Preparation method of chlorinated polyethylene modified TPU film

Abstract

The invention provides a chlorinated polyethylene modified TPU (thermoplastic polyurethane) film and a preparation method thereof. The chlorinated polyethylene modified TPU film comprises the following components in parts by weight: 60-80 parts of TPU particles, 10-20 parts of chlorinated polyethylene, 1-8 parts of coupling agent modified silicon dioxide, 1-8 parts of foamed silicone master batch and 5-10 parts of polycarbonate. The TPU film has good elasticity, toughness and aging resistance; wherein the chlorinated polyethylene and the coupling agent modified silicon dioxide act together, so that the toughness and the aging resistance of the TPU film can be improved; the foamed silicone master batch and the polycarbonate are combined together, so that the elasticity of the TPU film can be improved; the preparation method of the TPU film is simple, raw materials are easy to obtain, the price is low, implementation is easy, and industrial development and application are facilitated.

Description

Technical Field

[0001] The invention belongs to the field of polymer compounds and relates to a method for preparing a chlorinated polyethylene modified TPU film. Background Art

[0002] Thermoplastic polyurethane elastomer (TPU) is a mature environmentally friendly and non-toxic material. It has high strength, high elasticity, excellent wear resistance, low temperature resistance and other properties that other plastics and natural materials cannot match, and has high pressure bearing capacity. Although thermoplastic polyurethane elastomer has excellent performance, it also has certain limitations, such as elasticity, toughness and aging resistance, which still need to be improved.

[0003] CN109694458A provides a high-performance polymer TPU polyurethane elastomer, wherein the mass ratio of the A component to the B component is 11:2. The components of the A component are as follows by mass: 35-60 parts of polyether polyol, 10-20 parts of polyethylene glycol diol, 4-5 parts of dioctyl phthalate, and 5-8 parts of diisocyanate. The components of the B component are as follows by mass: 25-40 parts of polyether polyol, 5-8 parts of ultraviolet absorber UV-9, 10-14 parts of 1,4-cyclohexane diisocyanate, 2-6 parts of 1,4-butanediol, 4-8 parts of antioxidant 1010, and 20-30 parts of inorganic nanofiller. The TPU film provided by the invention has good aging resistance and toughness, but its elasticity still needs to be improved.

[0004] CN 105647162A provides a high-toughness TPU-based foam 3D printing material, which comprises the following components by weight: 85-95 parts of TPU, 1-3 parts of powder foaming agent, 7-10 parts of PSF, 0.5-1.5 parts of dispersing lubricant, 3-8 parts of toughening agent, 1-2.5 parts of stabilizer, 0.5-1 part of antioxidant, and an interfacial coupling agent selected from the group consisting of a silane coupling agent, a titanate coupling agent, and a zirconium coupling agent. The TPU-based foam 3D printing material obtained by the invention has good toughness, but its elasticity and aging resistance still need to be improved.

[0005] Therefore, it is very necessary to develop a TPU film with good elasticity, high toughness and good aging resistance. Summary of the invention

[0006] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for preparing a chlorinated polyethylene modified TPU film. The prepared chlorinated polyethylene modified TPU film has high toughness, elasticity and aging resistance, and the preparation method is simple, the raw materials are easily available, the price is low, it is easy to implement, and it is convenient for large-scale industrial production and application.

[0007] In order to achieve the above object, the present invention adopts the following technical solution:

[0008] A method for preparing a chlorinated polyethylene modified TPU film comprises the following steps:

[0009] 60-80 parts by weight of TPU particles, 10-20 parts by weight of chlorinated polyethylene, 1-8 parts by weight of coupling agent modified silica, 1-8 parts by weight of foamed silicone masterbatch, 5-10 parts by weight of polycarbonate and 1-5 parts by weight of processing aid are mixed to obtain the chlorinated polyethylene modified TPU film.

[0010] In the present invention, the chlorinated polyethylene modified TPU film includes TPU particles, chlorinated polyethylene, coupling agent modified silica, foamed silicone masterbatch and polycarbonate, so that the TPU film has good elasticity, toughness and aging resistance; wherein the chlorinated polyethylene and coupling agent modified silica work together to increase the toughness and aging resistance of the TPU film; the foamed silicone masterbatch and polycarbonate are combined together to improve the elasticity of the TPU film.

[0011] In the present invention, the added amount of TPU particles can be 60 parts by weight, 62 parts by weight, 65 parts by weight, 67 parts by weight, 70 parts by weight, 72 parts by weight, 75 parts by weight, 77 parts by weight, 80 parts by weight, etc.

[0012] In the present invention, the addition amount of chlorinated polyethylene can be 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, etc.

[0013] In the present invention, the addition amount of the coupling agent-modified silica can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, etc.

[0014] In the present invention, the added amount of the foamed silicone masterbatch can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, etc.

[0015] In the present invention, the added amount of polycarbonate can be 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, or 10 parts by weight.

[0016] In the present invention, the TPU particles are polyester TPU particles and / or polyether TPU particles.

[0017] In the present invention, the TPU particles are a combination of polyester TPU particles and polyether TPU particles.

[0018] In the present invention, the mass ratio of the polyester TPU particles to the polyether TPU particles is (1-5):1, for example, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, etc.

[0019] In the present invention, by selecting polyester TPU particles and polyether TPU particles to work together, and the mass ratio of the two is within the range defined by the present invention, the elasticity, toughness and anti-aging properties of the TPU film can be increased; if the mass ratio of the two is not within the range defined by the present invention, or if either of the two is missing, the performance of the TPU film will be reduced.

[0020] In the present invention, the chlorinated polyethylene includes any one of CPE135B, CPE702P or CPE135A or a combination of at least two thereof.

[0021] In the present invention, the coupling agent used in the coupling agent-modified silica is a silane coupling agent.

[0022] In the present invention, the silane coupling agent includes any one of KH-172, KH-171 or KH-151, or a combination of at least two of them.

[0023] In the present invention, the particle size of the silica used in the coupling agent-modified silica is 0.1-5 μm, for example, 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, 5 μm, etc.

[0024] In the present invention, the preparation method of the coupling agent modified silica comprises: adding silica to a solvent, dispersing to obtain a dispersion, and then adding a coupling agent to the dispersion, mixing, reacting, and separating to obtain the coupling agent modified silica.

[0025] In the present invention, the solvent is toluene.

[0026] In the present invention, the dispersion method is ultrasonic dispersion.

[0027] In the present invention, the dispersion time is 30-60 min, for example, 30 min, 32 min, 35 min, 37 min, 40 min, 42 min, 45 min, 47 min, 50 min, 52 min, 55 min, 57 min, 60 min, etc.

[0028] In the present invention, the mixing method is ultrasonic mixing.

[0029] In the present invention, the reaction temperature is 80-100°C, for example, 80°C, 82°C, 85°C, 87°C, 90°C, 92°C, 95°C, 97°C, 100°C, etc.

[0030] In the present invention, the reaction time is 5-8h, for example, 5h, 5.2h, 5.5h, 5.7h, 6h, 6.2h, 6.5h, 6.7h, 7h, 7.2h, 7.5h, 7.8h, 8h and the like.

[0031] In the present invention, the separation method is centrifugation.

[0032] In the present invention, polymer resin, silicone powder, antioxidant and foaming agent are mixed and extruded to obtain foamed silicone masterbatch.

[0033] In the present invention, based on 100 parts by weight of the polymer resin, the amount of silicone powder added is 80-100 parts by weight (for example, 80 parts by weight, 85 parts by weight, 90 parts by weight, 95 parts by weight, 100 parts by weight, etc.), the amount of antioxidant added is 0.5-1 part by weight (for example, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, etc.), and the amount of foaming agent added is 2-8 parts by weight (for example, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, etc.).

[0034] In the present invention, the polymer resin includes any one of polyethylene, polypropylene, polystyrene or nylon, or a combination of at least two of them.

[0035] In the present invention, the antioxidant includes antioxidant 1010 and / or antioxidant 168.

[0036] In the present invention, the foaming agent includes any one of sodium bicarbonate, sodium citrate or methylsulfonyl urea or a combination of at least two thereof.

[0037] In the present invention, the number average molecular weight of the polycarbonate is 30,000-80,000, for example, 30,000, 35,000, 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000, 75,000, or 80,000.

[0038] In the present invention, the polycarbonate includes any one of PC2805, PC2407 or PC110, or a combination of at least two of them.

[0039] In the present invention, the chlorinated polyethylene modified TPU film also includes 1-5 parts by weight (e.g., 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, etc.) of additives.

[0040] In the present invention, the additive comprises any one of a defoamer, a flame retardant or a light stabilizer, or a combination of at least two thereof.

[0041] The second object of the present invention is to provide a method for preparing the chlorinated polyethylene modified TPU film as described in the first object, the preparation method comprising the following steps: mixing TPU particles, chlorinated polyethylene, coupling agent modified silica, foaming silicone masterbatch, polycarbonate and optional processing aids to obtain the chlorinated polyethylene modified TPU film.

[0042] The TPU film preparation method of the present invention is simple, the raw materials are readily available, the price is low, it is easy to realize, and it is convenient for industrial large-scale production and application.

[0043] In the present invention, the mixing temperature is 80-120°C, for example, 80°C, 82°C, 85°C, 87°C, 90°C, 92°C, 95°C, 97°C, 100°C, 102°C, 105°C, 107°C, 110°C, 112°C, 115°C, 117°C, 120°C, etc.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] The TPU film prepared in the present invention has good elasticity, toughness and aging resistance; wherein the tensile strength can reach 96.5MPa, the bending strength can reach 178MPa, the tear strength can reach 171kg / cm2, the impact strength can reach 60J / m2, and the tensile strength retention rate can reach 93.2%; the chlorinated polyethylene and the coupling agent modified silicon dioxide can work together to increase the toughness and aging resistance of the TPU film; the foamed silicone masterbatch and the polycarbonate can be combined together to improve the elasticity of the TPU film; the preparation method of the TPU film is simple, the raw materials are easily available, the price is low, it is easy to realize, and it is convenient for industrial development and application. DETAILED DESCRIPTION

[0046] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0047] Example 1

[0048] The components used in the preparation of the chlorinated polyethylene modified TPU film of the present invention are:

[0049] 70 parts by weight of TPU particles, 15 parts by weight of chlorinated polyethylene, 5 parts by weight of coupling agent modified silica, 5 parts by weight of foamed silicone masterbatch, and 8 parts by weight of polycarbonate;

[0050] The TPU particles are a combination of polyester TPU particles (Bayer 5377, Germany) and polyether TPU particles (BASF 1185A), and the mass ratio of polyester TPU particles to polyether TPU particles is 3:1; the chlorinated polyethylene is CPE135B; the silane coupling agent for coupling agent-modified silica is KH-172, and the particle size of silica is 3 μm; the preparation method of coupling agent-modified silica comprises: adding silica to toluene, ultrasonically dispersing for 40 minutes, and obtaining dispersion, and then adding a silane coupling agent to the dispersion, ultrasonically mixing, reacting at 90° C. for 6 hours, and centrifuging to obtain coupling agent-modified silica; the preparation method of the foamed silicone masterbatch comprises: mixing 100 parts by weight of polyethylene resin (high-density polyethylene resin 5000S), 90 parts by weight of silicone powder (ST-SL100), 1 part by weight of antioxidant 1010 and 5 parts by weight of sodium bicarbonate, extruding, dehydrating and drying to obtain a foamed silicone masterbatch; the polycarbonate is PC2805.

[0051] This embodiment also provides a method for preparing a chlorinated polyethylene modified TPU film, the preparation method comprising: mixing TPU particles, chlorinated polyethylene, coupling agent modified silica, foamed silicone masterbatch and polycarbonate at 100° C. for 5 hours to obtain the chlorinated polyethylene modified TPU film.

[0052] Example 2

[0053] The components used in the preparation of the chlorinated polyethylene modified TPU film of the present invention are:

[0054] 60 parts by weight of TPU particles, 20 parts by weight of chlorinated polyethylene, 1 part by weight of coupling agent modified silica, 8 parts by weight of foamed silicone masterbatch, and 5 parts by weight of polycarbonate;

[0055] The TPU particles are a combination of polyester TPU particles (Bayer 5377 from Germany) and polyether TPU particles (BASF 1185A), and the mass ratio of the polyester TPU particles to the polyether TPU particles is 1:1; the chlorinated polyethylene is CPE702P; the silane coupling agent used for coupling agent-modified silica is KH-171, and the particle size of silica is 0.1 μm; the preparation method of coupling agent-modified silica comprises: adding silica to toluene, ultrasonically dispersing for 30 minutes, and obtaining to a dispersion, and then adding a silane coupling agent to the dispersion, ultrasonically mixing, reacting at 100° C. for 5 hours, and centrifuging to obtain coupling agent-modified silica; the preparation method of the foamed silicone masterbatch comprises: mixing 100 parts by weight of a polyethylene resin (high-density polyethylene resin 5000S), 80 parts by weight of a silicone powder (ST-SL100), 1 part by weight of an antioxidant 168, and 2 parts by weight of sodium bicarbonate, extruding, dehydrating, and drying to obtain a foamed silicone masterbatch; the polycarbonate is PC2407.

[0056] This embodiment also provides a method for preparing a chlorinated polyethylene modified TPU film, the preparation method comprising: mixing TPU particles, chlorinated polyethylene, coupling agent modified silica, foamed silicone masterbatch and polycarbonate at 80° C. for 8 hours to obtain the chlorinated polyethylene modified TPU film.

[0057] Example 3

[0058] The components used in the preparation of the chlorinated polyethylene modified TPU film of the present invention are:

[0059] 80 parts by weight of TPU particles, 10 parts by weight of chlorinated polyethylene, 8 parts by weight of coupling agent modified silica, 1 part by weight of foamed silicone masterbatch, and 10 parts by weight of polycarbonate;

[0060] The TPU particles are a combination of polyester TPU particles (Bayer 5377, Germany) and polyether TPU particles (BASF 1185A), and the mass ratio of polyester TPU particles to polyether TPU particles is 5:1; the chlorinated polyethylene is CPE135A; the silane coupling agent used for coupling agent-modified silica is KH-151, and the particle size of silica is 5 μm; the preparation method of coupling agent-modified silica comprises: adding silica to toluene, ultrasonically dispersing for 60 minutes, and obtaining dispersion, and then adding a silane coupling agent to the dispersion, ultrasonically mixing, reacting at 80° C. for 8 hours, and centrifuging to obtain coupling agent-modified silica; the preparation method of the foamed silicone masterbatch comprises: mixing 100 parts by weight of polyethylene resin (high-density polyethylene resin 5000S), 100 parts by weight of silicone powder (ST-SL100), 0.5 parts by weight of antioxidant 168 and 8 parts by weight of sodium bicarbonate, extruding, dehydrating and drying to obtain a foamed silicone masterbatch; the polycarbonate is PC110.

[0061] This embodiment also provides a method for preparing a chlorinated polyethylene modified TPU film, the preparation method comprising: mixing TPU particles, chlorinated polyethylene, coupling agent modified silica, foamed silicone masterbatch and polycarbonate at 120° C. for 2 hours to obtain the chlorinated polyethylene modified TPU film.

[0062] Example 4

[0063] The only difference from Example 1 is that the mass ratio of polyester TPU particles to polyether TPU particles is 0.5:1, and the rest of the composition and preparation method are the same as those in Example 1.

[0064] Example 5

[0065] The only difference from Example 1 is that the mass ratio of polyester TPU particles to polyether TPU particles is 8:1, and the rest of the composition and preparation method are the same as those in Example 1.

[0066] Comparative Example 1

[0067] The only difference from Example 1 is that the TPU particles are only polyester TPU particles and do not include polyether TPU particles. The rest of the composition and preparation method are the same as those in Example 1.

[0068] Comparative Example 2

[0069] The only difference from Example 1 is that the TPU particles are only polyether TPU particles and do not include polyester TPU particles. The rest of the composition and preparation method are the same as those in Example 1.

[0070] Comparative Example 3

[0071] The only difference from Example 1 is that the TPU film does not include chlorinated polyethylene, the amount of coupling agent modified silica added is the sum of the amounts of chlorinated polyethylene and coupling agent modified silica added in Example 1, and the rest of the composition and preparation method are the same as Example 1.

[0072] Comparative Example 4

[0073] The only difference from Example 1 is that the TPU film does not include coupling agent modified silica, the amount of chlorinated polyethylene added is the sum of the amounts of chlorinated polyethylene and coupling agent modified silica added in Example 1, and the rest of the composition and preparation method are the same as Example 1.

[0074] Comparative Example 5

[0075] The only difference from Example 1 is that the TPU film does not include the foamed silicone masterbatch, the amount of polycarbonate added is the sum of the amounts of the foamed silicone masterbatch and polycarbonate added in Example 1, and the rest of the composition and preparation method are the same as those in Example 1.

[0076] Comparative Example 6

[0077] The only difference from Example 1 is that the TPU film does not include polycarbonate, the amount of foamed silicone masterbatch added is the sum of the amounts of foamed silicone masterbatch and polycarbonate added in Example 1, and the rest of the composition and preparation method are the same as those in Example 1.

[0078] The TPU films obtained in Examples 1-5 and Comparative Examples 1-6 were tested for elasticity, toughness and aging resistance, and mechanical properties were tested according to the method of GB / T528-1998 (ISO37:2005); aging properties (i.e., tensile strength retention) were tested according to the method of ASTM D1148-2013. The test results are shown in Table 1:

[0079] Table 1

[0080]

[0081] As shown in Table 1, the chlorinated polyethylene modified TPU film has good toughness (tear strength and impact strength), elasticity (tensile strength and flexural strength) and aging resistance (tensile strength retention rate), among which the tensile strength can reach 96.5MPa, the flexural strength can reach 178MPa, the tear strength can reach 171kg / cm, and the impact strength can reach 60J / m 2, the tensile strength retention rate can reach 93.2%; from the comparison of Example 1 and Examples 4-5, it can be seen that when the mass ratio of polyester TPU particles and polyether TPU particles is not within the range specified by the present invention, the tensile strength, bending strength, tear strength and impact strength of the chlorinated polyethylene modified TPU film will be reduced; from the comparison of Example 1 and Comparative Examples 1-2, it can be seen that when the TPU particles select any one of polyether TPU particles or polyester TPU particles, the tensile strength, bending strength, tear strength and impact strength of the chlorinated polyethylene modified TPU film will be greatly reduced; from the comparison of Example 1 and Comparative Examples 3-4, it can be seen that when the chlorinated polyethylene modified TPU film does not include chlorinated polyethylene or coupling agent modified silica, the toughness and aging resistance of the TPU film will be greatly reduced; from the comparison of Example 1 and Comparative Examples 5-6, it can be seen that when the chlorinated polyethylene modified TPU film does not include any one of foaming silicone masterbatch and polycarbonate, the elasticity of the TPU film will be greatly reduced.

[0082] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.

[0083] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a chlorinated polyethylene modified TPU film, characterized in that: The steps include: 60-80 parts by weight of TPU particles, 10-20 parts by weight of chlorinated polyethylene, 1-8 parts by weight of coupling agent modified silica, 1-8 parts by weight of foamed silicone masterbatch, 5-10 parts by weight of polycarbonate and 1-5 parts by weight of processing aid are mixed to obtain the chlorinated polyethylene modified TPU film.

2. The method for preparing a chlorinated polyethylene modified TPU film according to claim 1, characterized in that: The preparation method of the coupling agent modified silica comprises: adding silica into a solvent, dispersing to obtain a dispersion, then adding a coupling agent into the dispersion, mixing, reacting, and separating to obtain the coupling agent modified silica.

3. The method for preparing a chlorinated polyethylene modified TPU film according to claim 1, characterized in that: The preparation method of the foamed silicone masterbatch comprises: mixing a polymer resin, silicone powder, an antioxidant and a foaming agent, and extruding the mixture to obtain the foamed silicone masterbatch.

4. The method for preparing a chlorinated polyethylene modified TPU film according to claim 1, characterized in that: The number average molecular weight of the polycarbonate is 30,000-80,000; preferably, the polycarbonate includes any one of PC2805, PC2407 or PC110, or a combination of at least two of them.

5. The method for preparing a chlorinated polyethylene modified TPU film according to claim 1, characterized in that: The additive comprises any one of a defoamer, a flame retardant or a light stabilizer, or a combination of at least two of them.

6. The method for preparing a chlorinated polyethylene modified TPU film according to claim 1, characterized in that: The mixing temperature is 80-120° C. and the mixing time is 2-8 hours.

7. The method for preparing a chlorinated polyethylene modified TPU film according to claim 1, characterized in that: The TPU particles are polyester TPU particles and / or polyether TPU particles.

8. The method for preparing a chlorinated polyethylene modified TPU film according to claim 1, characterized in that: The coupling agent used in the coupling agent-modified silica is a silane coupling agent.

9. The method for preparing a chlorinated polyethylene modified TPU film according to claim 1, characterized in that: The chlorinated polyethylene includes any one of CPE135B, CPE702P or CPE135A or a combination of at least two thereof.

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