TWI585079B - Urethane compound - Google Patents

Description

Carbamate compound

This invention relates to a carbamate compound, and more particularly to a carbamate compound for use in synthesizing a copolymerizable monomer with a copolymerizable monomer.

In recent years, thermoplastic resins have been widely used in various fields, such as households, because of their good formability, physical and mechanical properties, especially the good appearance and gloss of molded articles. Electrical appliances, mechanical parts, office supplies, electronic components and the automotive industry.

In general, thermoplastic resins can be processed by molding methods such as injection molding, extrusion molding, and blow molding. In addition, in the case of a specific processing, the resin is first formed into a sheet and then molded. In order to achieve this, the resin must have a high melt strength (i.e., increase the molecular weight of the resin) to maintain good thickness uniformity and dimensional stability during thermoforming or vacuum forming.

However, when the molecular weight of the resin is increased, disadvantages such as a decrease in fluidity, deterioration in workability, and reduction in productivity are caused. In order to improve this disadvantage, it is usually improved by adding a diverging agent. In the prior art, the added divergent agent is polyfunctional. a reactive monomer such as a divinyl compound or a polyvalent acrylate compound; however, if such a monomer is used in the process, it is easy to cause disadvantages such as reduced fluidity and poor processability. Cross-linking causes the resin to adhere to the surface of the pipe to form carbides, which causes the process to be unsmooth and causes the resulting resin to have a poor hue.

In summary, how to improve the degree of divergence to increase the melt tension of the resin, and at the same time contribute to the thin meat processing and improve the production stability, is a subject that has long been a breakthrough in the field of technology.

The present invention provides a novel carbamate compound for synthesizing into a divergent copolymer with a copolymerizable monomer, so that the molded article has a high melt tension, contributes to thin meat processing and improves production stability.

The carbamate compound of the present invention is represented by the formula (1),

In the formula (1), R ₁ , R ₂ and R ₃ are each independently -(CH ₂ ) _n -, n is an integer of 2 to 12, and X ₁ is a residue of hydrogen removed from the hydroxyl group of caprolactone acrylate Base, X ₂ is a residue of a hydrogen residue on the hydroxyl group of pentaerythritol triacrylate, and X ₃ is a residue of a hydrogen group on the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound.

In an embodiment of the invention, the hydroxyl group-containing (meth) acrylate compound comprises pentaerythritol triacrylate or caprolactone.

In one embodiment of the present invention, the carbamate compound is obtained by reacting pentaerythritol triacrylate and caprolactone with a triisocyanate compound, and the triisocyanate compound is represented by formula (2).

In the formula (2), R _a , R _b and R _c are each independently -(CH ₂ ) _n -, and n is an integer of 2 to 12.

In an embodiment of the invention, the carbamate compound is represented by formula (3) or formula (4).

In the formulae (3) and (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer of 2 to 12, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ are —(CH ₂ ) ₅ —.

In an embodiment of the present invention, in the formulas (3) and (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer from 2 to 10.

In an embodiment of the present invention, in the formulas (3) and (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer from 4 to 8.

In an embodiment of the present invention, in the formulas (3) and (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is 6.

In one embodiment of the invention, a carbamate compound is used to synthesize a copolymerizable monomer into a divalent copolymer.

In an embodiment of the invention, the copolymerizable monomer comprises at least one selected from the group consisting of a styrene monomer, an acrylonitrile monomer, and a (meth) acrylate monomer.

In an embodiment of the invention, the conjugated copolymer has a molar mass in the range of 2 x 10 ⁵ to 3 x 10 ⁶ g/mol and an average radius of gyration of 30 nm to 50 nm.

Based on the above, the carbamate compound provided by the present invention is suitable for polymer synthesis, and is used for synthesizing with a copolymerizable monomer to have a molar mass of 2 × 10 ⁵ to 3 × 10 ⁶ g / mol. A divergent copolymer having an average radius of rotation of 30 nm to 50 nm has a function of a diverging agent to impart high melt tension to the molded article, contribute to thin meat processing and improve production stability.

The above described features and advantages of the invention will be apparent from the following description.

Fig. 1 is a ¹ H-NMR chart of the carbamate compound of Synthesis Example 1.

2 is a GPC chart of the carbamate compound of Synthesis Example 1.

Fig. 3 is a ¹ H-NMR chart of the carbamate compound of Synthesis Example 2.

4 is a GPC chart of a carbamate compound of Synthesis Example 2.

In the specification and patent application of the present invention, the term "(meth) propylene The "ester" means "acrylate and/or methacrylate".

The present invention provides a urethane compound represented by the formula (1),

In the formula (1), R ₁ , R ₂ and R ₃ are each independently -(CH ₂ ) _n -, n is an integer of 2 to 12, and X ₁ is a hydroxyl group of caprolactone acrylate. A hydrogen residue, X ₂ is a residue of a pentaerythritol triacrylate that removes a hydrogen from a hydroxyl group, and X ₃ is a hydroxyl group-containing (meth) acrylate compound that removes a hydrogen residue from a hydroxyl group.

More specifically, in the formula (1), R ₁ , R ₂ and R ₃ are each independently -(CH ₂ ) _n -, preferably, n is an integer of 2 to 10; more preferably, n is An integer from 4 to 8; optimally, n is 6.

The hydroxyl group-containing (meth) acrylate compound contains pentaerythritol triacrylate or caprolactone.

The carbamate compound of the present invention is obtained by reacting pentaerythritol triacrylate and caprolactone with a triisocyanate compound.

The triisocyanate compound is represented by the formula (2).

In the formula (2), R _a , R _b and R _c are each independently -(CH ₂ ) _n -, and n is an integer of 2 to 12.

More specifically, in the formula (2), R _a , R _b , R _c are each independently -(CH ₂ ) _n -, preferably, n is an integer of 2 to 10; more preferably, n is An integer from 4 to 8; optimally, n is 6.

Specific examples of the triisocyanate compound are represented by the following formula.

Pentaerythritol triacrylate is represented by the following formula.

A specific example of caprolactone acrylate is represented by the following formula.

Specific examples of the hydroxyl group-containing (meth) acrylate compound include, but are not limited to 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, methacrylic acid-3- Hydroxypropyl ester, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, methyl 4-hydroxybutyl acrylate, dipropylene glycol acrylate, dipropylene glycol methacrylate, butane diol acrylate, butane diol methacrylate, polyethylene glycol methyl Polyethylene glycol methacrylate, polypropylene glycol acrylate, polypropylene glycol methacrylate, polyethylene glycol-polypropylene glycol methacrylate, Polyethylene glycol-1,4-butanediol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate (2-hydroxy-3-phenoxy- Propyl acrylate) Pentaerythritol triacrylate and caprolactone acrylate. Preferably, the hydroxyl group-containing (meth) acrylate compound is pentaerythritol triacrylate or caprolactone acrylate.

The carbamate compound of the present invention is preferably represented by the formula (3) or the formula (4).

In the formulae (3) and (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer of 2 to 12, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ are —(CH ₂ ) ₅ —.

More specifically, in the formulae (3) and (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, preferably, n is an integer of 2 to 10; more preferably, n is an integer of 4 to 8; optimally, n is 6.

The urethane compound of the present invention is used for synthesizing a copolymerizable monomer into a divalent copolymer, wherein the copolymerizable monomer may comprise a styrene monomer, an acrylonitrile monomer, and a (meth)acrylic acid. At least one of the groups consisting of ester monomers. More specifically, the copolymerizable monomer is preferably a styrene monomer. That is, the carbamate compound of the present invention functions as a diverging agent, enables the molded article to have a high melt tension, contributes to thin meat processing, and improves production stability.

Specific examples of the styrene monomer may include, but are not limited to, styrene, α-methylstyrene, p-t-butylstyrene, p-methylstyrene, o-methylstyrene, m-methyl. Styrene, 2,4-dimethylstyrene, ethylstyrene, α-methyl-p-methylstyrene or bromostyrene. Preferably, the styrenic monomer is styrene, alpha-methyl styrene, or a combination thereof. The styrene monomer used in the present invention may be used alone or in combination of two or more monomers.

The acrylonitrile-based monomer may also be used singly or in combination, and the acrylonitrile-based monomer includes, but not limited to, acrylonitrile or α-methacrylonitrile. Preferably, the acrylonitrile monomer is acrylonitrile.

Specific examples of the (meth) acrylate-based monomer include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, polyethylene glycol diacrylate, methyl methacrylate, Ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, methacrylic acid 2 -Hydroxyethyl ester, glycidyl methacrylate, dimethylamino methacrylate Ethyl ester, ethylene dimethacrylate, neopentyl dimethacrylate, and the like. Preferably, the (meth) acrylate monomer is butyl acrylate, methyl methacrylate and butyl methacrylate. The (meth) acrylate type monomer used in the present invention may be used alone or in combination of two or more kinds of monomers.

Hereinafter, the above-mentioned carbamate compound proposed by the present invention will be described in detail by way of experimental examples. However, the following experimental examples are not intended to limit the invention.

Experimental example

In order to prove that the urethane compound proposed by the present invention can be synthesized as a divergent copolymer with a copolymerizable monomer, whereby the molded article has a high melt tension, the following experimental examples are particularly preferred.

Preparation of carbamate compounds Synthesis Example 1

The carbamate compound of Synthesis Example 1 can be produced by the following Reaction Scheme 1.

[Reaction Scheme 1] Y represents the residue of SR495B (caprolactone acrylate) which removes a hydrogen on the hydroxyl group.

1.9 parts by weight of MEHQ (Monomethyl ether hydroquinone), 600 parts by weight of HDT manufactured by Bayer Corporation (trade name Desmodur® N3300, which is hexamethylene diisocyanate ( Hexamethylene diisocyanate (HDI) triad), 1361 parts by weight of EB (Ethylene glycol monobutyl ether) and 1.9 parts by weight of DBDTL (dibutyltin dilaurate) After entering the four reaction bottles, the mixture was stirred to form a mixed solution. Thereafter, 757 parts by weight of a brand name SR495B (Caprolactone acrylate) manufactured by Sartomer Co., Ltd. was slowly dropped into the above mixed solution at room temperature, and the temperature was raised to 50 ° C. hour. Next, 514 parts by weight of PETIA (trade name: EM235-1 (pentaerythritol triacrylate)) manufactured by Eternal Materials Co., Ltd. was dissolved in 514 parts by weight of EB, and then dropped. The reaction was carried out, and then the temperature was raised to 75 ° C for 5 hours. After the reaction was completed, the temperature was lowered to room temperature, and then the product was filtered and precipitated to obtain a carbamate compound.

Fig. 1 is a ¹ H-NMR chart of the carbamate compound of Synthesis Example 1. The results of ¹ H-NMR (hydrogen nuclear magnetic resonance) were measured using a nuclear magnetic resonance spectrometer Ultrashield 400 MHz manufactured by Bruker. As shown in Fig. 1, the H (3.5 ppm) signal of the SR495B functional group OH disappeared, and the H (3.2 ppm) signal shift of the HDT was confirmed. Therefore, it was confirmed that the reaction proceeded.

2 is a GPC chart of the carbamate compound of Synthesis Example 1. A gel permeation chromatograph (GPC) manufactured by Waters, equipped with a differential refractive index detector (Waters RI-2414) and an ultraviolet visible light detector (Waters PDA-2996) for analysis and analysis. For the column: MZ-Gel Sdplus linear 5 μm 300×8.0 mm, mobile phase: THF (flow rate 0.5 ml/min). As shown in Fig. 2, the low molecular weight disappeared and the high molecular weight appeared, and therefore, it was confirmed that the reaction proceeded.

Synthesis Example 2

The carbamate compound of Synthesis Example 2 can be produced by the following Reaction Scheme 2.

Y represents the residue of SR495B (caprolactone acrylate) which removes a hydrogen on the hydroxyl group.

2 parts by weight of MEHQ (hydroquinone monomethyl ether), 600 parts by weight of HDT (trade name Desmodur® N3300) manufactured by Bayer, 1036.5 parts by weight of EB (ethylene glycol monobutyl ether), and 2 weights A portion of DBDTL (dibutyltin dilaurate) was placed in a four-neck reaction flask and stirred to form a mixed solution. Thereafter, 432.5 parts by weight of a brand name SR495B (Caprolactone acrylate) manufactured by Satowa Co., Ltd. was slowly dropped into the above mixed solution at room temperature, and the mixture was further heated to 50 ° C for 1 hour. Next, 955 parts by weight of PETIA (trade name: EM235-1 (pentaerythritol triacrylate)) was dissolved in 955 parts by weight of EB, and then dropped into the reaction, followed by raising the temperature to 75 ° C for 5 hours, and the temperature after the reaction was completed. After the temperature was lowered to room temperature, the product was filtered and precipitated to obtain a carbamate compound.

Fig. 3 is a ¹ H-NMR chart of the carbamate compound of Synthesis Example 2. As shown in Fig. 3, the H (3.5 ppm) signal of the SR495B functional group OH disappeared, and the H (3.2 ppm) signal shift of the HDT was confirmed. Therefore, it was confirmed that the reaction proceeded.

4 is a GPC chart of a carbamate compound of Synthesis Example 2. As shown in Fig. 4, the low molecular weight disappeared and the high molecular weight appeared, and therefore, it was confirmed that the reaction proceeded.

3 ¹ H-NMR spectrum of the measurement method and the H-NMR spectrum of the ^same as in FIG. 1, FIG. 4 is a GPC chart of the spectrum and the GPC measurement method of the same FIG. 2, it is not repeated herein.

Synthesis of copolymer Example 1

150 ppm of 1,1-di-peroxide tert-butyl-3,3,5-trimethylcyclohexane (TX-29A) was added to 92.4 parts by weight of styrene monomer and 7.4 parts by weight of ethylbenzene. ), 250 ppm of n-dodecyl mercaptan and 110 ppm of 3-(3',5'-bis-tert-butyl-4'-hydroxyphenyl)propanoic acid n-octadecane Alcohol ester (Octadecyl-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate) (IX-1076, manufactured by CIBA) and 220 ppm of tris-(2,4-bis-third In the presence of tri-(2,4-di-t-butyl-phenyl)phosphate (P-168), 650 ppm of the carbamate compound of Synthesis Example 1 was added to carry out the reaction. The condition is: a flow rate of 40 liters per hour is pumped into three columnar flow reactors with a capacity of 110 liters, and the reaction inlet temperatures are maintained at 115 ° C, 130 ° C, 150 ° C, and the final conversion rate is 80% by weight. After heating by a heater at 260 ° C, the devolatilization apparatus operated under a vacuum of 15 torr removes unreacted monomers and an inert solvent, and after being extruded by an extrusion apparatus, a copolymer is obtained.

Example 2

The synthesis method was the same as in Example 1, except that 500 ppm of the carbamate compound of Synthesis Example 2 was added to carry out the reaction instead of adding 650 ppm of the carbamate compound of Synthesis Example 1 to carry out the reaction.

Reference example 1

The synthesis method was the same as in Example 1, except that the carbamate compound of Synthesis Example 1 or Synthesis Example 2 was not added to carry out the reaction.

Evaluation: Determination of the average radius of rotation of the copolymer

For the copolymers of Example 1, Example 2, and Reference Example 1, the average radius of rotation (average radius) was carried out in the range of 2 × 10 ⁵ to 3 × 10 ⁶ g / mol in terms of Molar Mass. Of gyration). A multi-angle laser light scattering (MALLS) model of DAWN8+ manufactured by Wyatt Technology Corporation was used by a gel permeation chromatography (GPC) manufactured by Waters Corporation. The viscostat of the model ViscoStar-II was measured under the following conditions: MZ-Gel Sdplus linear 5 μm 300×8.0 mm, mobile phase: THF (flow rate 0.5 ml/min). The results of the measurements are shown in Table 1 below.

As can be seen from the above Table 1, in the synthesis of the copolymer of Comparative Example 1, the carbamate compound of Synthesis Example 1 or Synthesis Example 2 was not added for the reaction, and therefore, the molar mass was 2 × 10 ⁵ In the range of 3 × 10 ⁶ g / mol, the value of the average radius of gyration is small (19.4 nm), which means that the divergence effect is poor.

In contrast, Example 1 and Example 2 are reacted using the carbamate compound proposed by the present invention to synthesize a copolymer. Since the carbamate compound of the present invention has a diverging action, it can be co-produced. The polymerizable monomer is synthesized into a divalent copolymer, and therefore, the average radius of rotation of the copolymers synthesized in Example 1 and Example 2 is in the range of 2 × 10 ⁵ to 3 × 10 ⁶ g/mol in terms of molar masses, respectively. For 35.2 nm and 42.0 nm (that is, the average radius of rotation is 30 nm to 50 nm), the value of the average radius of gyration is large, indicating that the divergence effect is better.

In summary, the urethane compound proposed by the present invention is used to synthesize a copolymerizable monomer into a divalent copolymer, wherein the copolymerizable monomer may comprise a monomer selected from the group consisting of a styrene monomer and an acrylonitrile. At least one of a group consisting of a body and a (meth) acrylate monomer. The synthesized bifurcated copolymer has a molar mass of 2 × 10 ⁵ to 3 × 10 ⁶ g/mol and an average radius of rotation of 30 nm to 50 nm, and the divergence effect is good. Therefore, the carbamate compound of the present invention functions as a diverging agent, enables the molded article to have a high melt tension, contributes to thin meat processing, and improves production stability.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

Claims (10)

A carbamate compound represented by the formula (1), In the formula (1), R ₁ , R ₂ and R ₃ are each independently -(CH ₂ ) _n -, n is an integer of 2 to 12, and X ₁ is a residue of hydrogen removed from the hydroxyl group of caprolactone acrylate Base, X ₂ is a residue of a hydrogen residue on the hydroxyl group of pentaerythritol triacrylate, and X ₃ is a residue of a hydrogen group on the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound. The carbamate compound according to claim 1, wherein the hydroxyl group-containing (meth) acrylate compound comprises pentaerythritol triacrylate or caprolactone. The carbamate compound according to claim 1, wherein the carbamate compound is obtained by reacting pentaerythritol triacrylate and caprolactone with a triisocyanate compound, wherein the triisocyanate compound is obtained from Expression (2), In the formula (2), R _a , R _b and R _c are each independently -(CH ₂ ) _n -, and n is an integer of 2 to 12. The carbamate compound according to claim 1, wherein the carbamate compound is represented by formula (3) or formula (4). In the formulae (3) and (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer of 2 to 12, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ are —(CH ₂ ) ₅ —. The carbamate compound according to claim 4, wherein in the formulae (3) and (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer from 2 to 10. The carbamate compound according to claim 4, wherein in the formulae (3) and (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is an integer from 4 to 8. The carbamate compound according to claim 4, wherein in the formulae (3) and (4), R ₄ , R ₅ , R ₆ , R ₁₁ , R ₁₂ and R ₁₃ are each independently -(CH ₂ ) _n -, n is 6. The carbamate compound according to claim 1, wherein the carbamate compound is used to synthesize a copolymerizable monomer into a divalent copolymer. The carbamate compound according to claim 8, wherein the copolymerizable monomer comprises a monomer selected from the group consisting of a styrene monomer, an acrylonitrile monomer, and a (meth) acrylate monomer. At least one of the ethnic groups. The carbamate compound according to claim 8, wherein the bismuth copolymer has a molar mass in the range of 2 × 10 ⁵ to 3 × 10 ⁶ g / mol, and an average radius of rotation of 30 nm to 50 nm .