Method for producing polyurethane for bioapplication

Abstract

The present disclosure relates to a method for producing a polyurethane for bioapplication, comprising the steps of: (a) mixing and heating a polyester polyol and an extender to dissolve same; (b) cooling the melt of step (a); and (c) mixing and reacting an isocyanate with the cooled melt of step (b).

Description

Method for producing polyurethane for bioapplication

[0001] The present disclosure relates to a method for producing a polyurethane for bioapplication, and more particularly, to a method for producing a polyurethane for bioapplication that does not contain an N-nitroso-N-methyl-N-phenylamine derivative.

[0002] Polyurethane is one of the six major synthetic polymers and a family of plastics with excellent physical properties and a wide range of applications. Polyurethane is a general term for polymer compounds containing urethane bonds formed through the polymerization reaction of polyols and isocyanates.

[0003] Polyurethane is used as a material in a wide range of products, from commercial products such as automobiles, building materials, electronic products, packaging materials, furniture, and clothing, to daily necessities.

[0004] Conventional polyurethane manufacturing involves reacting adipic acid and glycol, which are refined from petroleum, with polyester polyol and isocyanate. However, the manufacturing process contains various environmental pollutants and carcinogens, which limits its application to living organisms (skin).

[0005] Therefore, there is a need for a technology to manufacture bio-applicable polyurethanes that not only reduce environmental pollution but also do not contain carcinogens such as N-nitroso-N-methyl-N-phenylamine derivatives.

[0006] [Prior Art Literature]

[0007] [Patent Document]

[0008] (Patent Document 1) Republic of Korea Patent No. 10-1824627 (announced on February 2, 2018)

[0009] The technical problem of the present disclosure is to provide a method for producing a bio-application polyurethane that does not contain an N-nitroso-N-methyl-N-phenylamine derivative.

[0010] In addition, the present invention provides a polyurethane that does not cause skin side effects even when applied to skin-attaching bands, dressings, patches, etc., as it does not contain N-nitroso-N-methyl-N-phenylamine derivatives.

[0011] The present disclosure provides, in one embodiment, a method for producing a polyurethane for bioapplication, comprising the steps of (a) mixing and heating a polyester polyol and an extender in a reactor to dissolve them, (b) cooling the melt of step (a), and (c) mixing and reacting an isocyanate in the cooled substance of step (b).

[0012] In addition, the polyol may be at least one selected from the group consisting of PEG 1000, PEG 2000, PEG 3000, PEG 4000, PPG 1000, PPG 2000, PPG 3000, PPG triol 3000, PPG 5000, PPG triol 5000, PPG 7000, PPG triol 7000, PTHF 1000, PTHF 2000, PTHF 3000, PTHF 5000, glycerin, sorbitol, pentaerythritol polycarbonate diol, polycarbonate diol and poly(tetramethylene ether) glycol.

[0013] Additionally, the extender may be at least one selected from the group consisting of isophorone diamine (IPDA), dibutylamine (DBA), ethylene glycol (EG), butylene glycol (BG), neopentyl glycol (NPG), and 1,3-propanediol.

[0014] In addition, in step (a), the extender can be mixed in an amount of 10 to 50 parts by weight based on 100 parts by weight of polyester polyol.

[0015] Additionally, step (a) can be performed at a temperature of 80 to 100 ℃ for 5 to 30 minutes.

[0016] Additionally, the isocyanate may be at least one selected from the group consisting of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), hydrated methylene diphenyl diisocyanate (HMDI), and naphthalene diisocyanate (NDI).

[0017] In addition, in step (c), the isocyanate may be included in an amount of 50 to 150 parts by weight based on 100 parts by weight of polyester polyol.

[0018] Additionally, step (c) can be performed at a temperature of 70 to 90 ° C for 60 to 180 minutes.

[0019] The present disclosure provides a polyurethane for bioapplication prepared by the method described above in another embodiment.

[0020] The present disclosure provides, in another embodiment, a bio-applicable article made of bio-applicable polyurethane.

[0021] According to the present disclosure, a method for producing a bio-applicable polyurethane that does not contain an N-nitroso-N-methyl-N-phenylamine derivative can be provided.

[0022] In addition, since it does not contain N-nitroso-N-methyl-N-phenylamine derivatives, it can be applied to various products such as bandages, tapes, and dressings for bio-(skin) applications.

[0023] FIG. 1 is a flowchart showing a method for manufacturing a polyurethane for bioapplication according to one embodiment of the present disclosure.

[0024] Figure 2a illustrates the structure of 1,6-hexamethylene diisocyanate (HDI).

[0025] Figure 2b shows 4,4'-diisocyanato dicyclohexylmethane (hydrated MDI, H 12 It shows the structure of MDI.

[0026] Figure 2c illustrates the structure of 4,4'-diisocyanato diphenylmethane (4,4'-MDI).

[0027] Figure 2d illustrates the structure of 2,4'-diisocyanato diphenylmethane (2,4'-MDI).

[0028] Figure 2e illustrates the structure of 2,2'-diisocyanato diphenylmethane (2,2'-MDI).

[0029] Figure 2f illustrates the structure of 2,4-toluene diisocyanate (2,4-TDI).

[0030] Figure 2g illustrates the structure of 2,6-toluene diisocyanate (2,6-TDI).

[0031] Figure 2h illustrates the structure of naphthalene-1,5-diisocyanate (NDI).

[0032] Figure 2i illustrates the structure of 1-isocyanato-3-isocyanatomethyl-3,4,4-trimethyl-cyclohexane (isophorone diisocyanate, IPDI).

[0033] The present disclosure provides, in one embodiment, a method for producing a polyurethane for bioapplication, comprising the steps of (a) mixing and heating a polyester polyol and an extender in a reactor to dissolve them, (b) cooling the melt of step (a), and (c) mixing and reacting an isocyanate in the cooled substance of step (b).

[0034] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily implement the present disclosure. However, the present disclosure may be implemented in various different embodiments and is not limited to the embodiments described herein. Like reference numerals designate similar parts throughout the specification.

[0035] The term "polyester polyol" used in this disclosure refers to a polymer compound formed by polymerization of ethylene glycol and adipic acid and containing a polyester group as a repeating unit in the main chain.

[0036] The bio-application polyurethane of the present disclosure can be manufactured using a 2-liter double-jacket glass reactor equipped with a stirrer, a thermometer, a nitrogen sealing tube, and a cooler.

[0037] The term “bio” as used in this disclosure means “skin”.

[0038] The present disclosure is specifically described with reference to FIG. 1.

[0039] The present disclosure provides a method for producing a polyurethane for bioapplication, comprising, in one embodiment, (a) a step of mixing and heating a polyester polyol and an extender in a reactor to dissolve them, (b) a step of cooling the melt of step (a) (S200), and (c) a step of mixing and reacting an isocyanate with the cooled melt of step (b) (S300).

[0040] Dissolution stage (a)

[0041] First, as shown in Fig. 1, a step (S100) of mixing, heating, and dissolving polyester polyol and an extender in a reactor is performed.

[0042] Step (a) is a step of mixing and reacting an extender into polyester polyol to extend the chain of polyester polyol.

[0043] The polyester polyol used in step (a) is not limited to any polyester polyol used in the art, but may be at least one selected from the group consisting of glycerin, sorbitol, pentaerythritol polycarbonate diol, polycarbonate diol, and poly(tetramethylene ether) glycol. In addition, it may be commercially available brand names such as PEG 1000, PEG 2000, PEG 3000, PEG 4000, PPG 1000, PPG 2000, PPG 3000, PPG triol 3000, PPG 5000, PPG triol 5000, PPG 7000, PPG triol 7000, PTHF 1000, PTHF 2000, PTHF 3000, PTHF 5000, etc.

[0044] The extender used in step (a) is not limited as long as it extends the chain of the polyester polyol, but may be at least one selected from the group consisting of isophorone diamine (IPDA), dibutylamine (DBA), ethylene glycol (EG), butylene glycol (BG), neopentyl glycol (NPG), and 1,3-propanediol, and more specifically may be isophorone diamine.

[0045] The extender can extend the chain of the polyester polyol and increase its molecular weight.

[0046] In step (a), the extender can be mixed in an amount of 10 to 50 parts by weight based on 100 parts by weight of polyester polyol, and specifically, the extender can be mixed in an amount of 20 to 40 parts by weight based on 100 parts by weight of polyester polyol, and more specifically, 30 parts by weight can be mixed.

[0047] If the content of the extender in step (a) is less than 10 parts by weight, the chain extension effect of the polyester polyol is minimal, and if it exceeds 50 parts by weight, the content of the polyol is relatively low, which may result in a deterioration in the physical properties of the final polyurethane manufactured.

[0048] Step (a) can be performed at a temperature of 80 to 100 °C for 5 to 30 minutes, specifically, can be performed at a temperature of 85 to 95 °C for 7 to 15 minutes, and more specifically, can be performed at a temperature of 90 °C for 10 minutes.

[0049] If the temperature is lower than 80℃ and the time is less than 5 minutes, dissolution is not completely achieved, and polyurethane cannot be manufactured. If the temperature exceeds 100℃ and the time exceeds 30 minutes, overreaction may occur due to the high temperature, resulting in discoloration or generation of by-products.

[0050]

[0051] Cooling stage (b)

[0052] Next, as illustrated in Fig. 1, a step (S200) of cooling the melt of step (a) is performed.

[0053] In step (b), the cooling temperature of the melt of step (a) is not limited, but may be specifically 65°C or lower, specifically may be cooled to a temperature of 40 to 65°C, and more specifically may be cooled to a temperature of 60°C. In addition, the time for cooling the melt of step (a) to produce a cooled product is not limited.

[0054] Step (b) is not limited to a method that can cool the melt of step (a) to a level where the isocyanate can react.

[0055]

[0056] Reaction step (c)

[0057] Finally, as illustrated in Fig. 1, a step (S300) of mixing and reacting isocyanate with the coolant of step (b) is performed.

[0058] In step (c), the coolant of step (b) and isocyanate can be mixed and reacted to produce polyurethane.

[0059] At this time, by reacting a coolant with a specific isocyanate, a bio-applicable polyurethane that does not contain an N-nitroso-N-methyl-N-phenylamine derivative can be manufactured.

[0060] In step (c), the isocyanate may be at least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, hydrated methylene diphenyl diisocyanate and naphthalene diisocyanate, and may be specifically isophorone diisocyanate.

[0061] Additionally, in step (c), the isocyanate may be included in an amount of 50 to 150 parts by weight based on 100 parts by weight of polyester polyol, specifically 105 to 118 parts by weight based on 100 parts by weight of polyester polyol, and more specifically 115 parts by weight.

[0062] If the content of isocyanate is outside the above range, the chemical equivalent molar ratio of polyester polyol and isocyanate is not suitable, so an unreacted molar ratio remains, and the quality of the polyurethane produced may deteriorate.

[0063] Additionally, step (c) can be performed at a temperature of 70 to 90°C for 60 to 180 minutes, specifically at a temperature of 75 to 85°C for 90 to 150 minutes, and more specifically at a temperature of 80°C for 120 minutes.

[0064] In step (c), if the temperature is less than 70°C and the time is less than 60 minutes, the reaction between the polyester polyol and the isocyanate does not proceed completely, and if the temperature exceeds 90°C and the time exceeds 180 minutes, by-products may be generated due to overreaction.

[0065]

[0066] The present disclosure provides a polyurethane for bioapplication prepared by the method described above in another embodiment.

[0067] Specifically, the present disclosure provides a polyurethane for bioapplications that does not contain an N-nitroso-N-methyl-N-phenylamine derivative by synthesizing the polyurethane using a specific isocyanate and a polyester polyol.

[0068]

[0069] The present disclosure provides, in another embodiment, a bio-applicable article using the bio-applicable polyurethane described above. For example, the bio-applicable article may be a skin-attaching tape, bandage, patch, dressing, or mask pack.

[0070]

[0071] Hereinafter, the present disclosure will be described in more detail using examples. It will be apparent to those skilled in the art that these examples are intended solely to illustrate the present disclosure more specifically and that the scope of the present disclosure is not limited by them.

[0072] <Example>

[0073] Example 1

[0074] In a 2 ℓ double jacket glass reactor equipped with a stirrer, a thermometer, a nitrogen sealing tube, and a condenser, 100 parts by weight of brand name PEG 1000 (polyester polyol) was injected, 15 parts by weight of IPDA, and 15 parts by weight of DBA were injected, and heated to dissolve at 90°C at 1000 rpm for 10 minutes. Afterwards, it was cooled to 60°C at 700 rpm, 115 parts by weight of IPDI was injected, and then the reaction was carried out at 300 rpm and 80°C for 2 hours to produce a polyurethane for bioapplication with a viscosity of 7,000 cps.

[0075]

[0076] Example 2

[0077] Polyurethane for bioapplication was manufactured in the same manner as in Example 1, but using 115 parts by weight of HDI instead of 115 parts by weight of IPDI.

[0078]

[0079] Example 3

[0080] Polyurethane for bioapplication was manufactured in the same manner as in Example 1, but using 115 parts by weight of HMDI instead of 115 parts by weight of IPDI.

[0081]

[0082] Example 4

[0083] A polyurethane for bioapplication was manufactured in the same manner as in Example 1, but instead of 100 parts by weight of polyester polyol, 40 parts by weight of polyester polyol and 60 parts by weight of poly(tetramethylene ether) glycol were combined to manufacture a polyurethane for bioapplication.

[0084]

[0085] Example 5

[0086] A polyurethane for bioapplication was manufactured in the same manner as in Example 1, but using 30 parts by weight of EG instead of 15 parts by weight of IPDA and 15 parts by weight of DBA.

[0087]

[0088] Example 6

[0089] A polyurethane for bioapplication was manufactured in the same manner as in Example 1, but using 30 parts by weight of BG instead of 15 parts by weight of IPDA and 15 parts by weight of DBA.

[0090]

[0091] Example 7

[0092] A polyurethane for bioapplication was manufactured in the same manner as in Example 1, but using 30 parts by weight of NPG instead of 15 parts by weight of IPDA and 15 parts by weight of DBA.

[0093]

[0094] Example 8

[0095] Polyurethane for bioapplication was manufactured in the same manner as in Example 1, but using 115 parts by weight of NDI instead of 115 parts by weight of IPDI.

[0096]

[0097] Example 9

[0098] A polyurethane for bioapplication was manufactured in the same manner as in Example 1, but using 30 parts by weight of 1,3-propanediol instead of 15 parts by weight of IPDA and 15 parts by weight of DBA.

[0099]

[0100] <Comparative Example>

[0101] Comparative Example 1

[0102] Polyurethane was manufactured in the same manner as in Example 1, but using 115 parts by weight of toluene diisocyanate (TDI) instead of IPDI.

[0103]

[0104] Comparative Example 2

[0105] Polyurethane was manufactured in the same manner as in Example 1, but using 115 parts by weight of methylene diphenyl diisocyanate (MDI) instead of IPDI.

[0106]

[0107] Comparative Example 3

[0108] Polyurethane was manufactured in the same manner as in Example 1, but using 50 parts by weight of TDI and 60 parts by weight of MDI instead of 115 parts by weight of IPDI.

[0109]

[0110] <Example of an exam>

[0111] The presence or absence of N-nitroso-N-methyl-N-phenylamine derivatives in polyurethanes manufactured according to Examples 1 to 8 and Comparative Examples 1 to 3 was confirmed.

[0112] Test method: Measure about 1 to 5 g of the sample and place it in a conical flask, and add an artificial saliva test solution preheated at 40±2 ℃ in a volume corresponding to about 10 times the weight of the sample (about 10 ml of artificial saliva test solution per 1 g of sample).

[0113] Afterwards, prepare 4.2 g of sodium bicarbonate, 0.5 g of sodium chloride, 0.2 g of potassium carbonate, and 0.03 g of sodium nitrite, dissolve them in 950 mL of distilled water, adjust the pH to 9 with 0.1 mol / L NaOH solution, and add distilled water to make a total volume of 1,000 mL. After sufficiently immersing the sample in the solution, close the stopper, and let it stand at 40±2 ℃ for 60 minutes, then take 1 mL of the extracted solution into an LC analysis vial, and add 0.02 mL of the internal standard. Next, take 5 mL of the extracted solution and transfer it to a 20 mL vial, add 0.5 mL of 0.1 M hydrochloric acid solution, close the stopper, shake to mix well, and let it stand at 40±2 ℃ for 30 minutes. Afterwards, open the stopper and add 1 ml of 1 M sodium hydroxide solution and mix well.

[0114] 1 ml of the test solution was placed in a vial for LC analysis, and 0.02 ml of internal standard was added and analyzed by LC-MS / MS.

[0115] The analysis conditions were Agilent 6470 Triple Quad LC / MS, C18 (RRHD 2.1 mm ID × 100 mm, 1.8 μm) column, flow rate 0.3 ml / min, column temperature 30 °C. The mobile phase was A: 0.1% formic acid in diluted water, B: 0.1% formic acid in Acetonitrile, and the analysis was performed in MRM (Multiple reaction monitoring) mode under A:B gradient conditions (70:30→10:90→70:30).

[0116] The analysis results are shown in Table 1 below.

[0117] [Table 1]

[0118]

[0119] As can be seen in Table 1, in all of Comparative Examples 1 to 3, N-nitroso-N-methyl-N-phenylamine derivatives were detected, whereas in all of Examples 1 to 8, N-nitroso-N-methyl-N-phenylamine derivatives were not detected. In addition, when comparing Example 3 and Comparative Example 2, it can be seen that in Comparative Example 2, which used MDI, N-nitroso-N-methyl-N-phenylamine derivatives were detected, but in Example 3, which used hydrated MDI, no such derivatives were detected. In other words, it can be seen that there are differences depending on the presence or absence of hydration.

[0120] In summary, the present disclosure can produce a bio-applicable polyurethane that does not contain an N-nitroso-N-methyl-N-phenylamine derivative by producing polyurethane using a specific isocyanate, and the produced polyurethane can be applied to various products such as bandages, tapes, and dressings that can be applied to a bio(skin).

[0121] According to the present disclosure, since the polyurethane does not contain an N-nitroso-N-methyl-N-phenylamine derivative, it can be applied to various products such as bandages, tapes, and dressings for biomedical (skin) applications.

Claims

1. (a) A step of mixing polyester polyol and extender in a reactor and heating them to dissolve them. (b) a step of cooling the melt of step (a) and (c) a step of mixing and reacting isocyanate in the coolant of step (b), Method for producing polyurethane for bioapplication.

2. In paragraph 1, The above polyol is, At least one selected from the group consisting of PEG 1000, PEG 2000, PEG 3000, PEG 4000, PPG 1000, PPG 2000, PPG 3000, PPG triol 3000, PPG 5000, PPG triol 5000, PPG 7000, PPG triol 7000, PTHF 1000, PTHF 2000, PTHF 3000, PTHF 5000, Glycerine, Sorbitol, Pentaerythritol Polycarbonate diol, Polycaprolactone diol, and Poly(tetramethylene ether)glycol. Method for producing polyurethane for bioapplication.

3. In paragraph 1, The above extension agent is, At least one selected from the group consisting of isophoronediamine, dibutylamine, ethylene glycol, butylene glycol, neopentyl glycol and 1,3-propanediol. Method for producing polyurethane for bioapplication.

4. In paragraph 1, In the above step (a), the extender is mixed in an amount of 10 to 50 parts by weight based on 100 parts by weight of polyester polyol. Method for producing polyurethane for bioapplication.

5. In paragraph 1, The above step (a) is, Performed at a temperature of 80 to 100 ℃ for 5 to 30 minutes, Method for producing polyurethane for bioapplication.

6. In paragraph 1, The above isocyanate is, At least one selected from the group consisting of isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated methylene diphenyl diisocyanate and naphthalene diisocyanate. Method for producing polyurethane for bioapplication.

7. In paragraph 1, In the above step (c), the isocyanate is Containing 50 to 150 parts by weight based on 100 parts by weight of polyester polyol, Method for producing polyurethane for bioapplication.

8. In paragraph 1, The above step (c) is, Performed at a temperature of 70 to 90 ℃ for 60 to 180 minutes, Method for producing polyurethane for bioapplication.

9. Polyurethane for bioapplication manufactured by any one of the methods of clauses 1 to 8.

10. A bio-applicable article manufactured from the bio-applicable polyurethane of Article 9.

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