TW202214735A - Thermoplastic polyurethanes producing from recycled pet, its preparing formulation and making process - Google Patents

Abstract

The invention relates to an thermoplastic polyurethanes producing from recycled PET, its preparing formulation and making process. In particular, the thermoplastic polyurethanes producing from recycled PET has a stress more than 3.0MPa and a strain(%) more than 1000%.

Description

Thermoplastic polyurethane from recycled PET bottles, its formulation and manufacture method

The present invention provides a thermoplastic polyurethane derived from recycled PET bottles, a preparation formula and a manufacturing method thereof. The tensile strength of the thermoplastic polyurethane derived from recycled PET bottles is greater than 3.0 MPa and has an elongation rate of over 1000%.

With the advent of plastics, the quality of human life has been improved; at the same time, the increasing demand has also caused environmental burdens. Polyethylene terephthalate (PET) is a common raw material for plastic containers, that is, the raw material for PET bottles. Although the conventional PET bottle recycling system can reprocess and utilize discarded PET bottles, it cannot solve the shortcomings of residual additives such as catalysts, UV stabilizers and antioxidants in the recycled PET bottles. The high temperature in the reprocessing process further deteriorates the properties of the recycled material from the PET bottle, resulting in the recycled material from the PET bottle that can only be down-cycling and cannot be used in the high value-added material industry.

To sum up, in today's PET bottle recycling industry, a design of a The technology and application of recycled materials in the high value-added material industry is an urgent research and development topic.

In view of the above-mentioned background of the invention, in order to meet the requirements of the industry, the first object of the present invention is to provide a formulation for preparing thermoplastic polyurethane with high tensile strength. Specifically, the formula contains a derivative derived from recycled PET bottles (polyethylene terephthalate), and is designed with a novel formulation composition and its use weight ratio. Tensile strength thermoplastic polyurethane. The above-mentioned formulation for the preparation of thermoplastic polyurethane with high tensile strength comprises a first agent comprising a polyurethane oligomer and a second agent, the second agent comprising a Derivatives of ethylene terephthalate). Wherein the use weight ratio of the polyurethane oligomer and the derivative derived from the recycled PET bottle (polyethylene terephthalate) is 2-25.

The polyurethane oligomer contained in the above-mentioned first agent has the chemical formula shown in formula (1), which is prepared by the reaction of polyol and aromatic diisocyanate.

Formula 1).

In one embodiment, the Ar is derived from an aromatic diisocyanate; the polyol is derived from a polyol selected from the group consisting of: One or a combination thereof: aliphatic diols, polyether diols, polyester diols and bisphenol compounds; and the use weight ratio of the polyol and the aromatic diisocyanate is 2 to 20; and m is 1 to 10 .

In the preparation process of the above-mentioned polyurethane oligomer, an inert solvent or a reaction assistant can also be used, thereby improving and enhancing the compatibility and reaction rate of the polyol and the aromatic diisocyanate.

The inert solvent contains an aprotic solvent or a mixed solvent of an aprotic solvent and a protic solvent. The aprotic solvent comprises tetrahydrofuran, anisole, dimethylformamide, dimethylacetamide, N-methylpyrrolidone (NMP), dimethylnitrosamine, or a combination thereof.

The reaction aid contains stannous octoate or dibutyltin dilaurate.

The above-mentioned second agent-derived derivative derived from recycled PET bottles (polyethylene terephthalate) has the chemical formula shown in formula (2).

Formula (2).

In one embodiment, the R ₁ and R ₂ are derived from a diol compound, an amino alcohol or a combination thereof: the diol compound comprises aliphatic diol, aromatic diol or polyether diol; The alcoholamine compound includes aliphatic monoalcohol monoamine or aromatic monoalcohol monoamine.

Specifically, the derivative derived from recycled PET bottles is hydroxyethyl 2-hydroxyethylaminoacylbenzoate (BHETTA), which has the chemical formula shown in formula (3).

Formula (3).

To sum up, the main component of the first agent of the present invention is the polyurethane oligomer obtained by the reaction of the above-mentioned polyol and aromatic diisocyanate, which has the chemical formula shown in the above formula (1); the polyurethane oligomer and The above-mentioned derivatives derived from recycled PET bottles (polyethylene terephthalate) are subjected to chain extension reaction to produce the thermoplastic polyurethane disclosed in the present invention. Wherein the use weight ratio of the polyurethane oligomer and the derivative derived from recycled PET bottles (polyethylene terephthalate) is 2 to 25, thereby making thermoplastic polyurethane with a tensile strength greater than 3.0 MPa .

The above-mentioned thermoplastic polyurethane having a tensile strength of more than 3.0 MPa is derived from recycled bottles, and has a chemical formula as shown in formula (4).

Ar shown in the above formula (4) is derived from an aromatic diisocyanate; the polyol segment shown in the above formula (4) is derived from a polyol, and the polyol is selected from one of the following groups or a combination thereof: aliphatic family diols, polyether diols, polyester diols and The bisphenol compound; and the polyol and the aromatic diisocyanate are used in a weight ratio of 2 to 20; and m is 1 to 10. R represented by the above formula (4) is a derivative derived from recycled PET bottles (polyethylene terephthalate). The use weight ratio of the polyurethane oligomer and the derivative derived from recycled PET bottles (polyethylene terephthalate) is 2-25; and n is 2-30.

The second object of the present invention is to provide a thermoplastic polyurethane derived from recycled PET bottles, which has the chemical formula shown in formula (4).

Formula (4).

Ar shown in the above formula (4) is derived from an aromatic diisocyanate; the polyol segment shown in the above formula (1) is derived from a polyol, and the polyol is selected from one of the following groups or a combination thereof: aliphatic and the use weight ratio of the polyol and the aromatic diisocyanate is 2~20; and m is 1~10. R represented by the above formula (4) is a derivative derived from recycled PET bottles (polyethylene terephthalate). The use weight ratio of the polyurethane oligomer and the derivative derived from recycled PET bottles (polyethylene terephthalate) is 2-25; and n is 2-30.

Specifically, the tensile strength of the thermoplastic polyurethane derived from recycled PET bottles is greater than about 3.0 MPa. Preferably, the thermoplastic derived from recycled PET bottles The tensile strength of the polyurethane is greater than about 20.0 MPa and has an elongation of over 1000%.

Specifically, the weight-average molecular weight of the thermoplastic polyurethane derived from recycled PET bottles is 10,000-400,000 Da.

The third object of the present invention is to provide a method for producing a thermoplastic polyurethane with high tensile strength, the steps of which include performing a chain extension reaction using the formulation described in the first object of the present invention, thereby producing the above-mentioned high tensile strength thermoplastic polyurethane. The thermoplastic polyurethane with tensile strength has the chemical formula shown in formula (4); the tensile strength of the thermoplastic polyurethane with high tensile strength is greater than about 3.0 MPa. In particular, the above-mentioned manufacturing method uses a formulation containing derivatives derived from recycled PET bottles. Therefore, the manufacturing method of thermoplastic polyurethane with high tensile strength provided by the third object of the present invention also solves the problem of disposal of waste bottles (polyethylene terephthalate). Compared with the traditional waste polymer incineration treatment method, the manufacturing method of the present invention makes the chemical molecular structure of the waste bottle (polyethylene terephthalate) fixed in the novel thermoplastic polyurethane with high tensile strength again. within the structure. Therefore, the manufacturing method of thermoplastic polyurethane with high tensile strength described in the third object of the present invention is an environment-friendly and highly atom-efficient thermoplastic polyurethane manufacturing method.

Specifically, the temperature of the above-mentioned chain extension reaction is 60 to 120°C.

To sum up, the thermoplastic polyurethane derived from recycled PET bottles, its preparation formula and manufacturing method provided by the present invention have at least the following characteristics and advantages: (1) The formula for preparing thermoplastic polyurethane with high tensile strength provided by the present invention belongs to a two-component formula, which comprises the above-mentioned polyurethane oligomer as the first component as the main component and the above-mentioned source from Recycling Baote bottle (polyethylene terephthalate) derivative as the second agent of the main component; and prepared under the condition of specific use weight ratio range of the polyurethane oligomer and the derivative derived from recycled PET bottle Thermoplastic polyurethane with high tensile strength that cannot be made with known formula MPa tensile strength and over 1000% elongation. Accordingly, the thermoplastic polyurethane derived from recycled PET bottles provided by the present invention can exhibit excellent mechanical properties before being processed; and (3) the thermoplastic polyurethane with high tensile strength provided by the present invention has The manufacturing method can use waste PET bottles (polyethylene terephthalate) as a starting material. The manufacturing method of the thermoplastic polyurethane with high tensile strength innovatively solves the problem of disposal of waste bottles. The above-mentioned manufacturing method further fixes the benzene ring structure in the waste bottle again in the novel thermoplastic polyurethane structure with high tensile strength, so it is an environmentally friendly and highly atomic efficient thermoplastic polyurethane manufacturing. method.

[Fig. 1] is the hydroxyethyl 2-hydroxyethylcarbamoyl benzoate described in the first embodiment Hydrogen NMR spectrum of the ester (BHETTA).

[Fig. 2] is a thermal differential scanning (DSC) chart of thermoplastic polyurethane PU-1.

[Fig. 3] is a thermal differential scanning (DSC) chart of thermoplastic polyurethane PU-2.

[Fig. 4] is a graph showing the tensile strength and elongation ratio of thermoplastic polyurethane PU-1.

[Fig. 5] is a graph showing the tensile strength and elongation ratio of thermoplastic polyurethane PU-2.

The foregoing and other technical contents, features and effects of the present invention will be clearly presented in the following detailed description of a preferred embodiment with reference to the drawings. In order to provide a thorough understanding of the present invention, detailed steps and their components will be set forth in the following description. Obviously, the practice of the present invention is not limited to the specific details familiar to those skilled in the art. In other instances, well-known components or procedures have not been described in detail to avoid unnecessarily limiting the invention. The preferred embodiments of the present invention will be described in detail as follows, however, in addition to these detailed descriptions, the present invention can also be widely implemented in other embodiments, and the scope of the present invention is not limited, and the following patent scope shall prevail .

According to a first embodiment of the present invention, the present invention provides a formulation for preparing thermoplastic polyurethane with high tensile strength, the formulation comprising a first agent and a second agent, the first agent comprising a polyurethane oligomer; and the second dose contains a derivative derived from recycled PET bottles (polyethylene terephthalate). The use weight ratio of the polyurethane oligomer and the derivative derived from the recycled bottle is 2-25.

In one embodiment, the weight-average molecular weight of the polyurethane oligomer is 1,000-40,000 Da, and has the chemical formula shown in formula (1).

Formula 1).

In a specific embodiment, the Ar is derived from an aromatic diisocyanate; the polyol is derived from a polyol, and the polyol is selected from one of the following groups or a combination thereof: aliphatic diol, polyether diol , polyester diols and bisphenol compounds; and m is between 1 and 10.

In a specific embodiment, the aromatic diisocyanate comprises diphenylmethane diisocyanate (MDI), diphenyldifluoromethane diisocyanate, p-phenylene diisocyanate, o-phenylene diisocyanate, m-phenylene diisocyanate, 2,2 '-biphenyl diisocyanate, 3,3'-biphenyl diisocyanate, 4,4'-biphenyl diisocyanate, naphthalene diisocyanate, or a combination thereof.

In a specific embodiment, the aliphatic diol includes a linear diol with 2-40 carbon atoms or a branched diol with 2-40 carbon atoms. The relative positions of the diol groups of the above-mentioned aliphatic diols may be symmetrical or asymmetrical. Preferably, the linear dihydric alcohol having 2 to 40 carbon atoms comprises 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol.

In a specific embodiment, the polyether glycol comprises polyethylene glycol, polypropylene Diols or polyether diols of the polytetrahydrofuran series. Preferably, the weight average molecular weight of the polyether glycol is 100-5,000 Da.

In another specific embodiment, the polyether glycol of the polytetrahydrofuran series is selected from one of the following groups or a combination thereof: polytetramethylene ether glycol (PTMEG), polytetramethylene ether glycol (polytetramethylene ether glycol- ethylene glycol copolymer) and polytetramethylene ether glycol-propylene glycol copolymer.

In one embodiment, the polyester diol comprises polyester diol, polycarbonate diol, polycaprolactone diol, or a combination thereof.

In a specific embodiment, the weight-average molecular weight of the aforementioned polyurethane oligomer is 1,000-40,000 Da.

In one embodiment, the chemical formula of the derivative derived from recycled PET bottles is shown in formula (2).

Formula (2).

In one embodiment, the R ₁ and R ₂ are derived from diol compounds, alcohol amine compounds or a combination thereof. The diol compound comprises: aliphatic diol, aromatic diol, polyether diol or polyester diol; the alcoholamine compound comprises aliphatic monoalcohol monoamine or aromatic monoalcohol monoamine. Preferably, the aliphatic diol comprises 1,2-ethylene glycol, 1,4-butanediol or 1,6-hexanediol; the aliphatic monoalcohol monoamine comprises ethanolamine, 4-amino-1- Butanol or 6-amino-1-hexanol.

In one embodiment, the aliphatic diol or monoalcohol-amine is a straight-chain or branched compound having 2-40 carbon atoms. The relative positions of the functional groups of the aliphatic diol or monoalcohol-amine can be symmetrical or asymmetrical. Preferably, the linear compound having 2 to 40 carbon atoms is a diol compound, which comprises 1,2-ethylene glycol, 1,4-butanediol or 1,6-hexanediol; the carbon number 2 Linear compounds of ~40 are linear monoalcohol monoamine compounds comprising ethanolamine, 4-amino-1-butanol or 6-amino-1-hexanol.

In one embodiment, the weight average molecular weight of the polyether glycol is 100-5,000 Da. Preferably, the polyether glycol comprises polyethylene glycol, polypropylene glycol or polytetrahydrofuran series polyether glycol.

In a specific embodiment, the polyether glycol of the polytetrahydrofuran series is selected from one of the following groups: polytetramethylene ether glycol (PTMEG), polytetramethylene ether glycol-ethylene glycol copolymer (polytetramethylene ether glycol-ethylene glycol copolymer) And polytetrahydrofuran-propylene oxide (polytetramethylene ether glycol-propylene glycol copolymer).

In another embodiment, the polyester diol comprises polyester diol, polycarbonate diol, polycaprolactone diol, or a combination thereof.

In a preferred embodiment, the derivative derived from recycled PET bottles is hydroxyethyl 2-hydroxyethylaminoacylbenzoate (BHETTA), which has the formula (3) shown in chemical formula. BHETTA has characteristic peaks at the chemical shifts of about 8.60ppm-8.70ppm, 4.70-4.80ppm and 4.90-5.00ppm in the hydrogen nuclear magnetic resonance spectrum. The specific hydrogen NMR spectrum is shown in Figure 1.

Formula (3).

Specifically, the thermoplastic polyurethane with high tensile strength prepared from the above-mentioned formulation for preparing thermoplastic polyurethane with high tensile strength has the chemical formula shown in formula (4), and its tensile strength is greater than 3.0 MPa, preferably, the thermoplastic polyurethane with high tensile strength has a tensile strength of more than 20.0 MPa and an elongation of more than 1000%.

Formula (4).

Ar represented by formula (4) is derived from the above-mentioned aromatic diisocyanate; the polyol segment is derived from the above-mentioned polyol, and the polyol is selected from one of the following groups: aliphatic diol, polyether The diol, polyester diol and bisphenol compound; and the polyol and the aromatic diisocyanate are used in a weight ratio of 2 to 20; and m is 1 to 10. R is a derivative derived from the aforementioned recycled PET bottles. The use weight ratio of the polyurethane oligomer and the derivative derived from the recycled bottle is 2 to 25; and n is 2~30.

The second embodiment of the present invention provides a thermoplastic polyurethane derived from recycled PET bottles, the tensile strength of which is greater than 3.0 MPa and the chemical formula shown in formula (4).

Formula (4).

Ar shown in the above formula (4) is derived from an aromatic diisocyanate; the polyol segment shown in the above formula (4) is derived from a polyol, and the polyol is selected from one of the following groups or a combination thereof: aliphatic family diols, polyether diols, polyester diols and bisphenol compounds; and the use weight ratio of the polyol and the aromatic diisocyanate is 2 to 20; and m is 1 to 10; the above formula (4) R shown is a derivative derived from recycled PET bottles (polyethylene terephthalate). The use weight ratio of the polyurethane oligomer and the derivative derived from recycled PET bottles (polyethylene terephthalate) is 2-25; and n is 2-30.

In a specific embodiment, the aromatic diisocyanate comprises diphenylmethane diisocyanate (MDI), diphenyldifluoromethane diisocyanate, p-phenylene diisocyanate, o-phenylene diisocyanate, m-phenylene diisocyanate, 2,2 '-biphenyl diisocyanate, 3,3'-biphenyl diisocyanate, 4,4'-biphenyl diisocyanate, naphthalene diisocyanate, or a combination thereof.

In a specific embodiment, the aliphatic diol includes a linear diol with 2-40 carbon atoms or a branched diol with 2-40 carbon atoms. The relative positions of the diol groups of the above-mentioned aliphatic diols may be symmetrical or asymmetrical. Preferably, the straight-chain diol having 2 to 40 carbon atoms is 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol.

In a specific embodiment, the weight average molecular weight of the polyether glycol is 100-5,000 Da. Preferably, the polyether glycol comprises polyethylene glycol, polypropylene glycol or polyether glycol of polytetrahydrofuran series.

In another specific embodiment, the polyether glycol of the polytetrahydrofuran series is selected from one of the following groups or a combination thereof: polytetramethylene ether glycol (PTMEG), polytetramethylene ether glycol (polytetramethylene ether glycol- ethylene glycol copolymer) and polytetramethylene ether glycol-propylene glycol copolymer.

In one embodiment, the polyester diol comprises polyester diol, polycarbonate diol, polycaprolactone diol, or a combination thereof.

In one embodiment, the derivatives derived from recycled PET bottles have the chemical formula shown in formula (2).

Formula (2).

In one embodiment, the R ₁ and R 2 are derived from diol compounds, alcohol amine compounds or a combination thereof. The diol compound comprises: aliphatic diol, aromatic diol, polyether diol or polyester diol; the alcoholamine compound comprises aliphatic monoalcohol monoamine or aromatic monoalcohol monoamine. Preferably, the aliphatic diol comprises 1,2-ethylene glycol, 1,4-butanediol or 1,6-hexanediol, and the aliphatic monoalcohol monoamine comprises ethanolamine, 4-amino-1- Butanol or 6-amino-1-hexanol.

In one embodiment, the aliphatic diol or monoalcohol-amine is a straight-chain or branched compound having 2-40 carbon atoms. The relative positions of the functional groups of the aliphatic diol or monoalcohol-amine can be symmetrical or asymmetrical. Preferably, the linear compound having 2 to 40 carbon atoms is a diol compound, which comprises 1,2-ethylene glycol, 1,4-butanediol or 1,6-hexanediol; the carbon number 2 Linear compounds of ~40 are linear monoalcohol monoamine compounds comprising ethanolamine, 4-amino-1-butanol or 6-amino-1-hexanol.

In one embodiment, the weight average molecular weight of the polyether glycol is 100-5,000 Da. Preferably, the polyether glycol comprises polyethylene glycol, polypropylene glycol or polytetrahydrofuran series polyether glycol.

In a specific embodiment, the polyether glycol of the polytetrahydrofuran series is selected from one of the following groups: polytetramethylene ether glycol (PTMEG), polytetramethylene ether glycol-ethylene glycol copolymer (polytetramethylene ether glycol-ethylene glycol copolymer) And polytetrahydrofuran-propylene oxide (polytetramethylene ether glycol-propylene glycol copolymer).

In another embodiment, the polyester diol comprises polyester diol, polycarbonate diol, polycaprolactone diol (polycaprolactone diol) or a combination thereof.

In a preferred embodiment, the derivative derived from recycled PET bottles is hydroxyethyl 2-hydroxyethylaminoacylbenzoate (BHETTA), the chemical formula of which is shown in formula (3); The chemical shifts of the graph have characteristic peaks at about 8.60 ppm-8.70 ppm, 4.70-4.80 ppm and 4.90-5.00 ppm. The specific hydrogen NMR spectrum is shown in Figure 1.

Formula (3).

In a representative embodiment, the thermoplastic polyurethane represented by the formula (4) of the present invention derived from recycled PET bottles, the Ar is derived from diphenylmethane diisocyanate (MDI); the polyol segment is Derived from polyether diol (PTMEG2000), polycaprolactone diol (PCL2000) or polycarbonate diol (PCDL2000); the R is derived from hydroxyethyl 2-hydroxyethylaminoacylbenzoate (BHETTA) ); m is 1~10 and n is 2~30.

The third embodiment of the present invention provides a method for producing thermoplastic polyurethane with high tensile strength, the steps of which include using the formula described in the first embodiment to carry out chain extension reaction, thereby producing the high tensile strength thermoplastic polyurethane. The tensile strength of the thermoplastic polyurethane with high tensile strength is greater than about 3.0 MPa. Preferably, the thermoplastic polyurethane with high tensile strength The tensile strength of the ester is greater than about 22.0 MPa.

In one embodiment, the temperature of the chain extension reaction ranges from 60°C to 120°C.

In one embodiment, the weight average molecular weight of the thermoplastic polyurethane with high tensile strength is 10,000-400,000 Da.

In a representative example, the use of diphenylmethane diisocyanate (MDI) and polyether diol (PTMEG2000), polycaprolactone diol (PCL2000) or polycarbonate diol (PCDL2000) were made of polyurethane The oligomer and BHETTA, a derivative derived from recycled PET bottles, are used to make the thermoplastic polyurethane with high tensile strength according to the present invention, and its chemical formula is shown in formula (4).

Formula (4).

Wherein Ar is derived from diphenylmethane diisocyanate (MDI); the polyol segment is derived from polyether diol (PTMEG2000), polycaprolactone diol (PCL2000) or polycarbonate diol (PCDL2000); R is a derivative (BHETTA) derived from recycled PET bottles; m is 1-10 and n is 2-30.

The following examples and experimental examples are experiments carried out according to the above-mentioned content of the invention and the content described in the embodiments, and are used as a detailed description of the present invention accordingly.

Example 1: General preparation steps of the present invention for derivatives derived from recycled PET bottles (polyethylene terephthalate)

Combine the PET bottle (15.0g) and the glycol compound (10~50ml) Put it into a single-necked round flask with a magnetic stirring bar, stir at 60-250° C. for about 1-6 hours, and then dropwise into the alkanolamine compound (2-20 ml) and allow to react for about 3-12 hours. The mixture was passed through filter paper to remove impurities from the recovered polyethylene terephthalate. Subsequently, a precipitating agent (50-200 ml) was added, and the precipitating agent contained water, methanol, n-hexane, etc., and a large amount of white precipitate was formed, and then the filtrate was filtered and collected. Purification using column chromatography gave the described derivatives derived from recycled PET bottles (polyethylene terephthalate).

In an experimental example, the above-mentioned diol compound is ethylene glycol, and the above-mentioned alcoholamine compound is ethanolamine, and the recycled PET bottle (polyethylene terephthalate) produced by the general procedure described in example 1. ester) derivative is hydroxyethyl 2-hydroxyethylcarbamoylbenzoate ( BHETTA ). BHETTA structural identification data are shown below: ¹ H NMR (400MHz, DMSO-d ₆ ): δ = 3.32(q, J =5.9Hz, 2H), 3.50(q, J =5.8Hz, 2H), 3.70(q, J =4.6Hz,2H),4.28(t, J =4.6Hz,2H),4.74(t, J =5.6Hz,1H),4.94(t, J =5.6Hz,1H),8.00(dd, J = 26.7Hz, 8.3Hz, 4H), 8.63 (t, J = 5.1Hz, 1H). ¹³ C NMR (100MHz, DMSO-d ₅ ): δ =42.3, 59.0, 59.6, 66.8, 127.5, 129.2, 138.6, 165.4 ,165.5ppm.

In other experimental examples, the derivatives derived from recycled PET bottles (polyethylene terephthalate) were bis-2-hydroxyethyl phthalate (BHET) or bis-2-hydroxyethyl terephthalate ( BHETA); also prepared using the implementation procedure described in Example 1, and the NMR structure identification data are shown below.

NMR structure identification of bis-2-hydroxyethyl terephthalamide (BHETA): ¹ H NMR (400MHz, DMSO-d ₆ ): δ=3.35(q, J=5.9Hz, 4H), 3.53(t, J=6.2Hz, 4H), 4.75(br, 2H), 7.92(s, 4H), 8.56(t, J=5.5Hz, 2H). ¹³ C NMR (100MHz, DMSO-d ₆ ): δ=42.3, 59.7, 127.2, 136.7, 165.8ppm.

NMR structure identification of bis-2-hydroxyethyl phthalate (BHET): ¹ H NMR (400MHz, DMSO-d ₆ ): δ=3.73(q, J=5.2Hz, 4H), 4.32(t, J= 4.7 Hz, 4H), 4.97 (t, J=5.7 Hz, 2H), 8.10 (s, 4H). ¹³ C NMR (100 MHz, DMSO-d ₆ ): δ=59.0, 67.0, 129.5, 133.8, 165.2 ppm.

Example 2: General preparation steps of the polyurethane oligomer of the present invention

The polyurethane oligomer is prepared by polymer polymerization. Specifically, various diisocyanates such as diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) or 1,6-hexamethylene diisocyanate (HDI); and diols such as polycarbonate Dihydric alcohol (PCDL2000), condensation polymerization reaction is carried out between 60-100 ℃, the reaction process can be added with solvents such as dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, dimethylsulfoxide or anisole to help The reaction proceeded, and the characteristic peak of the carbamate functional group could be seen at the position of 1750±50 cm ^-1 in the FT-IR spectrum when the reaction was completed.

Example 3: General preparation steps of thermoplastic polyurethane according to the present invention

The above-mentioned polyurethane oligomers and various above-mentioned derivatives derived from recycling Baote bottles (polyethylene terephthalate) respectively; such as bis-2-hydroxyethyl phthalate (BHET), terephthalamide Bis-2-hydroxyethyl ester (BHETA) or 2-hydroxyethyl amido 2-Hydroxyethyl benzoate (BHETTA) is heated to carry out chain extension reaction, thereby obtaining various thermoplastic polyurethanes. The specific composition and weight ratio of the formula used in the experimental example PU-1 of the present invention are: PCDL (molecular weight 2000): MDI: BHETTA=70:15:15. The formulation composition and weight ratio used in the comparative example PU-2 are PCDL (molecular weight 2000 Da): aliphatic diisocyanate (IPDI): BHETA=70:15:15.

The thermal differential scanning (DSC) spectrum of the thermoplastic polyurethane PU-1 of the present invention is shown in FIG. 2 . The thermal differential scanning (DSC) spectrum of the thermoplastic polyurethane PU-2 of the control group is shown in FIG. 3 .

The above experimental examples used different types and weight ratios of derivatives derived from recycled plastic bottles or polyethylene terephthalate and polyurethane oligomers to conduct the synthesis and related experiments of thermoplastic polyurethane. According to the experimental results, it is clearly known that the thermoplastic polyurethane derived from recycled plastic bottles according to the present invention has a tensile strength greater than 3.0 MPa, a good elongation ratio and film expansion elasticity. Compared to reaction formulations containing aliphatic diisocyanates (eg IPDI), the formulations of the present invention comprising aromatic diisocyanates and derivatives derived from recycled PET bottles (BHETTA) can be made to have tensile strengths greater than 20.0 MPa and 1000% elongation thermoplastic polyurethane PU-1. As shown in FIG. 4 , it is obvious that the thermoplastic polyurethane PU-1 obtained from the formulation of the present invention has unpredictable tensile strength and good film stretch elasticity and stretch ratio. However, the experimental results of thermoplastic polyurethane PU-2 prepared by the reaction formula containing aliphatic diisocyanate (IPDI) are shown in Figure 5. The tensile strength of PU-2 cannot exceed 3.0MPa, and the elongation rate is only about 800%. Obviously, the mechanical properties of PU-2 cannot reach the mechanical properties of the thermoplastic polyurethane PU-1 derived from recycled PET bottles of the present invention, which proves that the derivatives provided by the present invention comprising aromatic diisocyanates and recycled PET bottles Compared with the conventional formula, the formula of the product does have unpredictable effects.

Although the present invention is described above with specific experimental examples, it does not limit the scope of the present invention. As long as it does not depart from the gist of the present invention, those skilled in the art will understand that various modifications or changes can be made without departing from the intent and scope of the present invention. In addition, the abstract section and the title are only used to aid the search of patent documents and are not intended to limit the scope of the present invention.

Claims (24)

A formulation for preparing thermoplastic polyurethane with high tensile strength, the formulation comprising a first dose and a second dose; the first dose comprising a polyurethane oligomer, the second dose comprising a recycled PET bottle The derivative of , and the use weight ratio of the polyurethane oligomer and the derivative derived from the recycled bottle is 2~25; The weight-average molecular weight of the polyurethane oligomer is 1,000-40,000 Da, and has the chemical formula shown in formula (1);

Wherein, the Ar is derived from aromatic diisocyanate; the polyol is derived from polyol, and the polyol is selected from one of the following groups or a combination thereof: aliphatic diol, polyether diol, polyester diol alcohols and bisphenol compounds; and m is 1 to 10; and The derivative derived from recycled PET bottles has the chemical formula shown in formula (2):

wherein, the R ₁ and R ₂ are derived from a diol compound, an alcoholamine compound or a combination thereof; the diol compound comprises aliphatic diol, aromatic diol, polyether diol or polyester diol; and The alcoholamine compound includes aliphatic monoalcohol monoamine or aromatic monoalcohol monoamine. The formulation for preparing thermoplastic polyurethane with high tensile strength according to claim 1, wherein the aromatic diisocyanate comprises diphenylmethane diisocyanate (MDI), diphenyldifluoromethane diisocyanate, p-phenylene diisocyanate , o-phenylene diisocyanate, isophenylene diisocyanate, 2,2'-biphenyl diisocyanate, 3,3'-biphenyl diisocyanate, 4,4'-biphenyl diisocyanate, naphthalene diisocyanate, or a combination thereof. According to the formulation for preparing thermoplastic polyurethane with high tensile strength according to claim 1, the aliphatic diol comprises a straight-chain diol having 2 to 40 carbon atoms or a branched diol having 2 to 40 carbon atoms. alcohol. According to the formulation for preparing thermoplastic polyurethane with high tensile strength according to claim 3, the linear diol having 2 to 40 carbon atoms comprises 1,4-butanediol, 1,5-pentanediol or 1,6-Hexanediol. The formulation for preparing thermoplastic polyurethane with high tensile strength as claimed in claim 1, the polyether diol comprises a polyether diol of polyethylene glycol, polypropylene glycol, or polytetrahydrofuran series, and the polyether diol The weight average molecular weight of the polyol is 100 to 5,000 Da. According to the formulation for preparing thermoplastic polyurethane with high tensile strength according to claim 5, the polyether glycol of the polytetrahydrofuran series is selected from one of the following groups or a combination thereof: polytetramethylene ether glycol (PTMEG), polytetramethylene ether glycol-ethylene glycol copolymer, and polytetramethylene ether glycol-propylene glycol copolymer. The formulation of claim 1 for preparing thermoplastic polyurethane with high tensile strength, the polyester diol comprises polyester diol, polycarbonate diol, polycaprolactone A polycaprolactone diol or a combination thereof. The formulation for preparing thermoplastic polyurethane with high tensile strength according to claim 1, wherein the aliphatic diol comprises 1,2-ethylene glycol, 1,4-butanediol or 1,6-hexanediol. The formulation for preparing a thermoplastic polyurethane with high tensile strength according to claim 1, the aliphatic monoalcohol monoamine comprises ethanolamine, 4-amino-1-butanol or 6-amino-1-hexanol. The formulation of claim 1 for the preparation of thermoplastic polyurethane with high tensile strength, the derivative derived from recycled PET bottles is hydroxyethyl 2-hydroxyethylaminoacylbenzoate (BHETTA), which has properties such as The chemical formula shown in formula (3):

According to the formula for preparing thermoplastic polyurethane with high tensile strength according to claim 1, the thermoplastic polyurethane with high tensile strength produced has the chemical formula shown in formula (4), and its tensile strength is greater than 3.0MPa;

Wherein the Ar is derived from the above-mentioned aromatic diisocyanate; the polyol segment is derived from the above-mentioned polyol, and the polyol is selected from one of the following groups: aliphatic diol, polyether diol, polyol ester diol and bisphenol compound; and the use weight ratio of the polyol and the aromatic diisocyanate is 2~20; and m is 1~10; the R is a derivative derived from the above-mentioned recycled PET bottles. The use weight ratio of the polyurethane oligomer to the recycled bottle-derived derivative is 2 to 25; and n is 2 to 30. A thermoplastic polyurethane derived from recycled PET bottles, the tensile strength of which is greater than 3.0 MPa, and the chemical formula shown in formula (4):

wherein the Ar is derived from an aromatic diisocyanate, the polyol segment is derived from a polyol, The polyol is selected from one of the following groups or a combination thereof: aliphatic diols, polyether diols, polyester diols and bisphenol compounds; the polyol and the aromatic diisocyanate are used in a weight ratio of 2 ~20, and m is 1~10; the R is a derivative derived from recycled PET bottles, and the use weight ratio of the polyurethane oligomer to the derivative derived from recycled PET bottles is 2~25; and n is 2~30. As claimed in claim 12, the thermoplastic polyurethane derived from recycled PET bottles, the aromatic diisocyanate comprises diphenylmethane diisocyanate (MDI), diphenyl difluoromethane diisocyanate, p-phenylene diisocyanate, o-phenylene diisocyanate Diisocyanate, isophenylene diisocyanate, 2,2'-biphenyl diisocyanate, 3,3'-biphenyl diisocyanate, 4,4'-biphenyl diisocyanate, naphthalene diisocyanate, or combinations thereof. As claimed in claim 12, the thermoplastic polyurethane derived from recycled PET bottles, the aliphatic diol comprises 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol. As claimed in claim 12, the thermoplastic polyurethane derived from recycled PET bottles, the polyether glycol comprises polyethylene glycol, polypropylene glycol, or polyether glycol of the polytetrahydrofuran series, and the polyether glycol of the polyether glycol The weight average molecular weight is 100 to 5,000 Da. As claimed in claim 15, the thermoplastic polyurethane originating from recycled PET bottles, the polytetrahydrofuran series polyether glycol is selected from one of the following groups or a combination thereof: polytetramethylene ether glycol (PTMEG), polytetrahydrofuran - Ethylene oxide (polytetramethylene ether glycol-ethylene glycol copolymer) and polytetramethylene ether glycol-propylene glycol copolymer. As claimed in claim 12, the thermoplastic polyurethane derived from recycled PET bottles, the polyester diol comprises polyester diol, polycarbonate diol, polycaprolactone diol ( polycaprolactone diol) or a combination thereof. As claimed in claim 12, the thermoplastic polyurethane derived from recycled PET bottles, the derivative derived from recycled PET bottles has the chemical formula shown in formula (2):

wherein, the R ₁ and R ₂ are derived from a diol compound, an alcoholamine compound or a combination thereof; the diol compound comprises aliphatic diol, aromatic diol, polyether diol or polyester diol; and The alcoholamine compound includes aliphatic monoalcohol monoamine or aromatic monoalcohol monoamine. As claimed in claim 12, the thermoplastic polyurethane derived from recycled PET bottles, the aliphatic diol comprises 1,2-ethylene glycol, 1,4-butanediol or 1,6-hexanediol. As claimed in claim 12, the thermoplastic polyurethane derived from recycled PET bottles, the aliphatic monoalcohol monoamine comprises ethanolamine, 4-amino-1-butanol or 6-amino-1-hexanol. As claimed in claim 12, the thermoplastic polyurethane derived from recycled PET bottles, the derivative derived from recycled PET bottles is hydroxyethyl 2-hydroxyethylaminoacylbenzoate (BHETTA). As claimed in claim 12, the thermoplastic polyurethane derived from recycled PET bottles has a weight average molecular weight of 10,000~400,000Da. A manufacturing method of thermoplastic polyurethane with high tensile strength, which comprises using the formula as claimed in items 1 to 10 to carry out chain extension reaction, thereby producing the thermoplastic polyurethane with high tensile strength, which has high tensile strength. The weight-average molecular weight of the thermoplastic polyurethane with tensile strength is 10,000~400,000 Da, its tensile strength is greater than 3.0 MPa, and has a chemical formula as shown in formula (4):

wherein the Ar is derived from an aromatic diisocyanate, the polyol segment is derived from a polyol, and the polyol is selected from one of the following groups or a combination thereof: aliphatic diol, polyether diol, polyester Diols and bisphenol compounds; the polyols and the aromatic diisocyanates The use weight ratio of ester is 2~20, and m is 1~10; the R is the derivative derived from recycled PET bottles, and the used weight of the polyurethane oligomer and the derivative derived from recycled PET bottles The ratio is 2~25; and n is 2~30. As claimed in claim 23, the production method of thermoplastic polyurethane with high tensile strength, the temperature of the chain extension reaction is 60 to 120°C.

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