KR102298818B1 - Composition for producing polyurethane - Google Patents

Abstract

The present invention relates to a composition for producing a polyurethane comprising a novel crosslinking agent compound, and a method for producing a crosslinked polyurethane using the composition.
The present invention provides a cross-linked polyurethane composition comprising a novel cross-linking agent formed by a condensation reaction of a triamine-based compound and a hydroxy aldehyde compound, so that injection molding can be easily performed when manufacturing golf ball covers and other urethane products.

Description

Polyurethane production composition {Composition for producing polyurethane}

The present invention relates to a composition for producing a polyurethane comprising a novel crosslinking agent compound, and a method for producing a crosslinked polyurethane using the composition.

As the material of the golf ball cover, ionomer resin and polyurethane-based materials are widely used.

The ionomer resin has advantages in that it has excellent rebound elasticity, durability, workability, etc., but has problems such as difficult ball control and low spinability due to its rigid nature. Therefore, in order to overcome this problem, a low-hardness ionomer is mixed and used, but even in this case, the problems are partially improved, but the fundamental disadvantages of the ionomer cannot be overcome.

For this reason, recently, polyurethane-based materials are used, and a curing agent is added to the polyurethane prepolymer to form a two-component type, and it is mainly manufactured by casting molding method. However, since this casting molding method is a two-component curing type in which the main agent and the curing agent are separated and mixed, the operation is difficult and it is difficult to control the curing speed.

In particular, the initial investment cost for the casting molding process equipment is high, so the equipment of the existing injection molding process cannot be used, so the burden of having a separate casting molding process equipment for urethane cover molding is high.

In order to solve this problem, research on a polyurethane resin composition capable of injection molding has been conducted, and in Korean Patent Registration No. 10-1937663, a cross-linkable block prepolymer is mixed with a thermoplastic polyurethane and polyamide to produce a self-healing cross-linked polyurethane. Although the manufacturing process is disclosed, there is a problem in that a plurality of steps are required.

Therefore, there is a need to develop a new cross-linking agent capable of producing cross-linked polyurethane while securing more economical efficiency.

Korean Patent No. 10-1937663

The present invention is to solve the above problems, and an object of the present invention is to provide a composition for preparing a polyurethane that can be easily injection molded, including a novel crosslinking agent compound.

In addition, it is another object of the present invention to provide a method for preparing a cross-linked polyurethane from the composition.

the present invention

It provides a composition for preparing a polyurethane comprising a crosslinking compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R1, R2 and R3 are each independently H, OH or a C ₁ ~ C ₁₀ alkoxy group, which may be the same as or different from each other,

Wherein x and y are each independently an integer of 1 to 2.

The crosslinking agent compound of the present invention may be prepared by reacting a compound represented by the following formula (2) and a compound represented by the following formula (3).

[Formula 2]

In Formula 2,

Wherein x and y are each independently an integer of 1 to 2.

[Formula 3]

In Formula 3,

R1, R2 and R3 are each independently H, OH, or a C ₁ to C ₁₀ alkoxy group, and may be the same as or different from each other.

The crosslinking agent compound may be a compound represented by the following formula (4).

[Formula 4]

In Formula 4,

Wherein x and y are each independently an integer of 1 to 2.

Also, the present invention

preparing a crosslinking agent represented by the following formula (1) by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3); and

It provides a method for producing a cross-linked polyurethane comprising the step of reacting the cross-linking agent and the thermoplastic polyurethane to prepare an injection-type cross-linked polyurethane.

[Formula 2]

In Formula 2,

Wherein x and y are each independently an integer of 1 to 2.

[Formula 3]

In Formula 3,

R1, R2 and R3 are each independently H, OH, or a C ₁ to C ₁₀ alkoxy group, and may be the same as or different from each other.

[Formula 1]

In Formula 1,

R1, R2 and R3 are each independently H, OH or a C ₁ ~ C ₁₀ alkoxy group, which may be the same as or different from each other,

Wherein x and y are each independently an integer of 1 to 2.

The present invention provides a cross-linked polyurethane composition comprising a novel cross-linking agent formed by a condensation reaction of a triamine-based compound and a hydroxy aldehyde compound, so that injection molding can be easily performed when manufacturing golf ball covers and other urethane products.

In addition, it is possible to secure the mechanical properties of the polyurethane elastic body due to the cross-linking of the polyurethane, it is possible to secure the rebound elasticity and reverse rotation performance when applied to the golf ball cover.

1 is an FT-IR spectrum of a crosslinking agent prepared according to Example 1.
2 is an FT-IR spectrum of vanillin (4-hydroxy-3-methoxybenzaldehyde).
3 is an FT-IR spectrum of Jeffamine® T-403.
^{4 is a 1} H NMR spectrum of a crosslinking agent prepared according to Example 1.
^{5 is a 1} H NMR spectrum of vanillin (4-hydroxy-3-methoxybenzaldehyde).
^{6 is a 1} H NMR spectrum of Jeffamine® T-403.
7 is a photograph showing the results of the DMF dissolution experiment of the thermoplastic polyurethane.
8 is a photograph showing the results of the DMF dissolution experiment of the cross-linked polyurethane of the present invention.

Hereinafter, the present invention will be described in detail. The terms or words used in the present specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. It should be interpreted as meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The present invention features a composition for preparing a polyurethane comprising a crosslinking compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R1, R2 and R3 are each independently H, OH or a C ₁ ~ C ₁₀ alkoxy group, which may be the same as or different from each other,

Wherein x and y are each independently an integer of 1 to 2.

Preferably, any one selected from R1, R2 and R3 is OH, and each independently may be H, OH or a methoxy group, and the sum of x and y may be 3 to 4.

More preferably, the crosslinking agent compound may be a compound represented by the following Chemical Formula 4, but is not limited thereto.

[Formula 4]

In Formula 4,

Wherein x and y are each independently an integer of 1 to 2.

In addition, the crosslinking agent compound may be prepared by reacting a compound represented by the following formula (2) and a compound represented by the following formula (3).

[Formula 2]

In Formula 2,

Wherein x and y are each independently an integer of 1 to 2.

[Formula 3]

In Formula 3,

R1, R2 and R3 are each independently H, OH, or a C ₁ to C ₁₀ alkoxy group, and may be the same as or different from each other.

The crosslinking agent compound includes an imine group formed by a condensation reaction of an amine group in the compound represented by Formula 2 and an aldehyde group in the compound represented by Formula 3 above.

In the compound represented by Formula 3, preferably, any one selected from R1, R2 and R3 is OH, and may each independently be H, OH or a methoxy group. More preferably, 4-hydroxybenzaldehyde (4-Hydroxybenzaldehyde), 4-hydroxy-3-methoxybenzaldehyde (4-Hydroxy-3-methoxybenzaldehyde, Vanillin), 2-hydroxybenzaldehyde (2-Hydroxybenzaldehyde, Salicylaldehyde), 2-hydroxy-4-methoxybenzaldehyde (2-Hydroxy-4-methoxybenzaldehyde, 4-Methoxysalicylaldehyde) may be used, but is not limited thereto.

The crosslinking agent compound includes an azomethine (-C=N-) structure in the molecule, and has three phenol OH groups at the terminal, thereby exhibiting a structure advantageous for the crosslinking reaction of the polyurethane at high temperature, improving the injection property of the polyurethane However, it is possible to secure the strength by crosslinking.

In addition, the present invention,

preparing a crosslinking agent represented by the following formula (1) by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3); and

It is characterized in that it comprises the step of preparing an injection-type cross-linked polyurethane by reacting the cross-linking agent with the thermoplastic polyurethane.

[Formula 2]

In Formula 2,

Wherein x and y are each independently an integer of 1 to 2.

[Formula 3]

In Formula 3,

R1, R2 and R3 are each independently H, OH, or a C ₁ to C ₁₀ alkoxy group, and may be the same as or different from each other.

[Formula 1]

In Formula 1,

R1, R2 and R3 are each independently H, OH or a C ₁ ~ C ₁₀ alkoxy group, which may be the same as or different from each other,

Wherein x and y are each independently an integer of 1 to 2.

In this case, the compound represented by Formula 2 and the compound represented by Formula 3 may be subjected to a condensation reaction at about 50 to 100° C., preferably at 70 to 80° C. Water formed in the condensation reaction process may be removed using a vacuum or the like.

The prepared crosslinking agent may react with the thermoplastic polyurethane to form a crosslink of the thermoplastic polyurethane, preferably 1 to 50 parts by weight, more preferably 5 to 20 parts by weight based on 100 parts by weight of the thermoplastic polyurethane can be used

Hereinafter, examples and experimental examples will be described in detail to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

Example 1: Preparation of a novel cross-linking agent compound

In a 1L round flask, 228 g (1.5 mol) of vanillin represented by the following formula (5) was put and dissolved while maintaining the temperature at 80 °C.

[Formula 5]

Accordingly, 110 g (0.5 mol) of Jeffamine® T-403, a triamine compound, was added, and then the reaction was carried out while completely removing water under vacuum for about 5 hours or more to prepare a cross-linking agent compound.

Experimental Example 1: Confirmation of the FT-IR spectrum of the cross-linking agent compound

FT-IR spectra of the cross-linking agent compound prepared in Example 1 and the reactants vanillin and Jeffamine T-403 are shown in FIGS. 1 to 3, respectively.

In Figure 2, the carbonyl peak of the aldehyde group in vanillin (C=O, 1666 cm ^-1 ), in Figure 3 the primary amine peak of Jeffamine T-403 (-NH ₂ stretching, 3369, 3288 cm ^-1 , NH stretching 1591 cm ^{- 1} ) could be clearly identified.

As shown in FIG. 1, in the crosslinking agent compound, the carbonyl peak and the amine peak disappeared, and a new imine peak (C=N, 1643 cm ⁻¹ ) appeared, indicating that an imine group was formed by the condensation reaction.

Experimental Example 2: Cross-linking agent compound ^One H NMR spectrum Confirm

¹ H NMR spectra of the cross-linking agent compound prepared in Example 1 and the reactants vanillin and Jeffamine T-403 are shown in FIGS. 4 to 6 , respectively.

4, the aldehyde peak δ 9.84 (s, 1H) of vanillin and the amine peak δ 2.2-2.6 (broad, 2H) of Jeffamine T-403 disappear, and the characteristic peak of the imine group is δ 8.20 ( d, 3H), it could be confirmed that the imine group was formed by the condensation reaction.

<Crosslinking agent compound of Example 1>

¹ H NMR (400 MHz, Acetone-d ₆ ): δ 0.77-0.92 (m, 3H), 1.0-1.2 (m, 9H), 1.20-1.50 (m, 9H), 2.90 (b, 2H), 3.1-3.8 (m, 18H), 3.85 (m, 9H), 6.85 (d, 3H), 7.18 (t, 3H), 7.45 (s, 3H), 8.20 (d, 3H)

<Vaniline>

¹ H NMR (400 MHz, Acetone-d ₆ ): δ 3.95(s, 3H), 7.02(d, 1H), 7.47(m, 2H), 8.72(s, 1H), 9.84 (s, 1H)

<Jepamine T-403>

¹ H NMR (400 MHz, Acetone-d ₆ ): δ 0.77-0.92 (m, 3H), 1.0-1.2 (m, 9H), 1.20-1.50 (m, 9H), 2.90 (b, 2H), 3.1-3.8 (m, 18H), 3.85 (m, 9H), 6.85 (d, 3H), 7.18 (t, 3H), 7.45 (s, 3H), 8.20 (d, 3H)

Example 2: Preparation of cross-linked polyurethane

A crosslinked polyurethane was prepared by mixing 10 parts by weight of the crosslinking agent compound of Example 1 with respect to 100 parts by weight of the thermoplastic polyurethane (Dongsung Hichem TPU 5198AP) and performing stirring and exchange reaction while maintaining 180°C.

7 and 8 show the results of dissolving the prepared cross-linked polyurethane and the thermoplastic polyurethane (Dongsung Hichem TPU 5198AP) in DMF for 24 hours.

As shown in FIG. 7 , the thermoplastic polyurethane was completely dissolved in DMF to show a transparent solution state, but as shown in FIG. 8 , the prepared cross-linked polyurethane showed a gel shape that did not dissolve in DMF.

The gel was filtered and dried, and the weight was measured. As a result, the gel content was 35 wt%, and it was confirmed that the crosslinking of the polyurethane was achieved at a certain level.

Claims (4)

delete delete delete preparing a crosslinking agent represented by the following formula (1) by reacting a compound represented by the following formula (2) with a compound represented by the following formula (3); and
and reacting the crosslinking agent with the thermoplastic polyurethane to prepare an injection-type crosslinked polyurethane.
[Formula 2]

In Formula 2,
Wherein x and y are each independently an integer of 1 to 2.

[Formula 3]

In Formula 3,
R1, R2 and R3 are each independently H, OH or a C ₁ to C ₁₀ alkoxy group, and any one of R1, R2 and R3 is OH.

[Formula 1]

In Formula 1,
R1, R2 and R3 are each independently H, OH or a C ₁ ~ C ₁₀ alkoxy group, any one of R1, R2 and R3 is OH,
Wherein x and y are each independently an integer of 1 to 2.

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