Polymer films, methods of making and using the same

Abstract

The application relates to the field of thin film materials, and discloses a polymer film and a preparation method and application thereof. The polymer film comprises a liquid contact layer, an intermediate layer and an outer layer arranged in sequence through co-extrusion molding; the intermediate layer contains ethylene-vinyl alcohol copolymer, maleic anhydride polyolefin plastomer A and polyethylene A; the outer layer contains polyethylene B and maleic anhydride polyolefin plastomer B; the maleic anhydride grafting rates of the maleic anhydride polyolefin plastomer A and the maleic anhydride polyolefin plastomer B are respectively in the range of 0.3-1.5%. The polymer film has self-bonding performance and high wrinkle resistance, the polymer film has only three layers, the preparation difficulty can be reduced, the obtained biological reaction bag has good wrinkle resistance, and the service life of the disposable biological reaction bag is improved.

Description

Technical Field

[0001] This invention relates to the field of thin film materials, specifically to a polymer film, its preparation method, and its applications. Background Technology

[0002] Disposable bioreactor bags are bags with a multi-layer co-extruded film structure as their main component. They can be used as culture carriers for cells and viruses and are widely used in the biopharmaceutical field. They offer significant advantages by effectively reducing production costs, increasing production flexibility, and reducing the probability of cross-infection. During use, one side of the bag is in direct contact with the culture liquid, while the other side is in contact with the external environment. It must also have good gas barrier properties to provide an environmental guarantee for cell growth. Typically, the bag is mainly composed of multi-layer co-extruded film and related accessories, with the film generally consisting of five or more layers. Taking the most commonly used and typical five-layer structure as an example, the film consists of an outer layer, an adhesive layer, a middle barrier layer, an adhesive layer, and an inner layer. The outer layer is usually made of high-strength, tough, puncture-resistant, and fold-resistant plastic to ensure the culture of internal cells or microorganisms. The inner layer is the liquid contact layer, directly contacting cells, microorganisms, culture media, etc. It needs to have low extractable / leached substances to meet the normal growth and metabolism of cells and create a suitable environment for cell culture. The barrier layer in the middle provides gas barrier properties, ensuring an environmental guarantee for cell growth. The function of the two adhesive layers is to bond the three layers together, ensuring the integrity of the membrane structure and preventing leakage of the reaction liquid.

[0003] Currently, many existing technologies disclose five-layer composite films used in the preparation of disposable bioreactor bags. Typically, the outermost and innermost layers are adhesive layers used to bond the remaining three layers, such as Satoruis' Flexsafe. The S805 layer structure is LLDPE / tie / EVOH / tie / LLDPE, while Renolit AG of Germany produces LLDPE / tie / EVOH / tie / LDPE, etc. However, the preparation process of a 5-layer co-extruded film is relatively complex, and due to the large number of layers, the bonding effect between each layer is difficult to guarantee. In addition, the bag structure of bioreactor bags, especially when used as reaction vessels, requires mechanical stirring inside, which places high demands on the toughness of the film. Therefore, how to prepare composite films with as few layers as possible while meeting the performance requirements of disposable bioreactor bags is a problem that needs to be considered. Summary of the Invention

[0004] The purpose of this invention is to overcome the problems of existing technologies in preparing bioreactor bags, such as the large number of film layers, difficulty in ensuring adhesion, and the need for further improvement in toughness. This invention provides a polymer film, its preparation method, and its application. The polymer film has self-adhesive properties and high tear resistance. Furthermore, the polymer film has only three layers, which can reduce the difficulty of polymer film preparation and enable the resulting bioreactor bag to have better tear resistance, thereby improving the service life of disposable bioreactor bags.

[0005] To achieve the above objectives, the present invention provides a polymer film comprising a liquid contact layer, an intermediate layer, and an outer layer arranged sequentially by co-extrusion.

[0006] The intermediate layer contains an ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyolefin plastic body A, and polyethylene A, and the outer layer contains polyethylene B and maleic anhydride-modified polyolefin plastic body B.

[0007] The maleic anhydride grafting rates in the maleic anhydride-modified polyolefin plastic body A and the maleic anhydride-modified polyolefin plastic body B are each in the range of 0.3-1.5%.

[0008] Preferably, the content of the maleic anhydride-modified polyolefin plastomer A in the intermediate layer is 3-15 wt%.

[0009] Preferably, the content of the maleic anhydride-modified polyolefin plastomer B in the outer layer is 3-10 wt%.

[0010] Preferably, the liquid contact layer contains a polyolefin elastomer.

[0011] Preferably, the polyolefin elastomer is polyolefin elastomer POP and / or polyolefin elastomer POE.

[0012] Preferably, in the intermediate layer, the weight ratio of the ethylene-vinyl alcohol copolymer, the maleic anhydride-modified polyolefin plastic body A, and the polyethylene A is (7.5-9.5):(0.5-1.5):1.

[0013] Preferably, in the outer layer, the weight ratio of the polyethylene B to the maleic anhydride-modified polyolefin plastide B is 1:0.03-0.16.

[0014] Preferably, the melt index of the maleic anhydride-modified polyolefin plastomer A is 0.2-14 g / 10 min.

[0015] Preferably, the density of the maleic anhydride-modified polyolefin plastomer A is 0.86-0.93 g / cm³. 3 .

[0016] Preferably, the content of free maleic anhydride in the maleic anhydride-modified polyolefin plastic body A is ≤100ppm, and more preferably ≤50ppm.

[0017] Preferably, the melt index of the maleic anhydride-modified polyolefin plastomer B is 0.2-14 g / 10 min.

[0018] Preferably, the density of the maleic anhydride-modified polyolefin plastomer B is 0.86-0.93 g / cm³. 3 .

[0019] Preferably, the content of free maleic anhydride in the maleic anhydride-modified polyolefin plastomer B is ≤100ppm, and more preferably ≤50ppm.

[0020] Preferably, in the ethylene-vinyl alcohol copolymer, the ethylene content is 24-44 mol%.

[0021] Preferably, the melt index of the ethylene-vinyl alcohol copolymer is 1-3 g / 10 min.

[0022] Preferably, the density of the ethylene-vinyl alcohol copolymer is 1.1-1.25 g / cm³. 3 .

[0023] Preferably, the melt index of the polyolefin elastomer is 0.1-5 g / 10 min.

[0024] Preferably, the density of the polyolefin elastomer is 0.86-0.93 g / cm³. 3 .

[0025] Preferably, the polymer film further contains antioxidants and light stabilizers.

[0026] Preferably, the thickness of the polymer film is 300-500 μm.

[0027] Preferably, the thickness of the intermediate layer is 20-100 μm.

[0028] Preferably, the grafting rate of maleic anhydride in the maleic anhydride-modified polyolefin plastic body B is 0.5-0.8% higher than that in the maleic anhydride-modified polyolefin plastic body A.

[0029] Preferably, the density of the maleic anhydride-modified polyolefin plastide B is 0.001-0.003 g / cm³ greater than the density of the maleic anhydride-modified polyolefin plastide A. 3 .

[0030] A second aspect of the present invention provides a method for preparing the polymer film, the method comprising: placing a material containing a polyolefin elastomer in a first channel; placing a mixture containing an ethylene-vinyl alcohol copolymer, a maleic anhydride-modified polyolefin plasticizer A, and polyethylene A in a second channel; placing a mixture containing polyethylene B and a maleic anhydride-modified polyolefin plasticizer B in a third channel; and then simultaneously performing melt extrusion on the materials in the three channels.

[0031] Preferably, the temperature of the melt extrusion is 160-230°C.

[0032] A third aspect of the present invention provides a polymer film prepared according to the method.

[0033] A fourth aspect of the present invention provides the application of the polymer membrane described herein in the preparation of disposable bioreactor bags.

[0034] The polymer film of this invention is a three-layer co-extruded film structure, consisting only of a liquid contact layer, an intermediate layer, and an outer layer. The polymer film possesses self-adhesive properties, and the three co-extruded layers are tightly bonded together without the need for additional adhesives or bonding layers, thus simplifying the structure and processing methods of the polymer film. Furthermore, the polymer film of this invention also exhibits excellent tear resistance, further enabling its better application in the preparation of disposable bioreactor bags and extending the lifespan of the prepared bioreactor bags. Detailed Implementation

[0035] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0036] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0037] In this invention, the melt index of the maleic anhydride-modified polyolefin plastic body A, the melt index of the maleic anhydride-modified polyolefin plastic body B, the melt index of the ethylene-vinyl alcohol copolymer, and the melt index of the polyolefin elastomer all refer to the melt index obtained by testing the material at 190°C. The specific testing method can refer to common techniques in the art.

[0038] The polymer film of the present invention comprises a liquid contact layer, an intermediate layer and an outer layer arranged sequentially by co-extrusion molding.

[0039] In this invention, the polymer membrane is a three-layer co-agent membrane, whose structure is simpler than the five-layer membrane commonly used in the prior art. Furthermore, the polymer membrane has self-adhesive properties, and the liquid contact layer, intermediate layer, and outer layer can self-adhere without the need for additional adhesives or additional adhesive layers. This not only simplifies the structure of the polymer membrane but also further reduces the disadvantages caused by poor adhesion between layers, making it better suited for the preparation of disposable bioreactor bags.

[0040] Specifically, in the polymer membrane, the liquid contact layer is used to directly contact materials such as cells, microorganisms or culture media; the intermediate layer is used to block gases, providing a suitable environment for cell growth and also to bond the three co-agent membranes together, thus possessing both gas barrier and self-adhesive properties; and the outer layer assists in the bonding process and also ensures the cultivation of internal cells or microorganisms.

[0041] In this invention, the specific composition of the liquid contact layer is not limited. More preferably, to further ensure the performance of the polymer film and make it better suited for the preparation of bioreactor bags, the liquid contact layer is limited to containing a polyolefin elastomer. More preferably, the polyolefin elastomer is a polyolefin elastomer POP and / or a polyolefin elastomer POE.

[0042] In a preferred embodiment, the melt index of the polyolefin elastomer is 0.1-5 g / 10 min, preferably 0.5-5 g / 10 min, and the density of the polyolefin elastomer is 0.86-0.93 g / cm³. 3 Specifically, the polyolefin elastomer POP and the polyolefin elastomer POE can be commercially available products, as long as they meet the melt index and density specified in this invention. For example, they can be Affinity PL1881G, Affinity PL1850G, Affinity PL1280G, Affinity PL1840G, Engage 8100, or Engage 8200 from Dow Chemical Company.

[0043] In this invention, the intermediate layer contains an ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyolefin plastomer A, and polyethylene A. Through the synergistic effect of these three components, the intermediate layer simultaneously possesses excellent gas barrier properties and self-adhesive properties, allowing the polymer film to meet the performance requirements of bioreactor bags while maintaining a simpler structure.

[0044] In a preferred embodiment, to further improve the self-adhesive properties of the polymer film, the content of the maleic anhydride-modified polyolefin plasticizer A in the intermediate layer is 3-15 wt%, more preferably 6-12 wt%. Specifically, the content of the maleic anhydride-modified polyolefin plasticizer A can be 4 wt%, 5 wt%, 7 wt%, 9 wt%, 10 wt%, 12 wt%, 14 wt%, or 15 wt%.

[0045] In a preferred embodiment, the maleic anhydride grafting rate of the maleic anhydride-modified polyolefin plastic body A is 0.3-1.5%, preferably 0.5-1%, and more preferably 0.68-0.93%. By limiting the maleic anhydride grafting rate of the maleic anhydride-modified polyolefin plastic body A, the self-adhesive properties of the polymer film can be further improved, thereby further reducing the risk of interlayer cracking in the polymer film. Specifically, the maleic anhydride grafting rate of the maleic anhydride-modified polyolefin plastic body A can be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.

[0046] In a preferred embodiment, the melt index of the maleic anhydride-modified polyolefin plastic body A is 0.2-14 g / 10 min, more preferably 0.8-8 g / min. Specifically, the melt index of the maleic anhydride-modified polyolefin plastic body A can be 1 g / 10 min, 5 g / 10 min, 10 g / 10 min, or 14 g / 10 min.

[0047] In this invention, the lower the density of the selected maleic anhydride-modified polyolefin plastic body A, the better the toughness and tear resistance of the polymer film. Preferably, the density of the maleic anhydride-modified polyolefin plastic body A is 0.86-0.93 g / cm³. 3 By limiting the density of the maleic anhydride-modified polyolefin plastic body A, the tear resistance of the polymer film can be further improved, making it more suitable for the preparation of bioreactor bags. Specifically, the density of the maleic anhydride-modified polyolefin plastic body A can be 0.89 g / cm³. 3 0.9g / cm 3 0.91g / cm 3 0.92g / cm 3 Or 0.93g / cm 3 .

[0048] In a preferred embodiment, the content of free maleic anhydride in the maleic anhydride-modified polyolefin plastic body A is ≤100ppm, preferably ≤50ppm, and more preferably 20-50ppm.

[0049] In a preferred embodiment, the ethylene content in the ethylene-vinyl alcohol copolymer is 24-44 mol%, preferably 24-32 mol%. Specifically, the ethylene content can be 24 mol%, 30 mol%, 34 mol%, 40 mol%, or 44 mol%.

[0050] In a preferred embodiment, the melt index of the ethylene-vinyl alcohol copolymer is 1-3 g / 10 min. Specifically, the melt index of the ethylene-vinyl alcohol copolymer can be 1 g / 10 min, 2 g / 10 min, or 3 g / 10 min.

[0051] In a preferred embodiment, the density of the ethylene-vinyl alcohol copolymer is 1.1-1.25 g / cm³. 3 Specifically, the density of the ethylene-vinyl alcohol copolymer can be 1.1 g / cm³. 3 1.12 g / cm 3 1.14 g / cm 3 1.15g / cm 3 1.18 g / cm 3 or 1.2g / cm 3 .

[0052] In some specific embodiments, the ethylene-vinyl alcohol copolymer can be a commercially available product, such as products manufactured by Kuraray of Japan with the grades EVAL F171B, EVAL H171B and EVAL E150B, products manufactured by Sinopec Chongqing Chuanwei with the grade EW3201, and products manufactured by Sinopec Chongqing Chuanwei with the grade EW3801.

[0053] In a preferred embodiment, the weight ratio of the ethylene-vinyl alcohol copolymer, the maleic anhydride-modified polyolefin plasticizer A, and the polyethylene A in the intermediate layer is (7.5-9.5):(0.5-1.5):1, more preferably (7.8-8.6):(0.8-1.2):1. By limiting the amount of the ethylene-vinyl alcohol copolymer, the maleic anhydride-modified polyolefin plasticizer A, and the polyethylene A in the intermediate layer, the self-adhesive properties and toughness of the polymer film can be further improved.

[0054] In some specific embodiments, the thickness of the intermediate layer is 20-100 μm, more preferably 40-80 μm. Specifically, the thickness of the intermediate layer can be 20 μm, 40 μm, 60 μm, 80 μm, or 100 μm.

[0055] In this invention, the outer layer contains polyethylene B and maleic anhydride-modified polyolefin plastic body B. Through the interaction between the two components, the outer layer can be bonded to the middle layer while still maintaining excellent toughness. The bioreactor bag prepared using the polymer film has excellent tear resistance.

[0056] In a preferred embodiment, to further improve the self-adhesive properties of the polymer film, the content of the maleic anhydride-modified polyolefin plasticizer B in the outer layer is 3-10 wt%, more preferably 3.5-7 wt%. Specifically, the content of the maleic anhydride-modified polyolefin plasticizer B can be 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%.

[0057] In a preferred embodiment, the maleic anhydride grafting rate in the maleic anhydride-modified polyolefin plastic body B is 0.3-1.5%, preferably 0.5-1%, and more preferably 0.68-0.93%. By limiting the maleic anhydride grafting rate in the maleic anhydride-modified polyolefin plastic body B, the adhesion between the outer layer and the intermediate layer can be made tighter, resulting in a denser polymer film structure and superior performance of the prepared bioreactor bag.

[0058] Specifically, the maleic anhydride grafting rate of the maleic anhydride-modified polyolefin plastomer B can be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, or 1%.

[0059] In a preferred embodiment, the melt index of the maleic anhydride-modified polyolefin plastide B is 0.2-14 g / 10 min, more preferably 0.8-8 g / 10 min. Specifically, the melt index of the maleic anhydride-modified polyolefin plastide A can be 0.2 g / 10 min, 1 g / 10 min, 5 g / 10 min, 10 g / 10 min, or 14 g / 10 min.

[0060] In this invention, the lower the density of the selected maleic anhydride-modified polyolefin plastic body B, the better the toughness and tear resistance of the polymer film. Preferably, the density of the maleic anhydride-modified polyolefin plastic body B is 0.86-0.93 g / cm³. 3 The tumble resistance of the polymer film can be further improved by limiting the density of the maleic anhydride-modified polyolefin plastic body B. Specifically, the density of the maleic anhydride-modified polyolefin plastic body B can be 0.86 g / cm³. 3 0.89g / cm 3 0.91g / cm 3 0.92g / cm 3 Or 0.93g / cm3 .

[0061] In a preferred embodiment, the content of free maleic anhydride in the maleic anhydride-modified polyolefin plastomer B is ≤100ppm, preferably ≤50ppm, and more preferably 20-50ppm.

[0062] In this invention, both the maleic anhydride-modified polyolefin plastic body A and the maleic anhydride-modified polyolefin plastic body B can be commercially available products, such as one or more products selected independently from Shanghai Jiayirong Co., Ltd.'s product with brand name CMG-5805L, Dow Chemical Company's product with brand name M2265, and BYK Company's product with brand name PRIEX 18003.

[0063] In this invention, both polyethylene A and polyethylene B can be commercially available products, such as one or more of the following: Yanshan Petrochemical LDPE, Yanshan Petrochemical LLDPE, Yanshan Petrochemical ULDPE, DuPont ULDPE-4404G, Tianjin Petrochemical PE-LF081-8, ENGAGE8480K, EXACT 5101MX, AFFINITY PL1881G, and AFFINITY EG8100G.

[0064] In a preferred embodiment, the weight ratio of polyethylene B to maleic anhydride-modified polyolefin plastic body B in the outer layer is 1:0.03-0.16, preferably 1:0.04-0.1. Further optimization of the self-adhesive properties and tear resistance of the polymer film can be achieved by limiting the amount of polyethylene B and maleic anhydride-modified polyolefin plastic body B in the outer layer. Specifically, the weight ratio of polyethylene B to maleic anhydride-modified polyolefin plastic body B can be 1:0.03, 1:0.05, 1:0.1, 1:0.12, 1:0.13, 1:0.15, or 1:0.16.

[0065] In a preferred embodiment, by strictly controlling the maleic anhydride grafting rate and the amount added of the maleic anhydride-modified polyolefin plastic body A and the maleic anhydride-modified polyolefin plastic body B, the polymer film can possess excellent self-adhesive properties. Simultaneously, the disposable bioreactor bag prepared from the polymer film can have good cleaning properties, is less prone to adhesion of various impurities, and is more conducive to the survival and growth of cells or organisms. When the maleic anhydride grafting rate and the amount added of the maleic anhydride-modified polyolefin plastic body A and the maleic anhydride-modified polyolefin plastic body B exceed the range defined by this invention, the polymer film will easily adhere to various impurities, reducing its performance. When the maleic anhydride grafting rate and the amount added of the maleic anhydride-modified polyolefin plastic body A and the maleic anhydride-modified polyolefin plastic body B are below the range defined by this invention, the self-adhesive properties of the polymer film will decrease, easily leading to the detachment of the liquid contact layer, intermediate layer, and outer layer, affecting the application of the polymer film.

[0066] In some preferred embodiments, the grafting rate of maleic anhydride in the maleic anhydride-modified polyolefin plastic body B is 0.5-0.8% higher than that in the maleic anhydride-modified polyolefin plastic body A. By limiting the difference in the grafting rates of maleic anhydride between the two, the self-adhesive properties of the polymer film can be further improved.

[0067] In some preferred embodiments, the density of the maleic anhydride-modified polyolefin plastide B is 0.001-0.003 g / cm³ greater than the density of the maleic anhydride-modified polyolefin plastide A. 3 By limiting the density difference between the two, the polymer film can be made more resilient and more resistant to tearing, thereby resulting in a more superior performance of the prepared disposable bioreactor bag.

[0068] In this invention, the liquid contact layer, intermediate layer, and outer layer of the polymer film all further contain antioxidants and light stabilizers. Specifically, the specific components of the antioxidants and light stabilizers are not limited. In some preferred embodiments, the antioxidant is selected from one or more of antioxidant 1010, antioxidant 1076, antioxidant DLTP, antioxidant 2246, antioxidant 264, BHA, 2,4-di-tert-butylphenol, antioxidant 425, antioxidant 300, antioxidant 1076, antioxidant 168, and antioxidant 626, more preferably at least one of antioxidant 1010, antioxidant 626, and antioxidant 168; the light stabilizer is selected from light stabilizer U. V119, light stabilizer UV120, light stabilizer UV612, light stabilizer UV622, light stabilizer UV770, light stabilizer UV783, light stabilizer UV791, light stabilizer UV944, light stabilizer UV1084, light stabilizer UV2020, light stabilizer UV3346, light stabilizer UV3529, light stabilizer UV3853, light stabilizer UV4050, or two or more thereof, more preferably light stabilizer UV119 and / or light stabilizer UV622.

[0069] In some preferred embodiments, the content of the antioxidant in the liquid contact layer, the intermediate layer and the outer layer is 0.05-0.3 wt%, more preferably 0.05-0.2 wt%.

[0070] In some preferred embodiments, the content of the light stabilizer in the liquid contact layer, the intermediate layer and the outer layer is 0.1-0.5 wt%, more preferably 0.15-0.4 wt%.

[0071] In this invention, the thickness of the polymer film is 300-500 μm, preferably 330-450 μm. Specifically, the thickness of the polymer film can be 300 μm, 400 μm, 450 μm or 500 μm.

[0072] The present invention further provides a method for preparing the polymer film, the method comprising: placing a material containing a polyolefin elastomer in a first channel, placing a mixture containing an ethylene-vinyl alcohol copolymer, a maleic anhydride-modified polyolefin plasticizer A, and polyethylene A in a second channel, placing a mixture containing polyethylene B and a maleic anhydride-modified polyolefin plasticizer B in a third channel, and then simultaneously performing melt extrusion on the materials in the three channels.

[0073] In a preferred embodiment, the melt extrusion temperature is 160-230°C. Specifically, the melt extrusion temperature can be 160°C, 180°C, 200°C, 220°C, or 230°C.

[0074] The polymer membrane structure described in this invention is simple and has good self-adhesive and tear-resistant properties, making it well-suited for preparing disposable bioreactor bags.

[0075] The present invention will be described in detail below through embodiments, but the scope of protection of the present invention is not limited thereto.

[0076] The twin-screw extruders used in the examples and comparative examples were purchased from HAAKE, Germany, model Polylab OS; the casting equipment was purchased from Labtech Engineering, model LMCR-300.

[0077] The melt flow indexes given in the following examples and comparative examples are the melt flow indexes obtained by testing the materials at 190°C.

[0078] The raw materials and their properties used in the following examples and comparative examples are as follows:

[0079] The polyolefin elastomer used in Example 1 was Affinity PL1850G from Dow Chemical Company, USA, with a melt flow index of 3 g / 10 min and a density of 0.902 g / cm³. 3 The ethylene-vinyl alcohol copolymer used was Kuraray EVAL F171B from Japan, with an ethylene content of 32 wt%, a melt index of 1.6 g / 10 min, and a density of 1.19 g / cm³. 3 The maleic anhydride-modified polyolefin plastomer A used was CMG-5805L from Shanghai Jiayirong Co., Ltd., with a maleic anhydride grafting rate of 0.5-1.0%, a melt index of 0.3-2 g / 10 min, and a density of 0.87 g / cm³. 3 The polyethylene A used is DuPont ULDPE-4404G; the polyethylene B used is DuPont ULDPE-4404G; the maleic anhydride-modified polyolefin plastomer B used is Shanghai Jiayirong Co., Ltd.'s CMG-5805L; the antioxidant used is antioxidant 1010; the light stabilizer used is light stabilizer UV622.

[0080] The polyolefin elastomer used in Example 2 was Affinity PL1850G from Dow Chemical Company, USA, with a melt flow index of 3 g / 10 min and a density of 0.902 g / cm³. 3 The ethylene-vinyl alcohol copolymer used was Sinopec Chongqing Chuanwei EW3201, with an ethylene content of 32wt%, a melt index of 1.5-2.5 g / 10 min, and a density of 1.17 g / cm³. 3The maleic anhydride-modified polyolefin plastomer A used was CMG-5805L from Shanghai Jiayirong Co., Ltd., with a maleic anhydride grafting rate of 0.5-1.0%, a melt index of 0.3-2 g / 10 min, and a density of 0.87 g / cm³. 3 The polyethylene A used is DuPont ULDPE-4404G; the polyethylene B used is Yanshan Petrochemical LD100-AC; the maleic anhydride-modified polyolefin plastomer B used is Shanghai Jiayirong Co., Ltd. CMG-5805L; the antioxidant used is antioxidant 1010; and the light stabilizer used is light stabilizer UV622.

[0081] The polyolefin elastomer used in Example 3 was Affinity PL1850G from Dow Chemical Company, USA, with a melt flow index of 3 g / 10 min and a density of 0.902 g / cm³. 3 The ethylene-vinyl alcohol copolymer used was Kuraray EVALF171B from Japan, with an ethylene content of 32 wt%, a melt index of 1.6 g / 10 min, and a density of 1.19 g / cm³. 3 The maleic anhydride-modified polyolefin plastomer A used was CMG-5805L from Shanghai Jiayirong Co., Ltd., with a maleic anhydride grafting rate of 0.5-1.0%, a melt index of 0.3-2 g / 10 min, and a density of 0.87 g / cm³. 3 The polyethylene A used is DuPont ULDPE-4404G; the polyethylene B used is Tianjin Petrochemical PE-LF081-8; the maleic anhydride-modified polyolefin plastomer B used is Shanghai Jiayirong Co., Ltd. CMG-5805L; the antioxidant used is antioxidant 1010; and the light stabilizer used is light stabilizer UV622.

[0082] The polyolefin elastomer used in Example 4 was a mixture of Dow Affinity PL1850G and Dow Engage 8100, with melt flow indices of 3 g / 10 min and 1.0 g / 10 min, and densities of 0.902 g / cm³, respectively. 3 and 0.870 g / cm 3 The ethylene-vinyl alcohol copolymer used was Kuraray EVAL F171B from Japan, with an ethylene content of 32 wt%, a melt index of 1.6 g / 10 min, and a density of 1.19 g / cm³. 3 The maleic anhydride-modified polyolefin plastomer A used was CMG-5805L from Shanghai Jiayirong Co., Ltd., with a maleic anhydride grafting rate of 0.5-1.0%, a melt index of 0.3-2 g / 10 min, and a density of 0.87 g / cm³. 3The polyethylene A used was DuPont ULDPE-4404G; the polyethylene B used was Tianjin Petrochemical PE-LF081-8; the maleic anhydride-modified polyolefin plastomer B used was Mitsui Chemicals MD715, with a maleic anhydride grafting rate of 1.5%, a melt index of 1.5-3 g / 10 min, and a density of 0.872 g / cm³. 3 The selected antioxidant is antioxidant 1010; the selected light stabilizer is light stabilizer UV622.

[0083] Example 1

[0084] (1) Stir the polyolefin elastomer, antioxidant and light stabilizer for 10 minutes to mix them thoroughly to obtain a mixture for preparing the liquid contact layer. The content of the antioxidant in the mixture is 0.08 wt% and the content of the light stabilizer is 0.15 wt%.

[0085] (2) Ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyolefin plastisol A and polyethylene A are mixed in a weight ratio of 80:10:10. Then antioxidant and light stabilizer are added and stirred for 10 minutes to make them fully mixed to obtain the mixture for preparing the intermediate layer. The content of antioxidant in the mixture is 0.08 wt% and the content of light stabilizer is 0.15 wt%.

[0086] (3) Mix polyethylene B and maleic anhydride-modified polyolefin plastic body B in a weight ratio of 95:5, then add antioxidant and light stabilizer and stir for 10 minutes to make them fully mixed to obtain the mixture for preparing the outer layer. The content of antioxidant in the mixture is 0.08 wt% and the content of light stabilizer is 0.15 wt%.

[0087] (4) The mixture for preparing the liquid contact layer, the mixture for preparing the intermediate layer and the mixture for preparing the outer layer are respectively added to the corresponding extrusion channels of the twin-screw extruder. The screw speed is 150 r / min, the extrusion temperature is 200℃, and the die temperature is set to 180℃. After extrusion, a polymer film is obtained. The thickness of the polymer film is 335 μm and the thickness of the intermediate layer is 58 μm.

[0088] Example 2

[0089] (1) Stir the polyolefin elastomer, antioxidant and light stabilizer for 10 minutes to mix them thoroughly to obtain a mixture for preparing the liquid contact layer. The content of the antioxidant in the mixture is 0.08 wt% and the content of the light stabilizer is 0.15 wt%.

[0090] (2) Ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyolefin plastisol A and polyethylene A are mixed in a weight ratio of 80:10:10. Then antioxidant and light stabilizer are added and stirred for 10 minutes to make them fully mixed to obtain the mixture for preparing the intermediate layer. The content of antioxidant in the mixture is 0.08 wt% and the content of light stabilizer is 0.15 wt%.

[0091] (3) Mix polyethylene B and maleic anhydride-modified polyolefin plastic body B in a weight ratio of 95:5, then add antioxidant and light stabilizer and stir for 10 minutes to make them fully mixed to obtain the mixture for preparing the outer layer. The content of antioxidant in the mixture is 0.08 wt% and the content of light stabilizer is 0.15 wt%.

[0092] (4) The mixture for preparing the liquid contact layer, the mixture for preparing the intermediate layer and the mixture for preparing the outer layer are respectively added to the corresponding extrusion channels of the twin-screw extruder. The screw speed is 150 r / min, the extrusion temperature is 200℃, and the die temperature is set to 180℃. After extrusion, a polymer film is obtained. The thickness of the polymer film is 335 μm and the thickness of the intermediate layer is 55 μm.

[0093] Example 3

[0094] (1) Stir the polyolefin elastomer, antioxidant and light stabilizer for 10 minutes to mix them thoroughly to obtain a mixture for preparing the liquid contact layer. The content of the antioxidant in the mixture is 0.08 wt% and the content of the light stabilizer is 0.15 wt%.

[0095] (2) Ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyolefin plastisol A and polyethylene A are mixed in a weight ratio of 80:10:10. Then antioxidant and light stabilizer are added and stirred for 10 minutes to make them fully mixed to obtain the mixture for preparing the intermediate layer. The content of antioxidant in the mixture is 0.08 wt% and the content of light stabilizer is 0.15 wt%.

[0096] (3) Mix polyethylene B and maleic anhydride-modified polyolefin plastic body B in a weight ratio of 95:5, then add antioxidant and light stabilizer and stir for 10 minutes to make them fully mixed to obtain the mixture for preparing the outer layer. The content of antioxidant in the mixture is 0.08 wt% and the content of light stabilizer is 0.15 wt%.

[0097] (4) The mixture for preparing the liquid contact layer, the mixture for preparing the intermediate layer and the mixture for preparing the outer layer are respectively added to the corresponding extrusion channels of the twin-screw extruder. The screw speed is 150 r / min, the extrusion temperature is 200℃, and the die temperature is set to 180℃. After extrusion, a polymer film is obtained. The thickness of the polymer film is 335 μm and the thickness of the intermediate layer is 59 μm.

[0098] Example 4

[0099] (1) Stir the polyolefin elastomer, antioxidant and light stabilizer for 10 minutes to mix them thoroughly to obtain a mixture for preparing the liquid contact layer. The content of the antioxidant in the mixture is 0.08 wt% and the content of the light stabilizer is 0.15 wt%.

[0100] (2) Ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyolefin plastisol A and polyethylene A are mixed in a weight ratio of 80:10:10. Then antioxidant and light stabilizer are added and stirred for 10 minutes to make them fully mixed to obtain the mixture for preparing the intermediate layer. The content of antioxidant in the mixture is 0.08 wt% and the content of light stabilizer is 0.15 wt%.

[0101] (3) Mix polyethylene B and maleic anhydride-modified polyolefin plastic body B in a weight ratio of 95:5, then add antioxidant and light stabilizer and stir for 10 minutes to make them fully mixed to obtain the mixture for preparing the outer layer. The content of antioxidant in the mixture is 0.08 wt% and the content of light stabilizer is 0.15 wt%.

[0102] (4) The mixture for preparing the liquid contact layer, the mixture for preparing the intermediate layer and the mixture for preparing the outer layer are respectively added to the corresponding extrusion channels of the twin-screw extruder. The screw speed is 150 r / min, the extrusion temperature is 200℃, and the die temperature is set to 180℃. After extrusion, a polymer film is obtained. The thickness of the polymer film is 335 μm and the thickness of the intermediate layer is 60 μm.

[0103] Example 5

[0104] The method of Example 1 was implemented, except that the ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyolefin plastomer A, and polyethylene A were mixed in a weight ratio of 87:3:10.

[0105] Example 6

[0106] The method was implemented according to Example 1, except that the selected maleic anhydride-modified polyolefin plastic body A and maleic anhydride-modified polyolefin plastic body B had a melt index of 1-3 g / 10 min and a density of 0.9 g / cm³.3 The grafting rate of maleic anhydride is 0.7-0.9%;

[0107] The selected maleic anhydride-modified polyolefin plastomer A and maleic anhydride-modified polyolefin plastomer B are products of Dow Chemical Company, USA, with the brand name M2265.

[0108] Example 7

[0109] The method was implemented according to Example 2, except that the selected maleic anhydride-modified polyolefin plastic body A and maleic anhydride-modified polyolefin plastic body B had a melt index of 1-3 g / 10 min and a density of 0.9 g / cm³. 3 The grafting rate of maleic anhydride is 0.7-0.9%;

[0110] The selected maleic anhydride-modified polyolefin plastomer A and maleic anhydride-modified polyolefin plastomer B are products of Dow Chemical Company, USA, with the brand name M2265.

[0111] Comparative Example 1

[0112] The method of Example 1 is implemented, except that maleic anhydride-modified polyolefin plastic body A and polyethylene A are not added to the intermediate layer, and maleic anhydride-modified polyolefin plastic body B is not added to the outer layer.

[0113] Comparative Example 2

[0114] The method of Example 2 was implemented, except that maleic anhydride-modified polyolefin plastic body A and polyethylene A were not added to the intermediate layer, and maleic anhydride-modified polyolefin plastic body B was not added to the outer layer.

[0115] Comparative Example 3

[0116] The method of Example 3 was implemented, except that maleic anhydride-modified polyolefin plastic body A and polyethylene A were not added to the intermediate layer, and maleic anhydride-modified polyolefin plastic body B was not added to the outer layer.

[0117] Comparative Example 4

[0118] The method described in Example 4 is implemented, except that maleic anhydride-modified polyolefin plastic body A and polyethylene A are not added to the intermediate layer, and maleic anhydride-modified polyolefin plastic body B is not added to the outer layer.

[0119] Comparative Example 5

[0120] The method of Example 1 was implemented, except that the maleic anhydride-modified polyolefin plastic body A and the maleic anhydride-modified polyolefin plastic body B were replaced with an equal weight of DuPont ULDPE-4404G.

[0121] Test case

[0122] The rub resistance of the polymer films prepared in Examples 1-7 and Comparative Examples 1-5 was tested according to the method of GB / T 41347-2022 "Test Method for Rub Resistance of Flexible Packaging Materials". The test data are shown in Table 1.

[0123] The carbon dioxide permeability of the polymer films prepared in Examples 1-7 and Comparative Examples 1-5 was tested according to the method of GB / T1038-2022 "Test Method for Gas Permeability of Plastic Films and Sheets". The test data are shown in Table 1.

[0124] Table 1

[0125]

[0126] Note: " / " indicates that layer-to-layer separation in the polymer membrane cannot be tested to obtain valid data.

[0127] As can be seen from the data in Table 1, the polymer film of the present invention has excellent rub resistance, and after testing, the layers still adhere well and there is no delamination. Therefore, the polymer film of the present invention has excellent performance and can be well used to prepare bioreactor bags.

[0128] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A polymer film, characterized in that, The polymer film comprises a liquid contact layer, an intermediate layer, and an outer layer arranged sequentially by co-extrusion. The intermediate layer contains an ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyolefin plastic body A, and polyethylene A, and the outer layer contains polyethylene B and maleic anhydride-modified polyolefin plastic body B. The maleic anhydride grafting rates in the maleic anhydride-modified polyolefin plastic body A and the maleic anhydride-modified polyolefin plastic body B are each in the range of 0.3-1.5%.

2. The polymer film according to claim 1, characterized in that, In the intermediate layer, the content of the maleic anhydride-modified polyolefin plastomer A is 3-15 wt%; and / or In the outer layer, the content of the maleic anhydride-modified polyolefin plastomer B is 3-10 wt%.

3. The polymer film according to claim 1, characterized in that, The liquid contact layer contains a polyolefin elastomer; Preferably, the polyolefin elastomer is polyolefin elastomer POP and / or polyolefin elastomer POE.

4. The polymer film according to claim 1 or 2, characterized in that, In the intermediate layer, the weight ratio of the ethylene-vinyl alcohol copolymer, the maleic anhydride-modified polyolefin plastomer A, and the polyethylene A is (7.5-9.50):(0.5-1.5):

1.

5. The polymer film according to claim 1 or 2, characterized in that, In the outer layer, the weight ratio of the polyethylene B to the maleic anhydride-modified polyolefin plastide B is 1:0.03-0.

16.

6. The polymer film according to any one of claims 1-5, characterized in that, The maleic anhydride-modified polyolefin plastide A has a melt index of 0.2-14 g / 10 min; and / or The density of the maleic anhydride-modified polyolefin plastide A is 0.86-0.93 g / cm³. 3 ; and / or The content of free maleic anhydride in the maleic anhydride-modified polyolefin plastomer A is ≤100ppm, preferably ≤50ppm.

7. The polymer film according to any one of claims 1-5, characterized in that, The maleic anhydride-modified polyolefin plastide B has a melt index of 0.2-14 g / 10 min; and / or The density of the maleic anhydride-modified polyolefin plastomer B is 0.86-0.93 g / cm³. 3 ; and / or The content of free maleic anhydride in the maleic anhydride-modified polyolefin plastomer B is ≤100ppm, preferably ≤50ppm.

8. The polymer film according to claim 1 or 4, characterized in that, In the ethylene-vinyl alcohol copolymer, the ethylene content is 24-44 mol%; and / or The melt index of the ethylene-vinyl alcohol copolymer is 1-3 g / 10 min; and / or The density of the ethylene-vinyl alcohol copolymer is 1.1-1.25 g / cm³. 3 .

9. The polymer film according to claim 3, characterized in that, The melt index of the polyolefin elastomer is 0.1-5 g / 10 min; and / or The density of the polyolefin elastomer is 0.86-0.93 g / cm³. 3 .

10. The polymer film according to any one of claims 1-9, characterized in that, The polymer film also contains antioxidants and light stabilizers.

11. The polymer film according to any one of claims 1-10, characterized in that, The thickness of the polymer film is 300-500 μm.

12. The polymer film according to any one of claims 1-11, characterized in that, The thickness of the intermediate layer is 20-100 μm.

13. The polymer film according to any one of claims 1-12, characterized in that, The grafting rate of maleic anhydride in the maleic anhydride-modified polyolefin plastic body B is 0.5-0.8% higher than that in the maleic anhydride-modified polyolefin plastic body A.

14. The polymer film according to any one of claims 1-13, characterized in that, The density of the maleic anhydride-modified polyolefin plastic body B is 0.001-0.003 g / cm³ greater than that of the maleic anhydride-modified polyolefin plastic body A. 3 .

15. A method for preparing a polymer film, characterized in that, The method includes: placing a material containing a polyolefin elastomer in a first channel, placing a mixture containing an ethylene-vinyl alcohol copolymer, maleic anhydride-modified polyolefin plastic body A, and polyethylene A in a second channel, placing a mixture containing polyethylene B and maleic anhydride-modified polyolefin plastic body B in a third channel, and then simultaneously performing melt extrusion on the materials in the three channels. Preferably, the temperature of the melt extrusion is 160-230°C.

16. The polymer film prepared by the method according to claim 15.

17. The use of the polymer membrane according to any one of claims 1-14 or 16 in the preparation of disposable bioreactor bags.

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