at a temperature of 60 to 80 DEG C, preferably 65 to 75 DEG C under vacuum, and then mixed at a weight ratio of 1: 0.11 to 9 respectively To prepare a polyol mixture.

Then, 50 to 80 parts by weight of diphenylmethane diisocyanate is mixed and stirred in the polyol mixture at a temperature of 40 to 60 ° C, preferably 45 to 55 ° C, per 100 parts by weight of the prepared polyol mixture to prepare a polyurethane prepolymer have.

The polyol (or glycol) used in the production of the polyurethane prepolymer, the kind, specification, physical properties, mixing ratio and the like of the polyisocyanate are as described above.

According to another aspect of the present invention, there is provided a method for preparing a polyurethane prepolymer, comprising the steps of: adding a chain extender to a polyurethane prepolymer and stirring to prepare a melt; And introducing the melt into a preheated mold to produce a polyurethane elastomer. The present invention also provides a method of manufacturing a non-pneumatic tire member.

Before the chain extender is added, the polyurethane prepolymer is degassed by stirring at 70 to 90 ° C, preferably 75 to 85 ° C, to remove the bubbles contained in the polyurethane prepolymer. The chain extender preheated to 30 to 50 ° C, preferably 35 to 45 ° C, may be added to the polyurethane prepolymer from which the air bubbles have been removed and then stirred to prepare a melt.

Then, the polyurethane elastomer can be prepared by using the mold preheated at 100 to 120 ° C. The polyurethane elastomer can be used as a non-pneumatic tire member as an elastic molding.

On the other hand, the reaction index of the polyurethane prepolymer and the chain extender may range from 80 to 120%, and the meaning and range of the reaction index are as described above.

In one embodiment, the chain extender is selected from the group consisting of 1,4-butanediol, hydroquinone-bis-hydroxyethyl ether, 1,4-cyclohexanedimethanol, trimethylolpropane, ethylenediamine, 1,2- 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine and 1,4-cyclohexanediamine And the like.

Meanwhile, in the production of the non-pneumatic tire member, additives and other auxiliary materials may be mixed. Incorporable additives or auxiliary substances include, but are not limited to, catalysts, stabilizers, UV stabilizers, hydrolytic stabilizers, emulsifiers, dyes, and color pigments.

Such catalysts include trialkylamines, diazabicyclooctanes, tin dioctanoate, dibutyltin dilaurate, N-alkyl morpholine, lead, zinc, calcium or magnesium octanoate and the corresponding naphthenates and p - Nitrophenate can be used.

Such stabilizers may be selected from the group consisting of Bronsted acid and Lewis acid such as hydrochloric acid, benzoyl chloride or organic mineral acids such as dibutyl phosphate and adipic acid, malic acid, succinic acid, tartaric acid or citric acid have.

As the UV stabilizer or the hydrolysis stabilizer, 2,6-dibutyl-4-methylphenol or a sterically hindered carbodiimide may be used.

As the dye, a dye having a Zeritivinov active hydrogen atom, i.e., capable of reacting with an NCO group, may be used.

The polyol (or glycol) used in the production of the polyurethane prepolymer, the kind, specification, physical properties, mixing ratio and the like of the polyisocyanate are as described above.

Hereinafter, embodiments of the present invention will be described in detail.

Example  One

60 parts by weight of 98.5% by weight of 4,4'-diphenylmethane diisocyanate (Cosmonate PH by Kumho) was heated to 50 DEG C in a stirring flask under nitrogen, 100 parts by weight of a mixture of tetramethylene ether glycol / polycaprolactone glycol 9: 1 (weight ratio) was added to the stirring flask and stirred to polymerize a polyurethane prepolymer having an NCO content of 10.0%. The reaction was allowed to proceed for another hour and then the physical properties were measured.

100 parts by weight of the polymerized polyurethane prepolymer was degassed under a vacuum at 80 캜 while stirring until the bubbles disappeared. The degassed polyurethane prepolymer was stirred with 9.75 parts by weight of 1,4-butanediol preheated at 40 DEG C for 30 to 80 seconds at 200 to 500 rpm, and the melt was preheated to 110 DEG C having dimensions corresponding to the test standards Mold. The melt was then heated at < RTI ID = 0.0 > 110 C < / RTI > for 24 hours and the mechanical properties were measured.

Example  2

60 parts by weight of 98.5% by weight of 4,4'-diphenylmethane diisocyanate (Cosmonate PH by Kumho) was heated to 50 DEG C in a stirring flask under nitrogen, 100 parts by weight of a mixture of tetramethylene ether glycol / polycaprolactone glycol 7: 3 (weight ratio) was added to the stirring flask and stirred to polymerize a polyurethane prepolymer having an NCO content of 10.0%. The reaction was allowed to proceed for another hour and then the physical properties were measured.

100 parts by weight of the polymerized polyurethane prepolymer was degassed under a vacuum at 80 캜 while stirring until the bubbles disappeared. The degassed polyurethane prepolymer was mixed with 9.75 parts by weight of 1,4-butanediol preheated at 40 DEG C for 30 to 80 seconds at 200 to 500 rpm, and the resulting melt was preheated to 110 DEG C having dimensions corresponding to the test specimen Respectively. The melt was then heated at < RTI ID = 0.0 > 110 C < / RTI > for 24 hours and the mechanical properties were measured.

Example  3

60 parts by weight of 98.5% by weight of 4,4'-diphenylmethane diisocyanate (Cosmonate PH by Kumho) was heated to 50 DEG C in a stirring flask under nitrogen, 100 parts by weight of a mixture of tetramethylene ether glycol / polycaprolactone glycol 3: 7 (weight ratio) was added to the stirring flask and stirred to polymerize a polyurethane prepolymer having an NCO content of 10.0%. The reaction was allowed to proceed for another hour and then the physical properties were measured.

100 parts by weight of the polymerized polyurethane prepolymer was degassed under a vacuum at 80 캜 while stirring until the bubbles disappeared. The degassed polyurethane prepolymer was stirred with 9.75 parts by weight of 1,4-butanediol preheated at 40 DEG C for 30 to 80 seconds at 200 to 500 rpm, and the melt was preheated to 110 DEG C having dimensions corresponding to the test standards Mold. The melt was then heated at < RTI ID = 0.0 > 110 C < / RTI > for 24 hours and the mechanical properties were measured.

Example  4

60 parts by weight of 98.5% by weight of 4,4'-diphenylmethane diisocyanate (Cosmonate PH by Kumho) was heated to 50 DEG C in a stirring flask under nitrogen, 100 parts by weight of a mixture of tetramethylene ether glycol / polycaprolactone glycol 1: 9 (weight ratio) was added to the stirring flask and stirred to polymerize a polyurethane prepolymer having an NCO content of 10.0%. The reaction was allowed to proceed for another hour and then the physical properties were measured.

100 parts by weight of the polymerized polyurethane prepolymer was degassed under a vacuum at 80 캜 while stirring until the bubbles disappeared. The degassed polyurethane prepolymer was stirred with 9.75 parts by weight of 1,4-butanediol preheated at 40 DEG C for 30 to 80 seconds at 200 to 500 rpm, and the melt was preheated to 110 DEG C having dimensions corresponding to the test standards Mold. The melt was then heated at < RTI ID = 0.0 > 110 C < / RTI > for 24 hours and the mechanical properties were measured.

Comparative Example  One

60 parts by weight of 98.5% by weight of 4,4'-diphenylmethane diisocyanate (Cosmonate PH by Kumho) was heated to 50 DEG C in a stirring flask under nitrogen, 100 parts by weight of tetramethylene ether glycol was added to the stirring flask and stirred to polymerize a polyurethane prepolymer having an NCO content of 10.0%. The reaction was allowed to proceed for another hour and then the physical properties were measured.

100 parts by weight of the polymerized polyurethane prepolymer was degassed under a vacuum at 80 캜 while stirring until the bubbles disappeared. The degassed polyurethane prepolymer was stirred with 9.75 parts by weight of 1,4-butanediol preheated at 40 DEG C for 30 to 80 seconds at 200 to 500 rpm, and the melt was preheated to 110 DEG C having dimensions corresponding to the test standards Mold. The melt was then heated at < RTI ID = 0.0 > 110 C < / RTI > for 24 hours and the mechanical properties were measured.

Comparative Example  2

60 parts by weight of 98.5% by weight of 4,4'-diphenylmethane diisocyanate (Cosmonate PH by Kumho) was heated to 50 DEG C in a stirring flask under nitrogen, 100 parts by weight of caprolactone glycol was added to the stirring flask and stirred to polymerize a polyurethane prepolymer having an NCO content of 10.0%. The reaction was allowed to proceed for another hour and then the physical properties were measured.

100 parts by weight of the polymerized polyurethane prepolymer was degassed under a vacuum at 80 캜 while stirring until the bubbles disappeared. The degassed polyurethane prepolymer was stirred with 9.75 parts by weight of 1,4-butanediol preheated at 40 DEG C for 30 to 80 seconds at 200 to 500 rpm, and the melt was preheated to 110 DEG C having dimensions corresponding to the test standards Mold. The melt was then heated at < RTI ID = 0.0 > 110 C < / RTI > for 24 hours and the mechanical properties were measured.

Table 1 shows the specifications of the polyurethane prepolymer prepared according to Examples 1 to 4 and Comparative Examples 1 and 2.

division NCO Range
(% NCO) Brookfield
Viscosity,
Poise @ 80 ° C Appearance
@ 25 ° C Pot Life,
min Color,
Gardner Specific
Gravity Example 1 9.85-10.2 490 Solid 3-4 0-2 1.12 Example 2 9.85-10.2 495 Solid 3-4 0-2 1.12 Example 3 9.85-10.2 495 Solid 3-4 0-2 1.13 Example 4 9.85-10.2 500 Solid 3-4 0-2 1.15 Comparative Example 1 9.85-10.2 482 Solid 3-4 0-2 1.11 Comparative Example 2 9.85-10.2 515 Solid 3-4 0-2 1.15

Experimental Example

The physical properties and mechanical properties of the polyurethane prepolymer and the polyurethane elastomer prepared according to Examples 1 to 4 and Comparative Examples 1 and 2 were measured according to the following test methods and the results are shown in Table 2, Respectively.

- Hardness: ASTM D2240

- Tensile strength: ASTM D412

- Elongation at break: ASTM D412

-300% Modulus of elasticity: ASTM D412

- Permanent Compression Ratio: ASTM D395

-Tan [delta]: ASTM D5992

- Abrasion resistance: ASTM D5963

- Rebound modulus: ASTM D2632

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 NCO% 10 10 10 10 10 10 Index (NCO / OH) 105 105 105 105 105 105 Hardness
(shorea) 95 95 94 94 96 93 Tensile Strength (MPa) 40 45 47 52 33 56 Elongation (%) 577 532 520 534 540 540 300% modulus of elasticity (MPa) 15.4 17 17.3 17.5 14.6 17.8 Permanent compression
Row tone rate (%) 19 19 18 18 20 17 Tg (占 폚) -47 -37 -30 -24 -53 -21 Tanδ
(@ Tg) 0.33 0.39 0.43 0.46 0.30 0.47 Abrasion resistance (g) 0.04 0.04 0.05 0.05 0.03 0.05 Resilience (%) 57 54 53 50 59 48

Referring to Table 2 and FIGS. 1 and 2, Comparative Examples 1 and 2 are polyurethane prepolymers and polyurethane elastomers, which are polyol-polyol-polyol synthesized using polytetramethylene ether polyol and polycaprolactone polyol alternatively, , Tensile strength, abrasion resistance, and physical and mechanical properties.

On the other hand, in the case of Examples 1 to 4, by mixing the polytetramethylene ether polyol and the polycaprolactone polyol at a certain ratio, specifically, in a weight ratio of 1: 0.11 to 9, the cold resistance of the polytetramethylene ether polyol and the polycaprolactone It was confirmed that the heat resistance and the tensile excellence of the polyol can be harmonized.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (16)

In the polyurethane prepolymer,
A polytetramethylene ether polyol and a polycaprolactone polyol are mixed at a weight ratio of 1: 0.11 to 9, respectively, with a polyisocyanate compound.
The method according to claim 1,
Wherein the polytetramethylene ether polyol is polytetramethylene ether glycol; and polyurethane prepolymer.
The method according to claim 1,
Wherein the polycaprolactone polyol is polycaprolactone glycol; and polyurethane prepolymer.
The method according to claim 1,
Wherein the polytetramethylene ether polyol and the polycaprolactone polyol have a number average molecular weight of 250 to 10,000, respectively.
The method according to claim 1,
Wherein the polyisocyanate compound is diphenylmethane diisocyanate.
The method according to claim 1,
Wherein the NCO% of the polyurethane prepolymer is in the range of 8.0 to 12.0%.
A non-pneumatic tire member characterized by comprising a polyurethane elastomer cast by adding a chain extender to the polyurethane prepolymer according to any one of claims 1 to 6.
8. The method of claim 7,
Wherein the reaction index of the polyurethane prepolymer and the chain extender is in the range of 80 to 120%.
8. The method of claim 7,
Wherein the chain extender is selected from the group consisting of 1,4-butanediol, hydroquinone-bis-hydroxyethyl ether, 1,4-cyclohexanedimethanol, trimethylolpropane, ethylenediamine, Propane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine and 1,4-cyclohexanediamine, A non-pneumatic tire member.
In the process for producing a polyurethane prepolymer,
Mixing polytetramethylene ether glycol and polycaprolactone glycol in a weight ratio of 1: 0.11 to 9, respectively, to prepare a polyol mixture; And
And polymerizing the polyurethane prepolymer by stirring the polyol mixture and the polyisocyanate compound to form a polyurethane prepolymer.
11. The method of claim 10,
Wherein the polytetramethylene ether glycol and the polycaprolactone glycol have a number average molecular weight of 250 to 10,000, respectively.
11. The method of claim 10,
Wherein the polyisocyanate compound is diphenylmethane diisocyanate.
11. The method of claim 10,
Wherein the NCO% of the polyurethane prepolymer is in the range of 8.0 to 12.0%.
13. A process for producing a polyurethane prepolymer, comprising the steps of: adding a chain extender to a polyurethane prepolymer prepared according to the process of any one of claims 10 to 13, followed by stirring to prepare a melt; And
And injecting the melt into a preheated mold to produce a polyurethane elastomer. ≪ RTI ID = 0.0 > 8. < / RTI >
15. The method of claim 14,
Wherein the reaction index of the polyurethane prepolymer and the chain extender is in the range of 80 to 120%.
15. The method of claim 14,
Wherein the chain extender is selected from the group consisting of 1,4-butanediol, hydroquinone-bis-hydroxyethyl ether, 1,4-cyclohexanedimethanol, trimethylolpropane, ethylenediamine, Propane, 1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane, 1,6-hexamethylenediamine and 1,4-cyclohexanediamine, A method of manufacturing a non-pneumatic tire member.

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