Modified tpu material, its preparation method and application

Abstract

The application discloses a modified TPU material and a preparation method and application thereof. The modified TPU material comprises the following raw material components in parts by weight: 100 parts of polyether type TPU, 6 to 20 parts of phosphorus-nitrogen type flame retardant, 10 to 35 parts of filling modifier and 1 to 5 parts of coupling agent. The prepared modified TPU material has excellent mechanical properties and low-temperature performance, and the preparation method is simple and environment-friendly.

Description

Technical Field

[0001] This invention specifically relates to a modified TPU material, its preparation method, and its application. Background Technology

[0002] Electrical insulating tape, commonly known as electrical tape, is a special type of adhesive tape used for insulation of electrical wiring. In the past, adhesive-backed insulating tape, i.e., black insulating cloth, was used on electrical circuits. Its base fabric (backing material) was made of woven fabric impregnated with insulating material. Currently, the most common insulating tapes are polyvinyl chloride (PVC) and polyolefin (PE) insulating tapes. PVC tapes are the most common, but their disadvantages are also quite obvious: insufficient strength, easy breakage, and hardening and brittleness at low temperatures.

[0003] Therefore, developing a tape with good mechanical strength, low temperature resistance, and insulation and flame retardant properties has become a new demand in the industry. Summary of the Invention

[0004] The technical problem this invention aims to solve is to overcome the poor strength and low-temperature performance of existing insulating tapes, and to provide a modified TPU material, its preparation method, and its applications. The modified TPU material obtained by this invention has excellent mechanical properties and low-temperature performance, and the preparation method is simple and environmentally friendly.

[0005] The present invention solves the above-mentioned technical problems through the following technical solutions.

[0006] This invention provides a modified TPU material, which, by weight, comprises the following raw material components: 100 parts of polyether-type TPU, 6-20 parts of phosphorus-nitrogen flame retardant, 10-35 parts of filler modifier, and 1-5 parts of coupling agent.

[0007] In this invention, the amount of the phosphorus-nitrogen flame retardant is preferably 10 to 20 parts, for example 10 parts, 12 parts, 15 parts or 18 parts.

[0008] In this invention, the amount of the filler modifier is preferably 12 to 35 parts, more preferably 15 to 30 parts, for example 20 parts, 25 parts or 30 parts.

[0009] In this invention, the amount of the coupling agent is preferably 2 to 5 parts, for example 3 or 4 parts.

[0010] In a preferred embodiment of the present invention, the modified TPU material comprises, by weight, the following components: 100 parts of polyether-type TPU, 10 parts of phosphorus-nitrogen flame retardant, 20 parts of filler modifier, and 4 parts of coupling agent.

[0011] In a preferred embodiment of the present invention, the modified TPU material comprises, by weight, the following components: 100 parts of polyether-type TPU, 15 parts of phosphorus-nitrogen flame retardant, 30 parts of filler modifier, and 4 parts of coupling agent.

[0012] In a preferred embodiment of the present invention, the modified TPU material comprises, by weight, the following components: 100 parts of polyether-type TPU, 10 parts of phosphorus-nitrogen flame retardant, 10 parts of filler modifier, and 4 parts of coupling agent.

[0013] In this invention, the polyether-type TPU can be conventional in the art, preferably Covestro 9380A, BSF-1198A15 or BASF 1180A.

[0014] In this invention, the molecular weight of the polyether-type TPU can be conventional in the art, preferably 130,000-170,000, for example 150,000.

[0015] In this invention, the raw material particles of the polyether-type TPU preferably have a hardness of 75-90 Shore A, more preferably 80-90 Shore A, for example 80 Shore A.

[0016] In this invention, the phosphorus-nitrogen flame retardant is preferably JZ-M4 flame retardant or BIORICH FR191.

[0017] In this invention, the filler modifier generally refers to a substance that can improve the electrical properties of the material.

[0018] In this invention, the filler modifier is preferably kaolin.

[0019] The preferred types of kaolin are Chaopai DG80VG, diatomaceous earth SD-303, or Sanxin XS-90A.

[0020] In this invention, the coupling agent is preferably a silane coupling agent, such as γ-aminopropyltriethoxysilane.

[0021] The γ-aminopropyltriethoxysilane is preferably Dow Corning Z-6011.

[0022] In this invention, the TPU modified particles preferably also include color powder.

[0023] The pigment can be a conventional inorganic pigment in the art.

[0024] The amount of pigment used is preferably 1 to 3 parts, for example 1.5 parts or 2 parts.

[0025] In this invention, the form of the modified TPU material is not limited, and it can be modified TPU particles or modified TPU film.

[0026] This invention also provides a method for preparing a modified TPU material, which includes the following steps:

[0027] The raw materials for the modified TPU material can be mixed together.

[0028] In this invention, the mixing method can be a conventional method in the art, preferably internal mixing. The internal mixing equipment can be conventional equipment in the art, generally an internal mixer.

[0029] In this invention, the mixing temperature can be conventional in the art, preferably 80-200°C, more preferably 100-180°C, for example 110°C, 120°C or 160°C.

[0030] In this invention, the mixing generally includes three dispersion processes.

[0031] The temperature of the first stage of dispersion in the three-stage dispersion process can be 80-200℃, preferably 100-150℃, more preferably 110-130℃, for example 120℃.

[0032] The dispersion time for the first stage in the three-stage dispersion process can be conventional in the art, generally enough to keep the raw material of the TPU modified particles in a molten state.

[0033] The rotational speed of the first dispersion stage in the three-stage dispersion process can be 10-70 rpm, preferably 20-60 rpm, such as 35 rpm, 40 rpm or 50 rpm.

[0034] The temperature of the second stage of dispersion in the three-stage dispersion process can be 90-200℃, preferably 100-160℃, more preferably 120-140℃, for example 130℃.

[0035] The rotational speed of the second stage of dispersion in the three-stage dispersion process can be 20-70 rpm, preferably 30-65 rpm, such as 50 rpm, 55 rpm or 60 rpm.

[0036] The dispersion time of the second dispersion stage in the three-stage dispersion process can be conventional in the art, preferably 5-30 min, for example 10 min.

[0037] The temperature of the third dispersion stage in the three-stage dispersion process can be 100-200℃, preferably 110-190℃, more preferably 160-180℃, for example 170℃.

[0038] The rotational speed of the third dispersion stage in the three-stage dispersion process can be 20-70 rpm, preferably 30-60 rpm, such as 40 rpm, 45 rpm or 50 rpm.

[0039] The dispersion time of the third dispersion stage in the three-stage dispersion process can be conventional in the art, preferably 5-30 min, for example 10 min.

[0040] In this invention, the polyether-type TPU is preferably dried before mixing. The drying temperature can be a conventional drying temperature in the art, generally 100-105℃. The drying time can be a conventional drying time in the art, generally 3-4 hours. The drying equipment can be conventional equipment in the art, generally a dehumidifier.

[0041] In this invention, after mixing, the resulting rubber compound is preferably granulated.

[0042] The granulation method can be a conventional method in the art, generally extrusion granulation. The extrusion granulation equipment can be conventional extrusion granulation equipment in the art, such as a granulator.

[0043] During the granulation process, the equipment temperature generally includes zone one temperature, zone two temperature, zone three temperature, zone four temperature, flange zone temperature, and die head temperature.

[0044] During the granulation process, the temperature of the first zone can be 120-250℃, preferably 150-200℃, for example 180-190℃.

[0045] During the granulation process, the temperature in the second zone can be 120-250℃, preferably 160-200℃, for example 185-195℃.

[0046] During the granulation process, the temperature of the three zones can be 120-250℃, preferably 165-200℃, for example 190-200℃.

[0047] During the granulation process, the temperature of the four zones can be 130-300℃, preferably 170-250℃, for example 195-205℃.

[0048] During the granulation process, the temperature of the flange area can be 130-300℃, preferably 170-250℃, for example 200-210℃.

[0049] During the granulation process, the die temperature can be 130-300℃, preferably 170-250℃, for example 190-200℃.

[0050] In this invention, after mixing, the resulting rubber compound is preferably granulated and film-formed.

[0051] The granulation operation and conditions are as described above.

[0052] The masterbatch obtained from granulation is typically dried and then used to form a film. The drying temperature can be 40-120℃, for example, 90℃-105℃. The drying time can be 2-10 hours, for example, 3-4 hours.

[0053] The film-forming method can be a conventional method in the art, such as extrusion film formation. The equipment used for extrusion film formation can be conventional equipment in the art, such as a casting machine.

[0054] During the film formation process, the equipment temperature generally includes zone 1 temperature, zone 2 temperature, zone 3 temperature, zone 4 temperature, flange zone temperature, die head temperature, screw speed, middle roller temperature, and front roller temperature.

[0055] During the film formation process, the temperature of the first zone can be 120-250℃, preferably 150-200℃, for example 180-190℃.

[0056] During the film formation process, the temperature of the second zone can be 120-250℃, preferably 150-200℃, for example 185-195℃.

[0057] During the film formation process, the temperature of the three zones can be 120-250℃, preferably 150-200℃, for example 190-200℃.

[0058] During the film formation process, the temperature of the four zones can be 120-250℃, preferably 150-220℃, for example 195-205℃.

[0059] During the film formation process, the temperature of the flange area can be 120-250℃, preferably 150-220℃, for example 200-210℃.

[0060] During the film formation process, the temperature of the die head can be 120-250℃, preferably 150-220℃, for example 190-200℃.

[0061] During the film formation process, the screw speed can be 10-100 rpm, preferably 15-60 rpm, for example 20-40 rpm.

[0062] During the film formation process, the temperature of the middle roller can be 10-100℃, preferably 20-90℃, for example 40-60℃.

[0063] During the film formation process, the temperature of the front roller can be 10-100℃, preferably 15-80℃, for example 30-50℃.

[0064] The present invention also provides a modified TPU material prepared by the method described above.

[0065] The present invention also provides an application of the modified TPU material as described above in the fields of packaging, home decoration, construction or insulating tape.

[0066] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0067] The reagents and raw materials used in this invention are all commercially available.

[0068] The positive and progressive effects of this invention are as follows:

[0069] The TPU film prepared by this invention has good mechanical properties and low-temperature resistance. Moreover, its preparation method is simple, the yield is high, and it has high economic and environmental friendliness, which meets the needs of the industry. Detailed Implementation

[0070] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0071] The types and manufacturers of the raw materials used in the following examples and comparative examples are shown in Table 1 below:

[0072] Table 1

[0073]

[0074] The polyether-type TPU raw material particles used in the examples and comparative examples have a hardness of 80A.

[0075] The manufacturers and models of the equipment used in the following embodiments and comparative examples are shown in Table 2 below:

[0076] Table 2

[0077] Equipment Name model factory Dehumidifier ED-9 Shanghai Yixin Plastic Technology Co., Ltd. Internal mixer KD-110-400D Guangdong Lina Industrial Co., Ltd. Granulator KD-FR-75 Guangdong Lina Industrial Co., Ltd. Casting machine GWS92 / 34 Suzhou Jinwei Machinery Co., Ltd.

[0078] Example 1

[0079] Preparation of TPU film

[0080] The TPU film, by weight, comprises the following raw material components: 100 parts TPU (Covestro 9380A), 10 parts flame retardant (Jingzhuan New Material JZ-M4), 20 parts filler modifier (Chaopai DG80VG), 4 parts coupling agent (Dow Corning Z-6011), and 1.5 parts colorant (commercially available black colorant).

[0081] Step 1: Preparation of modified TPU particles:

[0082] 1.1 Drying: Dry the polyether-type TPU base material. The drying conditions are 100-105℃ for 3-4 hours. Drying and dehumidification are generally achieved using a drying and dehumidification machine.

[0083] 1.2 Weighing: Weigh the required raw materials, including polyether-type TPU base material, flame retardant, filler modifier, coupling agent, and color powder, in a weight ratio of 100:10:20:4:1.5.

[0084] 1.3 Internal Mixing and Dispersion: First, the polyether-type TPU base material is internally mixed in a mixer until it reaches a molten state (stage one, temperature and speed as shown in Table 3). Then, the weighed flame retardant, filler modifier, coupling agent, and colorant are added, and the mixture is further internally mixed for 20 minutes (stage two: 10 minutes, stage three: 10 minutes) to fully disperse and form the compound. The mixing process conditions in the internal mixer are shown in Table 3.

[0085] Table 3. Mixing operating parameters of the internal mixer

[0086] A temperature range ℃ Second temperature range (°C) Three temperature ranges (°C) A speed of rpm Second speed rpm Three speed settings rpm 110 120 160 35 50 40

[0087] 1.4 Extrusion Granulation: The rubber compound is fed into a single screw extruder to prepare modified TPU granules. The operating parameters for single-screw granulation are shown in Table 4.

[0088] Table 4 Operating parameters of single-screw granulation

[0089]

[0090] The temperature parameters for each section in Tables 3 and 4 represent the most suitable processing temperatures for this equipment. In actual implementation, the temperature in each zone can be adjusted by ±5℃.

[0091] Step 2, preparing the thin film:

[0092] 2.1 Drying: Dry the modified TPU particles prepared above at 90-105℃ for 3-4 hours.

[0093] 2.2 Film Extrusion: The modified TPU granules were extruded into films using a casting machine. The operating parameters of the casting machine are shown in Table 5.

[0094] Table 5 Operating parameters of the casting machine

[0095]

[0096] 2.3 Cooling and winding: Cool and wind up the above film.

[0097] 2.4 Packaging the finished product: The finished product is obtained by packaging.

[0098] Example 2

[0099] The TPU film, by weight, consists of the following components: 100 parts TPU (BASF 1180A), 10 parts flame retardant (BIORICH FR191), 20 parts filler modifier (Sanxin XS-90A), 4 parts coupling agent (Dow Corning Z-6011), and 1.5 parts colorant (commercially available black colorant).

[0100] Apart from the different components, the other operations and conditions are the same as in Example 1.

[0101] Example 3

[0102] The TPU film, by weight, consists of the following components: 100 parts TPU (Covestro 9380A), 15 parts flame retardant (Jingzhuan New Material JZ-M4), 30 parts filler modifier (Chaopai DG80VG), 4 parts coupling agent (Dow Corning Z-6011), and 1.5 parts colorant (commercially available black colorant).

[0103] Apart from the different components, the other operations and conditions are the same as in Example 1.

[0104] Example 4

[0105] The TPU film, by weight, consists of the following components: 100 parts TPU (BASF BSF-1198A15), 10 parts flame retardant (Jingzhuan New Material JZ-M4), 20 parts filler modifier (Chaopai DG80VG), 4 parts coupling agent (Dow Corning Z-6011), and 1.5 parts colorant (commercially available black colorant).

[0106] Apart from the different components, the other operations and conditions are the same as in Example 1.

[0107] Example 5

[0108] The TPU film, by weight, consists of the following components: 100 parts TPU (Covestro 9380A), 10 parts flame retardant (Jingzhuan New Material JZ-M4), 10 parts filler modifier (Chaopai DG80VG), 4 parts coupling agent (Dow Corning Z-6011), and 1.5 parts colorant (commercially available black colorant).

[0109] Apart from the different components, the other operations and conditions are the same as in Example 1.

[0110] Example 6

[0111] The TPU film, by weight, comprises the following raw material components: 100 parts TPU (Covestro 9380A), 10 parts flame retardant (Jingzhuan New Material JZ-M4), 20 parts filler modifier (diatomaceous earth SD-303), 4 parts coupling agent (Dow Corning Z-6011), and 1.5 parts colorant (commercially available black colorant).

[0112] Apart from the different components, the other operations and conditions are the same as in Example 1.

[0113] Comparative Example 1

[0114] The TPU film, by weight, consists of the following components: 100 parts TPU (Covestro 9380A), 5 parts flame retardant (Jingzhuan New Material JZ-M4), 20 parts filler modifier (Chaopai DG80VG), 4 parts coupling agent (Dow Corning Z-6011), and 1.5 parts colorant (commercially available black colorant).

[0115] Apart from the different components, the other operations and conditions are the same as in Example 1.

[0116] Comparative Example 2

[0117] The TPU film, by weight, comprises the following raw material components: 100 parts TPU (Covestro 9380A), 10 parts flame retardant (aluminum hypophosphite HT-802), 20 parts filler modifier (Chaopai DG80VG), 4 parts coupling agent (Dow Corning Z-6011), and 1.5 parts colorant (commercially available black colorant).

[0118] Apart from the different components, the other operations and conditions are the same as in Example 1.

[0119] Comparative Example 3

[0120] It is a commercially available 3M brand 1500 general-purpose electrical insulating tape.

[0121] Comparative Example 4

[0122] The TPU film, by weight, consists of the following components: 100 parts TPU (Covestro 9380A) and 1.5 parts pigment (commercially available black pigment).

[0123] The films prepared in the above embodiments and comparative examples have a thickness of 0.1 mm and a width of 400 mm.

[0124] Effect Example

[0125] Test subjects: TPU films prepared in Examples 1-6 and Comparative Examples 1-4.

[0126] Test equipment and methods: The models and manufacturers of the test equipment are shown in Table 6 below:

[0127] Table 6

[0128] Equipment / Instrument Name model factory tensile testing machine 2101(A) Suzhou Qiantong Instrument Equipment Co., Ltd. Hardness tester LAC-J Wenzhou Haibao Instrument Co., Ltd. Combustion test chamber LT-UL94 Shanghai Litao Automation Technology Co., Ltd. Withstand voltage tester KD2670J Shanghai Zhunquan Instrument Equipment Co., Ltd. Low temperature embrittlement tester DWC-70P Wuhan Kaidi Zhengda Electric Co., Ltd.

[0129] Test results are shown in Table 7 below:

[0130] Table 7 Performance of the TPU film formulations prepared in the examples and comparative examples

[0131]

[0132] As shown in Table 7, when all raw material components of the TPU film are within the limits defined by this invention, the prepared TPU film not only has good mechanical properties, but also good flame retardant properties, voltage resistance, and low-temperature resistance. Compared with Example 1, the voltage resistance of Example 2 is slightly reduced; the low-temperature resistance and elongation of Example 3 are poor, but the voltage resistance is good; the low-temperature resistance of Example 4 is poor; and the voltage resistance of Examples 5 and 6 are poor. Overall, Example 1 has the best comprehensive performance.

[0133] As can be seen from Comparative Example 1, when the amount of flame retardant is not within the limits of this invention, the prepared TPU film has good mechanical properties but poor flame retardant properties.

[0134] As can be seen from Comparative Example 2, when the flame retardant is not a phosphorus-nitrogen flame retardant, the prepared TPU film has poor flame retardant properties.

[0135] As can be seen from Comparative Example 3, conventional insulating tapes have poor mechanical properties, voltage resistance, and low-temperature resistance.

[0136] As can be seen from Comparative Example 4, when no flame retardant, filler modifier, and coupling agent are added, the mechanical properties, flame retardant properties, voltage resistance properties, and low-temperature resistance properties of the prepared TPU film are all poor.

Claims

1. A modified TPU material, characterized in that, By weight, it comprises the following raw material components: 100 parts of polyether-type TPU, 10 or 12 parts of phosphorus-nitrogen flame retardant, 15 to 30 parts of filler modifier, and 1 to 5 parts of coupling agent. The filler modifier is kaolin, the phosphorus-nitrogen flame retardant is JZ-M4 flame retardant or BIORICH FR191, and the polyether-type TPU is Covestro 9380A.

2. The modified TPU material of claim 1, wherein, The modified TPU material described above meets one or more of the following conditions: (1) The amount of the filler modifier is 20 parts, 25 parts or 30 parts; (2) The amount of the coupling agent is 2 to 5 parts.

3. The modified TPU material as described in claim 2, characterized in that, The amount of the coupling agent used is 3 or 4 parts.

4. The modified TPU material of claim 1, wherein, The modified TPU material comprises the following components by weight: 100 parts of polyether-type TPU, 10 parts of flame retardant, 20 parts of filler modifier, and 4 parts of coupling agent.

5. The modified TPU material of claim 1, wherein, The modified TPU material described above meets one or more of the following conditions: (1) The molecular weight of the polyether-type TPU is 130,000 to 170,000; (2) The raw material particles of the polyether-type TPU have a hardness of 75-90 Shore A; (3) The model of the kaolin is Chao brand DG80VG or Sanxin XS-90A; (4) The coupling agent is a silane coupling agent.

6. The modified TPU material of claim 5, wherein, The modified TPU material described above meets one or more of the following conditions: (1) The molecular weight of the polyether-type TPU is 150,000; (2) The raw material particles of the polyether-type TPU have a hardness of 80-90 Shore A; (3) The coupling agent is γ-aminopropyltriethoxysilane.

7. The modified TPU material of claim 6, wherein, The modified TPU material described above meets one or more of the following conditions: (1) The raw material particles of the polyether-type TPU have a hardness of 80 Shore A; (2) The coupling agent is Dow Corning Z-6011.

8. The modified TPU material as described in claim 1, characterized in that, The TPU modified material also includes colorant.

9. The modified TPU material as described in claim 8, characterized in that, The amount of pigment used is 1 to 3 parts.

10. The modified TPU material of claim 9, wherein, The amount of pigment used is 1.5 parts or 2 parts.

11. A method of producing a modified TPU material according to any one of claims 1 to 10, characterized in that, It includes the following steps: The raw materials for the modified TPU material can be mixed together.

12. The method of claim 11, wherein the modified TPU material is prepared by a process comprising: The preparation method satisfies one or more of the following conditions: (1) The mixing method is intensive mixing; (2) The mixing temperature is 80-200℃; (3) The mixing process includes three dispersion stages; (4) After mixing, the rubber compound obtained after mixing is granulated; (5) After mixing, the rubber compound obtained after mixing is granulated and film-formed.

13. The method for preparing the modified TPU material as described in claim 12, characterized in that, The preparation method satisfies one or more of the following conditions: (1) The equipment used for internal mixing is an internal mixer; (2) The mixing temperature is 100-180℃.

14. The method for preparing the modified TPU material as described in claim 13, characterized in that, The mixing temperature is 110°C, 120°C, or 160°C.

15. The method for preparing the modified TPU material as described in claim 12, characterized in that, The granulation method is extrusion granulation; And / or, the film-forming method is extrusion film formation.

16. The method of claim 15, wherein the modified TPU material is prepared by a process comprising: The extrusion granulation equipment is a granulator; And / or, the equipment used for extrusion film formation is a casting machine.

17. A modified TPU material, characterized in that, It is prepared by the method for preparing the modified TPU material according to any one of claims 11 to 15.

18. The application of a modified TPU material as described in any one of claims 1-10, or the application of the modified TPU material as described in claim 17 in the fields of packaging, home improvement, construction, or insulating tape.

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