WO2022127069A1 - 一种低收缩率tpu薄膜及其制备方法 - Google Patents

一种低收缩率tpu薄膜及其制备方法 Download PDF

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WO2022127069A1
WO2022127069A1 PCT/CN2021/102965 CN2021102965W WO2022127069A1 WO 2022127069 A1 WO2022127069 A1 WO 2022127069A1 CN 2021102965 W CN2021102965 W CN 2021102965W WO 2022127069 A1 WO2022127069 A1 WO 2022127069A1
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tpu film
shrinkage
low
preparation
parts
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何建雄
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何建雄
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass

Definitions

  • the invention belongs to the technical field of polymer materials, and relates to a low shrinkage TPU film and a preparation method thereof.
  • Polyurethane materials are widely used in home appliances, furniture, instruments, clothing and other fields due to their own advantages such as flexibility, wear resistance, and transparency. Applications are limited to a certain extent.
  • CN111087947A discloses a low-shrinkage adhesive resin and a preparation method thereof.
  • the low-shrinkage adhesive resin in parts by weight, includes components: 20-40 parts of high-density polyethylene, low-modified linear 20-50 parts of density polyethylene, 20-50 parts of polypropylene, 5-15 parts of nucleating agent and 0.1-3 parts of stabilizer.
  • the adhesive resin has a low shrinkage rate, thereby reducing the local stress caused by the shrinkage of the adhesive resin at the connection interface between the various parts of the profile, and reducing the deformation and cracking of plastic products.
  • the binder resin is based on polyethylene and polypropylene materials, and there is no relevant report on how to reduce the shrinkage rate of polyurethane materials.
  • the purpose of the present invention is to provide a low shrinkage TPU film and a preparation method thereof.
  • the low shrinkage TPU film of the present invention has low shrinkage and good mechanical properties, and is suitable for many fields such as automobiles, household appliances, furniture, instruments, clothing, and machinery industries.
  • the present invention provides a kind of low-shrinkage TPU film
  • the preparation raw material of described low-shrinkage TPU film comprises the following components in parts by weight:
  • polypropylene can reduce the shrinkage rate of the TPU film, but the effect is not very ideal. Therefore, in the present invention, the combination of calcium carbonate, graphene and glass fiber is used to further reduce the shrinkage rate of the TPU film, and can ensure The flexibility of the TPU film as well as the good mechanical properties and processing properties.
  • the low shrinkage ratio means that the shrinkage ratio is tested according to the method of ISO2577, and its value is below 0.5%.
  • the dosage of TPU particles in the preparation raw material of low shrinkage TPU film, can be 2 parts by weight, 65 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 75 parts by weight, 78 parts by weight, etc.
  • the amount of polypropylene used in the raw material for the preparation of the low shrinkage TPU film, can be 22 parts by weight, 25 parts by weight, 27 parts by weight, 29 parts by weight, and the like.
  • the amount of calcium carbonate in the preparation raw material of low shrinkage TPU film, can be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight or 8 parts by weight.
  • the amount of the graphene material in the raw material for the preparation of the low shrinkage TPU film, can be 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight or 5 parts by weight.
  • the amount of glass fiber in the preparation raw material of the low shrinkage TPU film, 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.
  • the amount of the antioxidant in the preparation raw materials of the low shrinkage TPU film, can be 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 1.8 parts by weight or 2 parts by weight.
  • the TPU particles are polyether TPU particles.
  • the polypropylene is a copolymerized polypropylene, and its melt flow rate is 10-40g/10min, such as 10g/10min, 13g/10min, 15g/10min, 18g/ 10min, 20g/10min, 25g/10min, 28g/10min, 30g/10min, 35g/10min, 38g/10min or 40g/10min.
  • the graphene material is single-layer graphene, multi-layer graphene or graphene oxide, preferably graphene oxide.
  • the length of the glass fibers is 5mm-20mm, such as 5mm, 8mm, 10mm, 13mm, 15mm, 18mm or 20mm.
  • the antioxidant is any one of Antioxidant 3114, Antioxidant 1010, Antioxidant 168 or Antioxidant 618, or a combination of at least two of them.
  • the present invention provides the preparation method of the above-mentioned low shrinkage TPU film, and the preparation method comprises the following steps:
  • the glass fiber and the graphene material are first mixed, so that the glass fiber is interspersed into the sheet layer of the graphene material, the agglomeration of the graphene material is reduced, and its dispersibility is improved, and then it is mixed with TPU particles, polypropylene and Antioxidant mixing can make the glass fiber and graphene materials better mix with the main resin.
  • TPU particles, polypropylene and Antioxidant mixing can make the glass fiber and graphene materials better mix with the main resin.
  • These mixtures are added to the twin-screw extruder from the main feed port, and calcium carbonate is added to the twin-screw extruder from the side feed port.
  • calcium carbonate is spherical particles that can cooperate with glass fiber and graphene materials, and fully fill the structure of TPU particles and polypropylene materials to reduce the shrinkage rate of the material.
  • the rotational speed of the two mixing in step (1) is independently 600-1000r/min, such as 600r/min, 650r/min, 700r/min, 750r/min, 800r/min, 850r/min, 900r/min min, 950r/min or 1000r/min.
  • the time for the two times of mixing in step (1) is independently 10-20 min, such as 10 min, 12 min, 14 min, 15 min, 17 min, 19 min or 20 min.
  • the rotational speed of the twin-screw extruder during the extrusion in step (2) is 200-500r/min, such as 200r/min, 220r/min, 250r/min, 280r/min, 300r/min, 350r/min , 400r/min or 500r/min.
  • the temperature of the feeding section of the twin-screw extruder during the extrusion in step (2) is 160-170 °C (for example, 160 °C, 162 °C, 165 °C, 168 °C, 170 °C), and the temperature of the mixing section is 180 °C ⁇ 190°C (eg 180°C, 182°C, 185°C, 188°C, 190°C), the extrusion temperature is 200-220°C (eg 200°C, 205°C, 208°C, 210°C, 212°C, 215°C, 218°C, 220°C), and the head temperature is 210-220°C (for example, 210°C, 212°C, 215°C, 218°C, 220°C).
  • the present invention has the following beneficial effects:
  • polypropylene, calcium carbonate, graphene and glass fiber are used to reduce the shrinkage rate of the TPU film, especially the combination of calcium carbonate, graphene and glass fiber makes the shrinkage rate of the TPU film below 0.5%, and can ensure that the TPU film shrinks Film flexibility and good mechanical and processing properties.
  • a low-shrinkage TPU film is provided, and the preparation raw materials of the low-shrinkage TPU film include the following components in parts by weight:
  • the TPU particles are polyether TPU particles (BASF 1185A), and the polypropylene is K9026, a copolymerized polypropylene produced by Yanshan Petrochemical.
  • Objective Calcium carbonate (Foshan Bozhen Chemical Industry)
  • the graphene material is graphene oxide
  • the length of glass fiber is 10-13mm
  • the antioxidant is antioxidant 1010.
  • the preparation method includes the following steps:
  • step (2) adding calcium carbonate into the twin-screw extruder from the side feeding port, the rotational speed of the twin-screw extruder is 200r/min, and the temperature of the feeding section of the twin-screw extruder during the extrusion described in step (2) is 160° C., the temperature of the mixing section is 180° C., the temperature of the extrusion section is 200° C., and the temperature of the die head is 210° C., and extrusion molding is performed to obtain the low shrinkage TPU film.
  • a low-shrinkage TPU film is provided, and the preparation raw materials of the low-shrinkage TPU film include the following components in parts by weight:
  • the TPU particles are polyether TPU particles (BASF 1185A), and the polypropylene is K9026, a copolymerized polypropylene produced by Yanshan Petrochemical.
  • Objective Calcium carbonate (Foshan Bozhen Chemical Industry)
  • the graphene material is graphene oxide
  • the length of glass fiber is 10-13mm
  • the antioxidant is antioxidant 168.
  • the preparation method includes the following steps:
  • step (2) adding calcium carbonate into the twin-screw extruder from the side feeding port, the rotational speed of the twin-screw extruder is 500 r/min, and the temperature of the feeding section of the twin-screw extruder during the extrusion described in step (2) is 170°C, the temperature of the mixing section is 190°C, the temperature of the extrusion section is 220°C, and the temperature of the die head is 220°C, and extrusion molding is performed to obtain the low shrinkage TPU film.
  • a low shrinkage TPU film is provided, and the preparation raw material of the low shrinkage TPU film comprises the following components by weight:
  • the TPU particles are polyether TPU particles (BASF 1185A), and the polypropylene is K9026, a copolymerized polypropylene produced by Yanshan Petrochemical.
  • Objective Calcium carbonate (Foshan Bozhen Chemical Industry)
  • the graphene material is graphene oxide
  • the length of glass fiber is 10-13mm
  • the antioxidant is antioxidant 618.
  • the preparation method includes the following steps:
  • step (2) adding calcium carbonate into the twin-screw extruder from the side feeding port, the rotational speed of the twin-screw extruder is 400 r/min, and the temperature of the feeding section of the twin-screw extruder during the extrusion described in step (2) is 160° C., the temperature of the mixing section is 190° C., the temperature of the extrusion section is 220° C., and the temperature of the die head is 210° C., and extrusion molding is performed to obtain the low shrinkage TPU film.
  • a low-shrinkage TPU film is provided, and the preparation raw materials of the low-shrinkage TPU film include the following components in parts by weight:
  • the TPU particles are polyether TPU particles (BASF 1185A), and the polypropylene is K9026, a copolymerized polypropylene produced by Yanshan Petrochemical.
  • Objective Calcium carbonate (Foshan Bozhen Chemical Industry)
  • the graphene material is graphene oxide
  • the length of glass fiber is 15-18mm
  • the antioxidant is antioxidant 1010.
  • the preparation method includes the following steps:
  • step (2) adding calcium carbonate into the twin-screw extruder from the side feeding port, the rotational speed of the twin-screw extruder is 200r/min, and the temperature of the feeding section of the twin-screw extruder during the extrusion described in step (2) is 160° C., the temperature of the mixing section is 190° C., the temperature of the extrusion section is 200° C., and the temperature of the die head is 210° C., and extrusion molding is performed to obtain the low shrinkage TPU film.
  • a low-shrinkage TPU film is provided, and the preparation raw materials of the low-shrinkage TPU film include the following components in parts by weight:
  • the TPU particles are polyether TPU particles (BASF 1185A), and the polypropylene is K9026, a copolymerized polypropylene produced by Yanshan Petrochemical.
  • Objective Calcium carbonate (Foshan Bozhen Chemical Industry)
  • the graphene material is graphene oxide
  • the length of glass fiber is 18-20mm
  • the antioxidant is antioxidant 3114.
  • the preparation method includes the following steps:
  • step (2) adding calcium carbonate into the twin-screw extruder from the side feeding port, the rotational speed of the twin-screw extruder is 500 r/min, and the temperature of the feeding section of the twin-screw extruder during the extrusion described in step (2) is 170°C, the temperature of the mixing section is 185°C, the temperature of the extrusion section is 210°C, and the temperature of the die head is 220°C, and extrusion molding is performed to obtain the low shrinkage TPU film.
  • a low-shrinkage TPU film is provided, and the preparation raw materials of the low-shrinkage TPU film include the following components in parts by weight:
  • the TPU particles are polyether TPU particles (BASF 1185A), and the polypropylene is K9026, a copolymerized polypropylene produced by Yanshan Petrochemical.
  • Objective Calcium carbonate (Foshan Bozhen Chemical Industry)
  • the graphene material is graphene oxide
  • the length of glass fiber is 10-13mm
  • the antioxidant is antioxidant 1010.
  • the preparation method includes the following steps:
  • step (2) adding calcium carbonate into the twin-screw extruder from the side feeding port, the rotating speed of the twin-screw extruder is 300r/min, and the temperature of the feeding section of the twin-screw extruder during the extrusion described in step (2) is 170°C, the temperature of the mixing section is 190°C, the temperature of the extrusion section is 220°C, and the temperature of the die head is 220°C, and extrusion molding is performed to obtain the low shrinkage TPU film.
  • a low-shrinkage TPU film is provided, and the preparation raw materials of the low-shrinkage TPU film include the following components in parts by weight:
  • the TPU particles are polyether TPU particles (BASF 1185A), and the polypropylene is K9026, a copolymerized polypropylene produced by Yanshan Petrochemical.
  • Objective Calcium carbonate (Foshan Bozhen Chemical Industry)
  • the graphene material is graphene oxide
  • the length of glass fiber is 13-15mm
  • the antioxidant is antioxidant 1010.
  • the preparation method includes the following steps:
  • step (2) adding calcium carbonate into the twin-screw extruder from the side feeding port, the rotational speed of the twin-screw extruder is 400 r/min, and the temperature of the feeding section of the twin-screw extruder during the extrusion described in step (2) is 170°C, the temperature of the mixing section is 190°C, the temperature of the extrusion section is 220°C, and the temperature of the die head is 220°C, and extrusion molding is performed to obtain the low shrinkage TPU film.
  • a low-shrinkage TPU film is provided, and the preparation raw materials of the low-shrinkage TPU film include the following components in parts by weight:
  • the TPU particles are polyether TPU particles (BASF 1185A), and the polypropylene is K9026, a copolymerized polypropylene produced by Yanshan Petrochemical.
  • Objective Calcium carbonate (Foshan Bozhen Chemical Industry)
  • the graphene material is graphene oxide
  • the length of glass fiber is 10-13mm
  • the antioxidant is antioxidant 1010.
  • the preparation method includes the following steps:
  • step (2) adding calcium carbonate into the twin-screw extruder from the side feeding port, the rotational speed of the twin-screw extruder is 500 r/min, and the temperature of the feeding section of the twin-screw extruder during the extrusion described in step (2) is 170°C, the temperature of the mixing section is 180°C, the temperature of the extrusion section is 200°C, the temperature of the die head is 210°C, and extrusion molding is performed to obtain the low shrinkage TPU film.
  • Example 1 The difference between this comparative example and Example 1 is that calcium carbonate is not used in the preparation raw material of the TPU film, and the amount of graphene material and glass fiber is both 6.5 parts by weight.
  • the difference between this comparative example and Example 1 is that the graphene material is not used in the preparation raw material of the TPU film, the consumption of calcium carbonate is 5 parts by weight, and the consumption of glass fiber is 8 parts by weight.
  • Example 1 The difference between this comparative example and Example 1 is that glass fiber is not used in the preparation raw materials of the TPU film, the consumption of calcium carbonate is 5 parts by weight, and the consumption of graphene material is 8 parts by weight.
  • thermoplastic polyurethane elastomers of Examples 1-5 and Comparative Examples 1-7 were tested for performance, and the test method was as follows:
  • the shrinkage rate of the thermoplastic polyurethane elastomer of the present invention is 0.2-0.32%
  • the flexural modulus is 1602-1822MPa
  • the flexural strength is 30.2-33.5Mpa
  • the notched impact strength is 25-32KJ/m 2
  • tensile strength is 22.3-25.2Mpa
  • elongation at break is 33.4-38.9%, with low shrinkage and good flexibility as well as mechanical properties and processing properties.
  • the present invention illustrates the low shrinkage TPU film of the present invention and its preparation method through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented.
  • Those skilled in the art should understand that any improvement to the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

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Abstract

本发明提供一种低收缩率TPU薄膜及其制备方法，所述低收缩率TPU薄膜的制备原料按照重量份计包括以下成分：TPU颗粒60-80重量份、聚丙烯20-30重量份、碳酸钙2-8重量份、石墨烯材料1-5重量份、玻璃纤维5-10重量份和抗氧剂0.5-2重量份。本发明TPU薄膜的收缩率在0.5％以下，并且能够保证TPU薄膜的柔韧性以及良好的机械性能和加工。

Description

一种低收缩率TPU薄膜及其制备方法
本公开基于申请号为202011474876.1，申请日为2020年12月14日的中国专利申请提出，并要求该篇中国专利申请的优先权，该篇中国专利申请的全部内容在此引入本申请作为参考。
技术领域
本发明属于高分子材料技术领域，涉及一种低收缩率TPU薄膜及其制备方法。
背景技术
聚氨酯材料由于其自身具有的柔韧性、耐磨性、透明性等优势，广泛应用于家电、家具、仪表、服饰等领域，但是聚氨酯材料也具有易翘曲、收缩率大的缺点，这使得其应用在一定程度上受到限制。
CN111087947A公开了一种低收缩率的粘接树脂及其制备方法，所述低收缩率的粘接树脂按重量份数计，包括组分：高密度聚乙烯20-40份、改性线型低密度聚乙烯20-50份、聚丙烯20-50份、成核剂5-15份和稳定剂0.1-3份。该粘接树脂具有低的收缩率，从而使型材各部件之间的连接界面减少由于粘接树脂的收缩造成的局部应力，减少塑料制品的变形、开裂等现象。然而该粘结树脂是基于聚乙烯和聚丙烯材料，对于聚氨酯材料如何降低其收缩率并没有相关报道。
因此，在本领域中，期望开发一种低收缩率TPU薄膜及其制备方法。
发明内容
针对现有技术的不足，本发明的目的在于提供一种低收缩率TPU薄膜及其制备方法。本发明的低收缩率TPU薄膜收缩率低，力学性能良好，适用于汽车、家电、家具、仪表、服饰、机械工业等多个领域。
为达此目的，本发明采用以下技术方案：
一方面，本发明提供一种低收缩率TPU薄膜，所述低收缩率TPU薄膜的制备原料按照重量份计包括以下成分：
Figure PCTCN2021102965-appb-000001
Figure PCTCN2021102965-appb-000002
在本发明中，聚丙烯可以降低TPU薄膜的收缩率，但是效果并不是十分理想，因此在本发明中利用碳酸钙、石墨烯和玻璃纤维三者配合进一步降低TPU薄膜的收缩率，并且能够保证TPU薄膜的柔韧性以及良好的机械性能和加工性能。
在本发明中，所述的低收缩率是指收缩率按照ISO2577的方法进行测试，其值在0.5％以下。
在本发明中，低收缩率TPU薄膜的制备原料中，TPU颗粒的用量可以为2重量份、65重量份、68重量份、70重量份、72重量份、75重量份、78重量份等。
在本发明中，低收缩率TPU薄膜的制备原料中，聚丙烯的用量可以为22重量份、25重量份、27重量份、29重量份等。
在本发明中，低收缩率TPU薄膜的制备原料中，碳酸钙的用量可以为2重量份、3重量份、4重量份、5重量份、6重量份、7重量份或8重量份。
在本发明中，低收缩率TPU薄膜的制备原料中，石墨烯材料的用量可以为1重量份、2重量份、3重量份、4重量份或5重量份。
在本发明中，低收缩率TPU薄膜的制备原料中，玻璃纤维的用量可以为5重量份、6重量份、7重量份、8重量份、9重量份或10重量份。
在本发明中，低收缩率TPU薄膜的制备原料中，抗氧剂的用量可以为0.5重量份、0.8重量份、1重量份、1.5重量份、1.8重量份或2重量份。
优选地，所述TPU颗粒为聚醚性TPU颗粒。
优选地，所述聚丙烯为共聚聚丙烯，其在230℃、2.16kg的测试条件下的熔体流动速率为10-40g/10min，例如10g/10min、13g/10min、15g/10min、18g/10min、20g/10min、25g/10min、28g/10min、30g/10min、35g/10min、38g/10min或40g/10min。
优选地，所述石墨烯材料为单层石墨烯、多层石墨烯或氧化石墨烯，优选 氧化石墨烯。
优选地，所述玻璃纤维的长度为5mm-20mm，例如5mm、8mm、10mm、13mm、15mm、18mm或20mm。
优选地，所述抗氧剂为抗氧剂3114、抗氧剂1010、抗氧剂168或抗氧剂618中的任意一种或至少两种的组合。
另一方面，本发明提供了如上所述低收缩率TPU薄膜的制备方法，所述制备方法包括以下步骤：
(1)将玻璃纤维和石墨烯材料混合，而后将其与TPU颗粒、聚丙烯和抗氧剂混合，从主喂料口加入双螺杆挤出机中；
(2)将碳酸钙从侧喂料口加入双螺杆挤出机，挤出成型，得到所述低收缩率TPU薄膜。
在本发明中，首先将玻璃纤维和石墨烯材料混合，使得玻璃纤维穿插至石墨烯材料的片层中，降低石墨烯材料的团聚，提高其分散性，而后将其与TPU颗粒、聚丙烯和抗氧剂混合，能够使得玻璃纤维和石墨烯材料更好地与主体树脂进行混合，将这些混合物从主喂料口加入双螺杆挤出机中，将碳酸钙从侧喂料口加入双螺杆挤出机，碳酸钙为球状颗粒能够与玻璃纤维和石墨烯材料配合，充分填充在TPU颗粒、聚丙烯材料的结构中，降低材料的收缩率。
优选地，步骤(1)所述两次混合的转速独立地为600-1000r/min，例如600r/min、650r/min、700r/min、750r/min、800r/min、850r/min、900r/min、950r/min或1000r/min。
优选地，步骤(1)所述两次混合的时间独立地为10-20min，例如10min、12min、14min、15min、17min、19min或20min。
优选地，步骤(2)所述挤出时双螺杆挤出机的转速为200-500r/min，例如200r/min、220r/min、250r/min、280r/min、300r/min、350r/min、400r/min或500r/min。
优选地，步骤(2)所述挤出时双螺杆挤出机的喂料段温度为160～170℃(例如160℃、162℃、165℃、168℃、170℃)，混合段温度为180～190℃(例如180℃、182℃、185℃、188℃、190℃)，挤出段温度为200～220℃(例如200℃、205℃、208℃、210℃、212℃、215℃、218℃、220℃)，机头温度为210～220℃(例如 210℃、212℃、215℃、218℃、220℃)。
相对于现有技术，本发明具有以下有益效果：
本发明中利用聚丙烯、碳酸钙、石墨烯和玻璃纤维降低TPU薄膜的收缩率，特别是碳酸钙、石墨烯和玻璃纤维三者配合使得TPU薄膜的收缩率在0.5％以下，并且能够保证TPU薄膜的柔韧性以及良好的机械性能和加工性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本发明，不应视为对本发明的具体限制。
实施例1
在本实施例中，提供一种低收缩率TPU薄膜，所述低收缩率TPU薄膜的制备原料按照重量份计包括以下成分：
Figure PCTCN2021102965-appb-000003
其中TPU颗粒为聚醚型TPU颗粒(巴斯夫1185A)，聚丙烯为燕山石化生产的共聚聚丙烯K9026，在230℃、2.16kg的测试条件下的熔体流动速率为30g/10min，碳酸钙为3000目的碳酸钙(佛山市勃震化工)，石墨烯材料为氧化石墨烯，玻璃纤维的长度为10-13mm；抗氧剂为抗氧剂1010。
制备方法包括以下步骤：
(1)将玻璃纤维和石墨烯材料在600r/min下混合10min，而后将其与TPU颗粒、聚丙烯和抗氧剂在800r/min下混合15min，从主喂料口加入双螺杆挤出机中；
(2)将碳酸钙从侧喂料口加入双螺杆挤出机，双螺杆挤出机的转速为 200r/min，步骤(2)所述挤出时双螺杆挤出机的喂料段温度为160℃，混合段温度为180℃，挤出段温度为200℃，机头温度为210℃，挤出成型，得到所述低收缩率TPU薄膜。
实施例2
在本实施例中，提供一种低收缩率TPU薄膜，所述低收缩率TPU薄膜的制备原料按照重量份计包括以下成分：
Figure PCTCN2021102965-appb-000004
其中TPU颗粒为聚醚型TPU颗粒(巴斯夫1185A)，聚丙烯为燕山石化生产的共聚聚丙烯K9026，在230℃、2.16kg的测试条件下的熔体流动速率为30g/10min，碳酸钙为3000目的碳酸钙(佛山市勃震化工)，石墨烯材料为氧化石墨烯，玻璃纤维的长度为10-13mm；抗氧剂为抗氧剂168。
制备方法包括以下步骤：
(1)将玻璃纤维和石墨烯材料在800r/min下混合20min，而后将其与TPU颗粒、聚丙烯和抗氧剂在800r/min下混合20min，从主喂料口加入双螺杆挤出机中；
(2)将碳酸钙从侧喂料口加入双螺杆挤出机，双螺杆挤出机的转速为500r/min，步骤(2)所述挤出时双螺杆挤出机的喂料段温度为170℃，混合段温度为190℃，挤出段温度为220℃，机头温度为220℃，挤出成型，得到所述低收缩率TPU薄膜。
实施例3
在本实施例中，提供一种低收缩率TPU薄膜，所述低收缩率TPU薄膜的制 备原料按照重量份计包括以下成分：
Figure PCTCN2021102965-appb-000005
其中TPU颗粒为聚醚型TPU颗粒(巴斯夫1185A)，聚丙烯为燕山石化生产的共聚聚丙烯K9026，在230℃、2.16kg的测试条件下的熔体流动速率为30g/10min，碳酸钙为3000目的碳酸钙(佛山市勃震化工)，石墨烯材料为氧化石墨烯，玻璃纤维的长度为10-13mm；抗氧剂为抗氧剂618。
制备方法包括以下步骤：
(1)将玻璃纤维和石墨烯材料在600r/min下混合20min，而后将其与TPU颗粒、聚丙烯和抗氧剂在1000r/min下混合10min，从主喂料口加入双螺杆挤出机中；
(2)将碳酸钙从侧喂料口加入双螺杆挤出机，双螺杆挤出机的转速为400r/min，步骤(2)所述挤出时双螺杆挤出机的喂料段温度为160℃，混合段温度为190℃，挤出段温度为220℃，机头温度为210℃，挤出成型，得到所述低收缩率TPU薄膜。
实施例4
在本实施例中，提供一种低收缩率TPU薄膜，所述低收缩率TPU薄膜的制备原料按照重量份计包括以下成分：
Figure PCTCN2021102965-appb-000006
Figure PCTCN2021102965-appb-000007
其中TPU颗粒为聚醚型TPU颗粒(巴斯夫1185A)，聚丙烯为燕山石化生产的共聚聚丙烯K9026，在230℃、2.16kg的测试条件下的熔体流动速率为30g/10min，碳酸钙为3000目的碳酸钙(佛山市勃震化工)，石墨烯材料为氧化石墨烯，玻璃纤维的长度为15-18mm；抗氧剂为抗氧剂1010。
制备方法包括以下步骤：
(1)将玻璃纤维和石墨烯材料在1000r/min下混合10min，而后将其与TPU颗粒、聚丙烯和抗氧剂在1000r/min下混合20min，从主喂料口加入双螺杆挤出机中；
(2)将碳酸钙从侧喂料口加入双螺杆挤出机，双螺杆挤出机的转速为200r/min，步骤(2)所述挤出时双螺杆挤出机的喂料段温度为160℃，混合段温度为190℃，挤出段温度为200℃，机头温度为210℃，挤出成型，得到所述低收缩率TPU薄膜。
实施例5
在本实施例中，提供一种低收缩率TPU薄膜，所述低收缩率TPU薄膜的制备原料按照重量份计包括以下成分：
Figure PCTCN2021102965-appb-000008
其中TPU颗粒为聚醚型TPU颗粒(巴斯夫1185A)，聚丙烯为燕山石化生产的共聚聚丙烯K9026，在230℃、2.16kg的测试条件下的熔体流动速率为30g/10min，碳酸钙为3000目的碳酸钙(佛山市勃震化工)，石墨烯材料为氧化石墨烯，玻璃 纤维的长度为18-20mm；抗氧剂为抗氧剂3114。
制备方法包括以下步骤：
(1)将玻璃纤维和石墨烯材料在600-1000r/min下混合10-20min，而后将其与TPU颗粒、聚丙烯和抗氧剂在600-1000r/min下混合10-20min，从主喂料口加入双螺杆挤出机中；
(2)将碳酸钙从侧喂料口加入双螺杆挤出机，双螺杆挤出机的转速为500r/min，步骤(2)所述挤出时双螺杆挤出机的喂料段温度为170℃，混合段温度为185℃，挤出段温度为210℃，机头温度为220℃，挤出成型，得到所述低收缩率TPU薄膜。
实施例6
在本实施例中，提供一种低收缩率TPU薄膜，所述低收缩率TPU薄膜的制备原料按照重量份计包括以下成分：
Figure PCTCN2021102965-appb-000009
其中TPU颗粒为聚醚型TPU颗粒(巴斯夫1185A)，聚丙烯为燕山石化生产的共聚聚丙烯K9026，在230℃、2.16kg的测试条件下的熔体流动速率为30g/10min，碳酸钙为3000目的碳酸钙(佛山市勃震化工)，石墨烯材料为氧化石墨烯，玻璃纤维的长度为10-13mm；抗氧剂为抗氧剂1010。
制备方法包括以下步骤：
(1)将玻璃纤维和石墨烯材料在800r/min下混合20min，而后将其与TPU颗粒、聚丙烯和抗氧剂在1000r/min下混合15min，从主喂料口加入双螺杆挤出机中；
(2)将碳酸钙从侧喂料口加入双螺杆挤出机，双螺杆挤出机的转速为300r/min，步骤(2)所述挤出时双螺杆挤出机的喂料段温度为170℃，混合段温度为190℃，挤出段温度为220℃，机头温度为220℃，挤出成型，得到所述低收缩率TPU薄膜。
实施例7
在本实施例中，提供一种低收缩率TPU薄膜，所述低收缩率TPU薄膜的制备原料按照重量份计包括以下成分：
Figure PCTCN2021102965-appb-000010
其中TPU颗粒为聚醚型TPU颗粒(巴斯夫1185A)，聚丙烯为燕山石化生产的共聚聚丙烯K9026，在230℃、2.16kg的测试条件下的熔体流动速率为30g/10min，碳酸钙为3000目的碳酸钙(佛山市勃震化工)，石墨烯材料为氧化石墨烯，玻璃纤维的长度为13-15mm；抗氧剂为抗氧剂1010。
制备方法包括以下步骤：
(1)将玻璃纤维和石墨烯材料在600r/min下混合15min，而后将其与TPU颗粒、聚丙烯和抗氧剂在600r/min下混合15min，从主喂料口加入双螺杆挤出机中；
(2)将碳酸钙从侧喂料口加入双螺杆挤出机，双螺杆挤出机的转速为400r/min，步骤(2)所述挤出时双螺杆挤出机的喂料段温度为170℃，混合段温度为190℃，挤出段温度为220℃，机头温度为220℃，挤出成型，得到所述低收缩率TPU薄膜。
实施例8
在本实施例中，提供一种低收缩率TPU薄膜，所述低收缩率TPU薄膜的制备原料按照重量份计包括以下成分：
Figure PCTCN2021102965-appb-000011
其中TPU颗粒为聚醚型TPU颗粒(巴斯夫1185A)，聚丙烯为燕山石化生产的共聚聚丙烯K9026，在230℃、2.16kg的测试条件下的熔体流动速率为30g/10min，碳酸钙为3000目的碳酸钙(佛山市勃震化工)，石墨烯材料为氧化石墨烯，玻璃纤维的长度为10-13mm；抗氧剂为抗氧剂1010。
制备方法包括以下步骤：
(1)将玻璃纤维和石墨烯材料在700r/min下混合18min，而后将其与TPU颗粒、聚丙烯和抗氧剂在600r/min下混合20min，从主喂料口加入双螺杆挤出机中；
(2)将碳酸钙从侧喂料口加入双螺杆挤出机，双螺杆挤出机的转速为500r/min，步骤(2)所述挤出时双螺杆挤出机的喂料段温度为170℃，混合段温度为180℃，挤出段温度为200℃，机头温度为210℃，挤出成型，得到所述低收缩率TPU薄膜。
对比例1
该对比例与实施例1不同之处在于，TPU薄膜的制备原料中不使用碳酸钙，石墨烯材料和玻璃纤维的用量均为6.5重量份。
对比例2
该对比例与实施例1不同之处在于，TPU薄膜的制备原料中不使用石墨烯材料，碳酸钙的用量为5重量份，玻璃纤维的用量为8重量份。
对比例3
该对比例与实施例1不同之处在于，TPU薄膜的制备原料中不使用玻璃纤维，碳酸钙的用量为5重量份，石墨烯材料的用量为8重量份。
对实施例1-5以及对比例1-7的热塑性聚氨酯弹性体进行性能测试，测试方法如下：
(1)收缩率按照GB/T15585进行测试。
(2)拉伸强度、断裂伸长率测试：GB/T1040，《塑料拉伸性能试验方法》。
(3)弯曲强度测试：GB/T9341，《塑料弯曲性能试验方法》。
(4)悬臂梁缺口测试：GB/T1843，《硬质塑料冲击试验方法》。
性能测试结果如表1所示。
表1
Figure PCTCN2021102965-appb-000012
由表1可以看出，本发明所述热塑性聚氨酯弹性体的收缩率在0.2-0.32％，弯曲模量在1602-1822MPa，弯曲强度在30.2-33.5Mpa，缺口冲击强度为25-32KJ/m 2，拉伸强度为22.3-25.2Mpa，断裂伸长率为33.4-38.9％，具有低收缩率以及良好的柔韧性以及机械性能和加工性能。
申请人声明，本发明通过上述实施例来说明本发明的低收缩率TPU薄膜及其制备方法，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种低收缩率TPU薄膜，其特征在于，所述低收缩率TPU薄膜的制备原料按照重量份计包括以下成分：
    Figure PCTCN2021102965-appb-100001
  2. 根据权利要求1所述的低收缩率TPU薄膜，其特征在于，所述聚丙烯为共聚聚丙烯，其在230℃、2.16kg的测试条件下的熔体流动速率为10-40g/10min。
  3. 根据权利要求1或2所述的低收缩率TPU薄膜，其特征在于，所述石墨烯材料为单层石墨烯、多层石墨烯或氧化石墨烯，优选氧化石墨烯。
  4. 根据权利要求1-3中任一项所述的低收缩率TPU薄膜，其特征在于，所述玻璃纤维的长度为5mm-20mm。
  5. 根据权利要求1-4中任一项所述的低收缩率TPU薄膜，其特征在于，所述抗氧剂为抗氧剂3114、抗氧剂1010、抗氧剂168或抗氧剂618中的任意一种或至少两种的组合。
  6. 根据权利要求1-5中任一项所述的低收缩率TPU薄膜的制备方法，其特征在于，所述制备方法包括以下步骤：
    (1)将玻璃纤维和石墨烯材料混合，而后将其与TPU颗粒、聚丙烯和抗氧剂混合，从主喂料口加入双螺杆挤出机中；
    (2)将碳酸钙从侧喂料口加入双螺杆挤出机，挤出成型，得到所述低收缩率TPU薄膜。
  7. 根据权利要求6所述的制备方法，其特征在于，步骤(1)所述两次混合的转速独立地为600-1000r/min。
  8. 根据权利要求6或7所述的制备方法，其特征在于，步骤(1)所述两次混合的时间独立地为10-20min。
  9. 根据权利要求6-8中任一项所述的制备方法，其特征在于，步骤(2)所述挤出时双螺杆挤出机的转速为200-500r/min。
  10. 根据权利要求6-9中任一项所述的制备方法，其特征在于，步骤(2)所述挤出时双螺杆挤出机的喂料段温度为160～170℃，混合段温度为180～190℃，挤出段温度为200～220℃，机头温度为210～220℃。
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