Composition for hemodialysis shell, raw material for hemodialysis shell, and preparation method and application thereof

Abstract

The present application relates to the field of medical equipment, disclose a hemodialysis shell composition, hemodialysis shell raw material and its preparation method and application. The hemodialysis shell composition contains the following components stored independently or more than two mixed: the total weight of the composition as a basis, the content of propylene-ethylene copolymer is 91-95wt%, the content of styrene-ethylene-butadiene-styrene block copolymer is 4-9wt%, the content of antioxidant is 0.05-0.25wt%, the content of light stabilizer is 0.05-0.25wt%, the content of transparent agent is 0.01-0.25wt%. The hemodialysis shell raw material provided by the present application has no harmful substance residue, good transparency, high gloss, high strength, and is suitable for use in the medical field.

Description

Technical Field

[0001] This invention relates to the field of medical devices, specifically to compositions for hemodialysis shells, raw materials for hemodialysis shells, their preparation methods, and applications. Background Technology

[0002] Currently, polymer materials are widely used in the medical industry. With an aging population and increasing societal demands for medical technology, the industry's demand for medical-grade plastics will continue to rise.

[0003] Hemodialysis is one of the vital ways for uremia patients to maintain their lives. Hemodialysis machines generally use polycarbonate (PC) as the main material for the dialyzer shell and end caps. Polycarbonate has advantages such as high light transmittance, excellent mechanical properties, and low molding yield.

[0004] However, residual bisphenol A (BPA) in polycarbonate materials can cause endocrine disorders, induce precocious puberty, trigger metabolic disorders, and lead to obesity, threatening the health of fetuses and children. Therefore, the European Union has banned the production of baby bottles containing the chemical BPA. Furthermore, polycarbonate materials also pose safety risks when used in medical devices such as blood purification systems.

[0005] Compared to polycarbonate, polypropylene (PP) has advantages such as lower price, lower processing temperature, and no bisphenol A residue. Therefore, some medical devices previously made from polycarbonate are now being replaced by polypropylene.

[0006] CN110903549A discloses a polypropylene composite material, its preparation method, and its application. This composite material, in addition to polypropylene, also contains polyethylene, SEBS, paraffin oil, erucamide, several antioxidants, and toughening agents to meet the performance requirements for hemodialysis shells. However, because medical and health products are in prolonged contact with the human body, especially in hemodialysis, byproducts such as additives inevitably leach out, potentially causing harmful effects. Therefore, the types and amounts of additives added should be minimized in raw material formulations used in medical and health applications. Furthermore, products made from this composite material inevitably experience aging when exposed to light sources for extended periods, accelerating the precipitation of byproducts.

[0007] In summary, it is of great significance to provide a safe, non-toxic hemodialysis shell material that has excellent mechanical properties and meets the performance requirements of not having too many types of added raw materials. Summary of the Invention

[0008] The purpose of this invention is to overcome the problems of existing technologies, such as the need to add multiple substances during the preparation of dialysis shell raw materials, and the use of polycarbonate in the preparation of dialysis shells, which results in residual bisphenol A.

[0009] To achieve the above objectives, the present invention provides a composition for hemodialysis shells, which contains the following components, which may be stored independently or in combination:

[0010] Propylene-ethylene copolymer, styrene-ethylene-butadiene-styrene block copolymer, antioxidants, light stabilizers, and transparent agents;

[0011] Wherein, based on the total weight of the composition, the content of the propylene-ethylene copolymer is 91-95 wt%, the content of the styrene-ethylene-butadiene-styrene block copolymer is 4-9 wt%, the content of the antioxidant is 0.05-0.25 wt%, the content of the light stabilizer is 0.05-0.25 wt%, and the content of the transparent agent is 0.01-0.25 wt%.

[0012] In the propylene-ethylene copolymer, the molar ratio of monomers provided by ethylene to monomers provided by propylene is 1:20-95;

[0013] The styrene-ethylene-butadiene-styrene block copolymer is a star-shaped styrene-ethylene-butadiene-styrene block copolymer and / or a linear styrene-ethylene-butadiene-styrene block copolymer.

[0014] A second aspect of the present invention provides a method for preparing raw materials for hemodialysis shells, the method comprising using the components of the hemodialysis shell composition described in the first aspect above, including:

[0015] (1) At 15-28℃, propylene-ethylene copolymer, styrene-ethylene-butadiene-styrene block copolymer, antioxidant, light stabilizer and transparent agent are mixed to obtain a mixture;

[0016] (2) The mixture is melted on a twin-screw extruder at 180-210°C, and then extruded and granulated to obtain raw material for hemodialysis shells;

[0017] Based on the total weight of the propylene-ethylene copolymer, the styrene-ethylene-butadiene-styrene block copolymer, the antioxidant, the light stabilizer, and the transparent agent, the amount of the propylene-ethylene copolymer is 91-95 wt%, the amount of the styrene-ethylene-butadiene-styrene block copolymer is 4-9 wt%, the amount of the antioxidant is 0.05-0.25 wt%, the amount of the light stabilizer is 0.05-0.25 wt%, and the amount of the transparent agent is 0.01-0.25 wt%.

[0018] In the propylene-ethylene copolymer, the molar ratio of monomers provided by ethylene to monomers provided by propylene is 1:20-95;

[0019] The styrene-ethylene-butadiene-styrene block copolymer is a star-shaped styrene-ethylene-butadiene-styrene block copolymer and / or a linear styrene-ethylene-butadiene-styrene block copolymer;

[0020] The raw material used for the hemodialysis shell has a notched impact strength of 4.5-5 KJ / m at 23°C. 2 .

[0021] A third aspect of the present invention provides a raw material for hemodialysis shells prepared by the method described in the second aspect above.

[0022] The fourth aspect of the present invention provides the application of the raw material for hemodialysis shells described in the third aspect above in the field of medical devices.

[0023] The technical solution of this invention provides a raw material for hemodialysis shells that solves the safety hazards caused by bisphenol A residue in polycarbonate hemodialysis shells. The product has no harmful substance residue, good transparency, high gloss, and is impact resistant while having high strength, making it suitable for use in the medical field. Detailed Implementation

[0024] 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.

[0025] As previously described, a first aspect of the present invention provides a composition for hemodialysis shells, the composition containing the following components, which are stored individually or in combination:

[0026] Propylene-ethylene copolymer, styrene-ethylene-butadiene-styrene block copolymer, antioxidants, light stabilizers, and transparent agents;

[0027] Wherein, based on the total weight of the composition, the content of the propylene-ethylene copolymer is 91-95 wt%, the content of the styrene-ethylene-butadiene-styrene block copolymer is 4-9 wt%, the content of the antioxidant is 0.05-0.25 wt%, the content of the light stabilizer is 0.05-0.25 wt%, and the content of the transparent agent is 0.01-0.25 wt%.

[0028] In the propylene-ethylene copolymer, the molar ratio of monomers provided by ethylene to monomers provided by propylene is 1:20-95;

[0029] The styrene-ethylene-butadiene-styrene block copolymer is a star-shaped styrene-ethylene-butadiene-styrene block copolymer and / or a linear styrene-ethylene-butadiene-styrene block copolymer.

[0030] Preferably, the weight-average molecular weight of the star-shaped styrene-ethylene-butadiene-styrene block copolymer is 200,000-280,000; and the weight-average molecular weight of the linear styrene-ethylene-butadiene-styrene block copolymer is 200,000-280,000. The inventors have found that, under this preferred condition, the processing performance of the hemodialysis shell raw material and the impact resistance of the product prepared from the composition are optimized.

[0031] Preferably, the styrene-ethylene-butadiene-styrene block copolymer is a star-shaped styrene-ethylene-butadiene-styrene block copolymer or a linear styrene-ethylene-butadiene-styrene block copolymer; and

[0032] The weight ratio of the star-shaped styrene-ethylene-butadiene-styrene block copolymer to the linear styrene-ethylene-butadiene-styrene block copolymer is 1:5.

[0033] In a preferred embodiment, the weight ratio of the star-shaped styrene-ethylene-butadiene-styrene block copolymer to the linear styrene-ethylene-butadiene-styrene block copolymer is 1:3. The inventors have found that, in this preferred embodiment, the hemodialysis shell material prepared using the composition exhibits good impact resistance and performs well in drop tests.

[0034] Preferably, the melt flow index (MFR) of the propylene-ethylene copolymer at 230°C and a load of 2.16 kg is 8-25 g / 10 min.

[0035] Preferably, the transparent agent is a sorbitol-based transparent nucleating agent.

[0036] Preferably, the antioxidant is selected from at least one of tetramethyl[(3,5-di-tert-butyldilauryl thiodipropionate)]methane, thiodiethylidene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), thiobis(2-tert-butyl-5-methylphenol), tris(2,4-di-tert-butyl)phosphite, di-tert-butylphenyl-phosphite, 4,4-thiobis(6-tert-butyl-3-methylphenol), and 2,2-thiobis(6-tert-butyl-4-methylphenol).

[0037] More preferably, the antioxidant is 4,4-thiobis(6-tert-butyl-3-methylphenol).

[0038] In a preferred embodiment, the light stabilizer is a hindered amine light stabilizer.

[0039] More preferably, the light stabilizer is at least one of bis-2,2,6,6-tetramethylpiperidinol sebacate, poly[1-(2'hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidin succinate], and hindered amine light stabilizer HS-944.

[0040] More preferably, the light stabilizer is bis-2,2,6,6-tetramethylpiperidinol sebacate.

[0041] As previously described, a second aspect of the present invention provides a method for preparing raw materials for hemodialysis shells, the method comprising using the components of the hemodialysis shell composition described in the first aspect, including:

[0042] (1) At 15-28℃, propylene-ethylene copolymer, styrene-ethylene-butadiene-styrene block copolymer, antioxidant, light stabilizer and transparent agent are mixed to obtain a mixture;

[0043] (2) The mixture is melted on a twin-screw extruder at 180-210°C, and then extruded and granulated to obtain raw material for hemodialysis shells;

[0044] Based on the total weight of the propylene-ethylene copolymer, the styrene-ethylene-butadiene-styrene block copolymer, the antioxidant, the light stabilizer, and the transparent agent, the amount of the propylene-ethylene copolymer is 91-95 wt%, the amount of the styrene-ethylene-butadiene-styrene block copolymer is 4-9 wt%, the amount of the antioxidant is 0.05-0.25 wt%, the amount of the light stabilizer is 0.05-0.25 wt%, and the amount of the transparent agent is 0.01-0.25 wt%.

[0045] In the propylene-ethylene copolymer, the molar ratio of monomers provided by ethylene to monomers provided by propylene is 1:20-95;

[0046] The styrene-ethylene-butadiene-styrene block copolymer is a star-shaped styrene-ethylene-butadiene-styrene block copolymer and / or a linear styrene-ethylene-butadiene-styrene block copolymer;

[0047] The raw material used for the hemodialysis shell has a notched impact strength of 4.5-5 KJ / m at 23°C. 2 .

[0048] Preferably, the mixing is carried out under stirring conditions, and at least the following conditions are met: the rotation speed is 150-200 r / min, and the time is 0.5-5 min.

[0049] Preferably, the melting and the extrusion granulation are carried out in a twin-screw extruder, and the main rotor speed of the twin-screw extruder is 180-230 r / min.

[0050] As previously stated, a third aspect of the present invention provides a raw material for hemodialysis shells prepared by the method described in the second aspect above.

[0051] As previously stated, the fourth aspect of the present invention provides the application of the raw material for hemodialysis shells described in the third aspect above in the field of medical devices.

[0052] The present invention will be described in detail below by way of examples, but this does not mean that the present invention is limited in any way.

[0053] In the following examples, unless otherwise specified, all raw materials used are products of Sinopharm Chemical Reagent Co., Ltd.

[0054] Propylene-ethylene copolymer I: purchased from Sinopec Yanshan Petrochemical Company, grade 4912, wherein the molar ratio of monomers supplied by ethylene to monomers supplied by propylene is 1:33, and the melt flow index (MFR) at 230℃ and 2.16kg load is 12g / 10min;

[0055] Propylene-ethylene copolymer II: purchased from Sinopec Yanshan Petrochemical Company, grade 4908, wherein the molar ratio of monomers supplied by ethylene to monomers supplied by propylene is 1:33, and the melt flow index (MFR) at 230℃ and 2.16kg load is 8g / 10min;

[0056] Propylene-ethylene copolymer III: purchased from Sinopec Yanshan Petrochemical Company, grade MPP4016, wherein the molar ratio of monomers supplied by ethylene to monomers supplied by propylene is 1:18; the melt flow index (MFR) at 2.16 kg is 20 g / 10 min; and the weight average molecular weight is 200,000.

[0057] Homopolymer polypropylene: purchased from Sinopec Yanshan Petrochemical Company, grade K1118, with a melt flow index (MFR) of 20 g / 10 min at 2.16 kg; weight average molecular weight of 200,000.

[0058] Block copolymer I: Star-shaped styrene-ethylene-butadiene-styrene block copolymer: weight average molecular weight of 220,000, purchased from Yueyang Petrochemical, grade 602;

[0059] Block copolymer II: Linear styrene-ethylene-butadiene-styrene block copolymer: weight average molecular weight of 220,000, purchased from Asahi Kasei Corporation, grade H1221;

[0060] Block copolymer III: is a linear styrene-butadiene-styrene block copolymer with a weight-average molecular weight of 330,000. It was purchased from Sinopec Yanshan Petrochemical Company and its grade is 1301.

[0061] Antioxidant: Purchased from Sinopec Yanshan Petrochemical Company, model number Antioxidant 168;

[0062] Light stabilizer: Purchased from Sinopec Yanshan Petrochemical Company, model number 622;

[0063] Transparent agent: Purchased from Sinopec Yanshan Petrochemical Company, brand name sorbitol transparent agent 8000.

[0064] In this invention, unless otherwise specified, the ambient temperature or room temperature mentioned in the following examples is 25±5℃.

[0065] In the following examples, unless otherwise specified, each “parts by weight” means 100g.

[0066] In the following embodiments, the performance indicator parameters are tested according to the following standards:

[0067] Haze test for injection molding (1mm): conducted according to standard GB / T 2410-2008;

[0068] Flexural modulus test: conducted in accordance with standard GB / T 9341-2008;

[0069] Yellow index test: conducted in accordance with standard HG / T 3862-2006;

[0070] Notched impact strength test of simply supported beam (-20℃): conducted in accordance with standard GB / T 1043.1-2008;

[0071] Notched impact strength test of simply supported beam (23℃): conducted in accordance with standard GB / T 1043.1-2008;

[0072] Melt flow rate test: conducted in accordance with standard GB / T 3682.1-2018;

[0073] Shrinkage test: conducted in accordance with standard GB / T 17037.4-2003.

[0074] Example 1

[0075] This embodiment illustrates the preparation of raw materials for hemodialysis shells using the method provided by this invention, and is carried out with reference to the parameters in Table 1, etc., specifically including:

[0076] (1) At room temperature and with a stirring speed of 150 r / min, propylene-ethylene copolymer (propylene-ethylene copolymer I), styrene-ethylene-butadiene-styrene block copolymer, antioxidant, light stabilizer and transparent agent were mixed for 2 min to obtain a mixture;

[0077] (2) The mixture was melted on a twin-screw extruder at 210°C, and then the main speed of the twin-screw extruder was adjusted to 220 r / min for extrusion granulation to obtain raw material for hemodialysis shells, named P1.

[0078] Among them, the styrene-ethylene-butadiene-styrene block copolymer is a star-shaped styrene-ethylene-butadiene-styrene block copolymer and a linear styrene-ethylene-butadiene-styrene block copolymer; and the weight ratio of the content of the star-shaped styrene-ethylene-butadiene-styrene block copolymer to the linear styrene-ethylene-butadiene-styrene block copolymer is 1:3.

[0079] Example 2

[0080] This embodiment uses a method similar to that of Example 1, except that the propylene-ethylene copolymer used is propylene-ethylene copolymer II, and the amount of substance added is changed. For specific parameters, please refer to Table 1. The raw material for hemodialysis shell is obtained and named P2.

[0081] Example 3

[0082] This embodiment uses a method similar to that of Example 1, except that the weight ratio of the star-shaped styrene-ethylene-butadiene-styrene block copolymer to the linear styrene-ethylene-butadiene-styrene block copolymer is 1:4, and the process parameters are changed to obtain the raw material for hemodialysis shells. The specific parameters are shown in Table 1 and named P3.

[0083] Example 4

[0084] This embodiment uses a method similar to that of Example 1, except that the styrene-ethylene-butadiene-styrene block copolymers used are all star-shaped styrene-ethylene-butadiene-styrene block copolymers, and the raw material for hemodialysis shells is named P4.

[0085] Comparative Example 1

[0086] This comparative example uses a method similar to that of Example 1, except that block copolymer III is used instead of styrene-ethylene-butadiene-styrene block copolymer to obtain a raw material for hemodialysis shells, named DP1.

[0087] Comparative Example 2

[0088] This comparative example uses a method similar to that of Example 1, except that propylene-ethylene copolymer III is used instead of propylene-ethylene copolymer I to obtain a raw material for hemodialysis shells, named DP2.

[0089] Comparative Example 3

[0090] This comparative example uses a method similar to that of Example 1, except that homopolymer polypropylene is used instead of propylene-ethylene copolymer I to obtain a raw material for hemodialysis shells, named DP3.

[0091] Test Example 1

[0092] The melt flow rate, flexural modulus, yellow index, shrinkage rate, and other properties of some of the products in the above examples were measured. The test results are shown in Table 2.

[0093] Table 1

[0094]

[0095]

[0096] Table 2

[0097]

[0098] As can be seen from the above results, the raw material for hemodialysis shells provided by the present invention does not use polycarbonate, has no harmful substance residue, good transparency, high gloss, and is impact resistant while having high strength, making it suitable for use in the medical field.

[0099] 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 protected by the present invention.

Claims

1. A composition for use in hemodialysis shells, characterized in that, The hemodialysis shell composition contains the following components, which may be stored individually or in combination: Propylene-ethylene copolymer, styrene-ethylene-butadiene-styrene block copolymer, antioxidants, light stabilizers, and transparent agents; Wherein, based on the total weight of the composition, the content of the propylene-ethylene copolymer is 91-95 wt%, the content of the styrene-ethylene-butadiene-styrene block copolymer is 4-9 wt%, the content of the antioxidant is 0.05-0.25 wt%, the content of the light stabilizer is 0.05-0.25 wt%, and the content of the transparent agent is 0.01-0.25 wt%. In the propylene-ethylene copolymer, the molar ratio of monomers provided by ethylene to monomers provided by propylene is 1:20-95; The styrene-ethylene-butadiene-styrene block copolymer is either a star-shaped styrene-ethylene-butadiene-styrene block copolymer or a linear styrene-ethylene-butadiene-styrene block copolymer; and The weight ratio of the star-shaped styrene-ethylene-butadiene-styrene block copolymer to the linear styrene-ethylene-butadiene-styrene block copolymer is 1:

3.

2. The composition according to claim 1, wherein, The star-shaped styrene-ethylene-butadiene-styrene block copolymer has a weight-average molecular weight of 200,000-280,000; and The linear styrene-ethylene-butadiene-styrene block copolymer has a weight-average molecular weight of 200,000-280,000.

3. The composition according to claim 1 or 2, wherein, The propylene-ethylene copolymer has a melt flow index (MFR) of 8-25 g / 10 min at 230°C and a load of 2.16 kg; and / or The transparent agent is a sorbitol-based transparent nucleating agent.

4. The composition according to claim 1 or 2, wherein, The antioxidant is selected from at least one of tetramethyl[(3,5-di-tert-butyldilauryl thiodipropionate)]methane, thiodiethylidene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate), thiobis(2-tert-butyl-5-methylphenol), tris(2,4-di-tert-butyl)phosphite, di-tert-butylphenyl-phosphite, 4,4-thiobis(6-tert-butyl-3-methylphenol), and 2,2-thiobis(6-tert-butyl-4-methylphenol).

5. The composition according to claim 1 or 2, wherein, The antioxidant is 4,4-thiobis(6-tert-butyl-3-methylphenol).

6. The composition according to claim 1 or 2, wherein, The light stabilizer is a hindered amine light stabilizer.

7. The composition according to claim 1 or 2, wherein, The light stabilizer is at least one of bis-2,2,6,6-tetramethylpiperidinol sebacate, poly[1-(2'hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidin succinate], and hindered amine light stabilizer HS-944.

8. The composition according to claim 1 or 2, wherein, The light stabilizer is bis-2,2,6,6-tetramethylpiperidinol sebacate.

9. A method for preparing raw materials for hemodialysis shells, characterized in that, This method utilizes the components of the hemodialysis shell composition according to any one of claims 1-8, comprising: (1) At 15-28℃, propylene-ethylene copolymer, styrene-ethylene-butadiene-styrene block copolymer, antioxidant, light stabilizer and transparent agent are mixed to obtain a mixture; (2) The mixture is melted on a twin-screw extruder at 180-210°C, and then extruded and granulated to obtain raw material for hemodialysis shells; Based on the total weight of the propylene-ethylene copolymer, the styrene-ethylene-butadiene-styrene block copolymer, the antioxidant, the light stabilizer, and the transparent agent, the amount of the propylene-ethylene copolymer is 91-95 wt%, the amount of the styrene-ethylene-butadiene-styrene block copolymer is 4-9 wt%, the amount of the antioxidant is 0.05-0.25 wt%, the amount of the light stabilizer is 0.05-0.25 wt%, and the amount of the transparent agent is 0.01-0.25 wt%. In the propylene-ethylene copolymer, the molar ratio of monomers provided by ethylene to monomers provided by propylene is 1:20-95; The styrene-ethylene-butadiene-styrene block copolymer is either a star-shaped styrene-ethylene-butadiene-styrene block copolymer or a linear styrene-ethylene-butadiene-styrene block copolymer; and The weight ratio of the star-shaped styrene-ethylene-butadiene-styrene block copolymer to the linear styrene-ethylene-butadiene-styrene block copolymer is 1:

3.

10. The method according to claim 9, wherein, The mixing is carried out under stirring conditions, and at least meets the following requirements: a rotation speed of 150-200 r / min and a time of 0.5-5 min; and / or The melting and extrusion granulation are carried out in a twin-screw extruder, and the main rotor speed of the twin-screw extruder is 180-250 r / min.

11. Raw material for hemodialysis shells prepared by the method of claim 9 or 10.

12. The application of the raw material for hemodialysis shells as described in claim 11 in the field of medical devices.

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