An antistatic polyisoprene rubber anesthetic reservoir
By using a combination of raw materials with specific ratios and aging agent generated by complex chemical reactions in the antistatic polyisoprene rubber anesthetic airbags, the problem of insufficient migration resistance of the antistatic polyisoprene rubber anesthetic airbags in the prior art is solved, and excellent anti-aging and migration resistance are achieved, meeting strict usage standards.
Patent Information
- Application Number
- CN202510200937.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-24
- Publication Date
- 2025-05-30
- Estimated Expiration
- 2045-02-24
AI Technical Summary
The existing anti-static polyisoprene rubber anesthesia airbags have insufficient migration resistance and cannot meet the strict usage standards.
Using a combination of raw materials with specific ratios, including polyisoprene latex, stabilizers, aqueous sodium para-styrene sulfonate solution, nano-silica suspension dispersion, anti-aging agent, conductive graphite and vulcanization package, a complex chemical reaction is used to generate an anti-aging agent with excellent anti-aging properties and added to the polyisoprene rubber.
The anti-aging and migration resistance of anti-static polyisoprene rubber anesthetic airbags is significantly improved, making them meet strict standards, such as YY/T0978-2016 and GB9706.1-2007, which can replace natural latex anti-static anesthetic airbags.
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Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of anesthesia air bags, and particularly relates to an antistatic polyisoprene rubber anesthesia air bag. Background Art
[0002] An anesthesia air bag is a component used to store gas in the respiratory system of an anesthesia machine. It consists of an air bag and a connector, and its main function is to regulate the gas supply. When the gas supply is more than the gas required by the system, it temporarily stores the excess gas; when the gas supply is insufficient, it releases the stored gas for supplementation.
[0003] Anesthesia air bags are classified into non-antistatic anesthesia air bags and antistatic (conductive) anesthesia air bags according to their conductivity. The international standard for anesthesia air bags is ISO5362-2006, and there is already a corresponding national standard YY / T0978-2016. The standard not only requires the structural design and various performance indicators of the product, but also has clear requirements for materials, safety, testing and detection methods. Generally speaking, anesthesia air bags need to have good elasticity and durability to ensure effective storage and release of gas during use.
[0004] The Chinese patent application with the publication number CN118165385A discloses a polyisoprene rubber anesthesia air bag, and the prepared anesthesia air bag has good mechanical properties and antistatic properties, but insufficient migration resistance. Summary of the Invention
[0005] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide an antistatic polyisoprene rubber anesthesia air bag.
[0006] To achieve the above purpose, the present invention is realized through the following technical solutions:
[0007] An antistatic polyisoprene rubber anesthesia air bag, comprising the following raw materials in parts by weight:
[0008] Polyisoprene latex: 100 parts;
[0009] Stabilizer: 0.5 - 2 parts;
[0010] Sodium p-styrenesulfonate aqueous solution: 1 - 2 parts;
[0011] Nano-silica suspension dispersion: 3 - 6 parts;
[0012] Antioxidant: 1 - 2 parts;
[0013] Conductive graphite: 0.8 - 2 parts;
[0014] Vulcanization package: 3 - 6 parts;
[0015] Among them: The vulcanization package includes raw materials in the following parts by weight: sulfur: 5 - 10 parts; zinc oxide: 4 - 8 parts; accelerator: 5 - 10 parts; antioxidant 1010: 5 - 8 parts; Peregal O - 20: 3 - 6 parts;
[0016] The antioxidant is first prepared by reacting 3-(3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionic acid with glycerol 1 - ether - d5 to form an esterification product, and then epoxidizing it with hydrogen peroxide and formic acid and reacting with N - phenyl - 1,3 - phenylenediamine. The antioxidant is prepared by the following method:
[0017] S1: Put 3-(3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionic acid, glycerol 1 - ether - d5, p - toluenesulfonic acid and toluene into a reaction flask in sequence, stir, heat to 110 - 120 °C, remove the generated water through a water separator until no water is generated, react for 6 - 8 h, cool to room temperature, and perform post - treatment to obtain intermediate 1; The reaction equation is shown as follows:
[0018] ;
[0019] S2: Add DMF, intermediate 1 and strong acid cation exchange resin into a reactor, stir, and heat to 60 - 80 °C; Then mix formic acid and 30wt% H 2 O 2 evenly, slowly drop it into the reaction flask, after dropping, react for 6 - 8 h, and perform post - treatment to obtain intermediate 2; The reaction equation is shown as follows:
[0020] ;
[0021] S3: Put intermediate 2, N - phenyl - 1,3 - phenylenediamine, triethylamine and tetrahydrofuran into a reaction flask in sequence, stir, raise the temperature to 70 - 75 °C and react for 9 - 10 h, cool to room temperature, and perform post - treatment to obtain the antioxidant; The reaction equation is shown as follows:
[0022] ;
[0023] It should be noted that the above reaction equations are only for illustration to show the reactions between functional groups.
[0024] In step S1, the molar ratio of 3-(3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionic acid, glycerol 1 - ether - d5, and p - toluenesulfonic acid is 2:(1.1 - 1.5):0.05.
[0025] In step S2, the mass ratio of intermediate 1, strong acid cation exchange resin, formic acid and 30wt% H 2 O 2 is 10:(0.5 - 2):(1.5 - 3):(6 - 8).
[0026] In step S3, the molar ratio of intermediate 2, N-phenyl-1,3-phenylenediamine, and triethylamine in the feed is 1:(1.2 - 1.5):(1 - 2).
[0027] The sulfur, zinc oxide, accelerator, antioxidant, and conductive graphite are all water dispersions with a total solid content of 50 wt%; the water dispersions are all ground by a nano-abrasive machine until the D90 of the dispersion is not greater than 3 microns, and 0.2 - 0.8 wt% of sodium methylene dinaphthalene sulfonate is added as a surfactant to the ground water dispersion.
[0028] Due to the adoption of the above technical solutions, the beneficial effects of the present invention include:
[0029] (1) The antioxidant in the present invention improves the anti-aging ability through the combined action of hindered phenol and aromatic amine. After adding it to the antistatic polyisoprene rubber anesthesia storage bag, the anti-aging performance and migration resistance of the antistatic polyisoprene rubber anesthesia storage bag are improved.
[0030] (2) The antistatic polyisoprene rubber anesthesia storage bag provided by the present invention has physical properties that meet the requirements of the YY / T 0978-2016 standard, the product conductivity meets the requirements of 39.3b in GB 9706.1-2007, the product resistance value is less than 1 MΩ, and the anti-aging performance is excellent, and it can replace the natural latex-based antistatic anesthesia storage bag. Specific Embodiments
[0031] The following is further described in conjunction with embodiments, but the present invention is not limited to these embodiments.
[0032] Example 1 Preparation of antioxidant:
[0033] S1: Put 1000 ml of toluene, 2 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 1.1 mol of glycerol 1-ether-d5, and 0.05 mol of p-toluenesulfonic acid into a reaction flask in sequence, stir, heat to 110 °C, react for 8 h (remove the generated water through a water separator during the reaction process), cool to room temperature, and remove toluene by vacuum distillation at 70 °C for 3 h. The residue is dissolved in 500 ml of ethyl acetate, and is washed successively with 120 mL of 5 wt% NaHCO 3 solution and 120 ml of saturated brine, and rotary evaporate at 60 °C for 2 h to obtain intermediate 1;
[0034] S2: Put 1000 ml of DMF, 300 g of intermediate 1, and 15 g of strong acid cation exchange resin into a reactor, stir, and heat to 70 °C; then add 45 g of formic acid and 180 g of 30 wt% H 2 O 2After mixing evenly, slowly add dropwise into the reaction flask. After the addition is completed (the dropping takes 30 min), react for 6 h, then cool to room temperature, distill under reduced pressure at 70 °C for 2.5 h. The residue is dissolved in 500 ml of ethyl acetate and washed with deionized water (200 ml × 3 times), then distilled under reduced pressure at 70 °C for 2 h to obtain Intermediate 2;
[0035] S3: Under nitrogen protection, add 1200 ml of tetrahydrofuran, 1 mol of Intermediate 2, 1.2 mol of N-phenyl-1,3-phenylenediamine, and 1 mol of triethylamine into the reaction flask in sequence, stir, heat up to 70 °C and react for 10 h. Then cool to room temperature, wash with deionized water (200 ml × 3 times), distill under reduced pressure at 70 °C for 3 h to remove tetrahydrofuran, and dry at 70 °C for 10 h to obtain the antioxidant.
[0036] Example 2 Preparation of antioxidant:
[0037] S1: Add 1000 ml of toluene, 2 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 1.4 mol of glycerol 1-oleate-d5, and 0.08 mol of p-toluenesulfonic acid into the reaction flask in sequence, stir, heat up to 115 °C, and react for 7 h (remove the generated water through a water separator during the reaction process). Then cool to room temperature, distill under reduced pressure at 70 °C for 3 h to remove toluene. The residue is dissolved in 500 ml of ethyl acetate and washed successively with 120 mL of 5 wt% NaHCO 3 solution and 120 ml of saturated brine, and rotary evaporate at 60 °C for 2 h to obtain Intermediate 1;
[0038] S2: Add 1000 ml of DMF, 300 g of Intermediate 1, and 45 g of strong acid cation exchange resin into the reactor, stir, and heat up to 80 °C; then mix 75 g of formic acid and 210 g of 30 wt% H 2 O 2 After mixing evenly, slowly add dropwise into the reaction flask. After the addition is completed (the dropping takes 30 min), react for 7 h, then cool to room temperature, distill under reduced pressure at 70 °C for 2.5 h. The residue is dissolved in 500 ml of ethyl acetate and washed with deionized water (200 ml × 3 times), then distilled under reduced pressure at 70 °C for 2 h to obtain Intermediate 2;
[0039] S3: Under nitrogen protection, add 1200 ml of tetrahydrofuran, 1 mol of Intermediate 2, 1.4 mol of N-phenyl-1,3-phenylenediamine, and 1.6 mol of triethylamine into the reaction flask in sequence, stir, heat up to 70 °C and react for 10 h. Then cool to room temperature, wash with deionized water (200 ml × 3 times), distill under reduced pressure at 70 °C for 3 h to remove tetrahydrofuran, and dry at 70 °C for 10 h to obtain the antioxidant.
[0040] Example 3 Preparation of antioxidant:
[0041] S1: Put 1000 ml of toluene, 2 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 1.5 mol of glycerol 1-ether-d5, and 0.05 mol of p-toluenesulfonic acid into a reaction flask in sequence, stir, heat to 120 °C, react for 6 h (remove the generated water through a water separator during the reaction), cool to room temperature, and distill under reduced pressure at 70 °C for 3 h to remove toluene. The residue is dissolved in 500 ml of ethyl acetate and washed successively with 120 mL of 5 wt% NaHCO 3 solution and 120 ml of saturated brine, and rotary evaporate at 60 °C for 2 h to obtain Intermediate 1;
[0042] S2: Put 1000 ml of DMF, 300 g of Intermediate 1, and 60 g of strong acid cation exchange resin into a reactor, stir, and heat to 80 °C; then mix 90 g of formic acid and 240 g of 30 wt% H 2 O 2 After mixing evenly, slowly drop it into the reaction flask. After dropping (the dropping time is 30 min), react for 8 h, then cool to room temperature, distill under reduced pressure at 70 °C for 2.5 h, dissolve the residue in 500 ml of ethyl acetate, wash with deionized water (200 ml × 3 times), and distill under reduced pressure at 70 °C for 2 h to obtain Intermediate 2;
[0043] S3: Under nitrogen protection, put 1200 ml of tetrahydrofuran, 1 mol of Intermediate 2, 1.5 mol of N-phenyl-1,3-phenylenediamine, and 2 mol of triethylamine into a reaction flask in sequence, stir, heat to 75 °C and react for 9 h, cool to room temperature, wash with deionized water (200 ml × 3 times), distill under reduced pressure at 70 °C for 3 h to remove tetrahydrofuran, and dry at 70 °C for 10 h to obtain the antioxidant.
[0044] Example 4
[0045] An antistatic polyisoprene rubber anesthesia reservoir bag is composed of the following raw materials in parts by weight:
[0046] Polyisoprene latex: 100 parts, stabilizer (10 wt% potassium hydroxide aqueous solution): 2 parts, sodium p-styrenesulfonate aqueous solution (25 wt%): 1 part, nano-silica suspension dispersion: 3 parts, antioxidant (prepared in Example 1): 1 part, conductive graphite: 0.8 part, vulcanization package: 3 parts;
[0047] Among them: The vulcanization package includes the following raw materials in parts by weight: sulfur: 5 parts; zinc oxide: 4 parts; accelerator (accelerator TMTD): 5 parts; antioxidant 1010: 5 parts; Peregal O-20: 3 parts.
[0048] Among the above raw materials, sulfur, zinc oxide, accelerator, antioxidant 1010, and conductive graphite are all in the form of aqueous dispersions with a total solid content of 50 wt%; the aqueous dispersions are all ground by a nano-abrasive machine to a D90 of the dispersion not exceeding 3 microns, and 0.4 wt% of sodium methylene bisnaphthalene sulfonate is added as a surfactant to the ground aqueous dispersion.
[0049] Example 5
[0050] An antistatic polyisoprene rubber anesthetic reservoir bag is composed of the following raw materials in parts by weight:
[0051] Polyisoprene latex: 100 parts, stabilizer (20 wt% potassium hydroxide aqueous solution): 1 part, sodium p-styrenesulfonate aqueous solution (25 wt%): 1.5 parts, nano-silica suspension dispersion: 4.5 parts, antioxidant (prepared in Example 2): 1.5 parts, conductive graphite: 1.2 parts, vulcanization package: 4.5 parts;
[0052] Among them: the vulcanization package includes the following raw materials in parts by weight: sulfur: 8 parts; zinc oxide: 6 parts; accelerator (accelerator BZ): 8 parts; antioxidant 1010: 6 parts; Peregal O-20: 4.5 parts.
[0053] Among the above raw materials, sulfur, zinc oxide, accelerator, antioxidant 1010, and conductive graphite are all in the form of aqueous dispersions with a total solid content of 50 wt%; the aqueous dispersions are all ground by a nano-abrasive machine to a D90 of the dispersion not exceeding 3 microns, and 0.6 wt% of sodium methylene bisnaphthalene sulfonate is added as a surfactant to the ground aqueous dispersion.
[0054] Example 6
[0055] An antistatic polyisoprene rubber anesthetic reservoir bag is composed of the following raw materials in parts by weight:
[0056] Polyisoprene latex: 100 parts, stabilizer (25 wt% potassium hydroxide aqueous solution): 0.5 part, sodium p-styrenesulfonate aqueous solution (30 wt%): 2 parts, nano-silica suspension dispersion: 6 parts, antioxidant (prepared in Example 3): 2 parts, conductive graphite: 2 parts, vulcanization package: 6 parts;
[0057] Among them: the vulcanization package includes the following raw materials in parts by weight: sulfur: 10 parts; zinc oxide: 8 parts; accelerator (accelerator BZ): 10 parts; antioxidant 1010: 8 parts; Peregal O-20: 6 parts.
[0058] Among the above raw materials, sulfur, zinc oxide, accelerator, antioxidant 1010, and conductive graphite are all in the form of aqueous dispersions with a total solid content of 50 wt%; the aqueous dispersions are all ground by a nano-abrasive machine until the D90 of the dispersion is no more than 3 microns, and 0.8 wt% of sodium methylene bisnaphthalene sulfonate is added as a surfactant to the ground aqueous dispersion.
[0059] Comparative Example 1
[0060] The raw material components and ratios of the anesthesia storage airbag are basically the same as those in Example 5, except that the antioxidant (prepared in Example 2) is replaced with a mixture of equal mass of N-phenyl-1,3-phenylenediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid in a mass ratio of 1:1.5.
[0061] Comparative Example 2
[0062] The raw material components and ratios of the anesthesia storage airbag are basically the same as those in Example 5, except that the antioxidant (prepared in Example 2) is replaced with an antioxidant prepared by the following steps in equal mass:
[0063] S1: Put 1000 ml of toluene, 2 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 1.4 mol of allyl glycerol ether, and 0.08 mol of p-toluenesulfonic acid into a reaction flask in sequence, stir, heat to 115 °C, react for 7 h (remove the generated water through a water separator during the reaction), cool to room temperature, distill under reduced pressure at 70 °C for 3 h to remove toluene, dissolve the residue in 500 ml of ethyl acetate, and wash with 120 mL of 5 wt% NaHCO 3 solution and 120 ml of saturated brine in sequence, and rotary evaporate at 60 °C for 2 h to obtain Intermediate 1;
[0064] S2: Put 1000 ml of DMF, 300 g of Intermediate 1, and 45 g of strong acid cation exchange resin into a reactor, stir, and heat to 80 °C; then mix 75 g of formic acid and 210 g of 30 wt% H 2 O 2 evenly, slowly drop it into the reaction flask, after dropping (dropwise addition for 30 min), react for 7 h, then cool to room temperature, distill under reduced pressure at 70 °C for 2.5 h, dissolve the residue in 500 ml of ethyl acetate, wash with deionized water (200 ml × 3 times), and distill under reduced pressure at 70 °C for 2 h to obtain Intermediate 2;
[0065] S3: Under nitrogen protection, put 1200 ml of tetrahydrofuran, 1 mol of Intermediate 2, 1.4 mol of N-phenyl-1,3-phenylenediamine, and 1.6 mol of triethylamine into a reaction flask in sequence, stir, heat to 70 °C and react for 10 h, cool to room temperature, wash with deionized water (200 ml × 3 times), distill under reduced pressure at 70 °C for 3 h to remove tetrahydrofuran, and dry at 70 °C for 10 h to obtain the antioxidant.
[0066] Comparative Example 3
[0067] The raw material components and their ratios of the anesthesia storage airbag are basically the same as those in Example 5, except that the antioxidant (prepared in Example 2) is replaced with an antioxidant prepared by the following steps in an equal mass:
[0068] S1: Put 1000 ml of toluene, 2 mol of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 1.4 mol of 3-(2-allylphenoxy) propane-1,2-diol, and 0.08 mol of p-toluenesulfonic acid into a reaction flask in sequence, stir, heat to 115 °C, react for 7 h (remove the generated water through a water separator during the reaction), cool to room temperature, and distill under reduced pressure at 70 °C for 3 h to remove toluene. The residue is dissolved in 500 ml of ethyl acetate, and washed successively with 120 mL of 5 wt% NaHCO 3 solution and 120 ml of saturated brine, and rotary evaporate at 60 °C for 2 h to obtain Intermediate 1;
[0069] S2: Put 1000 ml of DMF, 300 g of Intermediate 1, and 45 g of strong acid cation exchange resin into a reactor, stir, and heat to 80 °C; then mix 75 g of formic acid and 210 g of 30 wt% H 2 O 2 After mixing evenly, slowly drop it into the reaction flask. After dropping, react for 7 h, then cool to room temperature, distill under reduced pressure at 70 °C for 2.5 h, dissolve the residue in 500 ml of ethyl acetate, wash with deionized water (200 ml × 3 times), and distill under reduced pressure at 70 °C for 2 h to obtain Intermediate 2;
[0070] S3: Under nitrogen protection, put 1200 ml of tetrahydrofuran, 1 mol of Intermediate 2, 1.4 mol of N-phenyl-1,3-phenylenediamine, and 1.6 mol of triethylamine into a reaction flask in sequence, stir, heat to 70 °C and react for 10 h, cool to room temperature, wash with deionized water (200 ml × 3 times), distill under reduced pressure at 70 °C for 3 h to remove tetrahydrofuran, and dry at 70 °C for 10 h to obtain the antioxidant.
[0071] Comparative Example 4
[0072] The raw material components and their ratios of the anesthesia storage airbag are basically the same as those in Example 5, except that the antioxidant (prepared in Example 2) is replaced with a modified antioxidant prepared by the following steps in an equal mass:
[0073] Put 1000 ml of toluene, 2 mol of 3-(3,5-ditert-butyl-4-hydroxyphenyl)propionic acid, 1.4 mol of glycerol 1-ether-d5, and 0.08 mol of p-toluenesulfonic acid into a reaction flask in sequence, stir, heat to 115 °C, and react for 7 h (remove the generated water through a water separator during the reaction process), cool to room temperature, and distill under reduced pressure at 70 °C for 3 h to remove toluene. The residue is dissolved in 500 ml of ethyl acetate and washed successively with 120 mL of 5 wt% NaHCO 3 solution and 120 ml of saturated brine, and rotary evaporate at 60 °C for 2 h to obtain Intermediate 1.
[0074] Comparative Example 5
[0075] The raw material components and their ratios of the anesthesia storage airbag are basically the same as those in Example 5, except that the antioxidant (prepared in Example 2) is replaced with an equal mass of the modified antioxidant prepared in Example 2 of the Chinese invention patent with the publication number CN118165385A.
[0076] The anesthesia storage airbags of Examples 4-6 and Comparative Examples 1-5 are prepared by the following process:
[0077] S1: Stir and mix evenly polyisoprene latex, stabilizer, aqueous solution of sodium p-styrenesulfonate, nano-silica suspension, antioxidant, conductive graphite, and vulcanization package, keep stirring at 45 °C, pre-vulcanize for 1.5 h, and then stand still at room temperature for 48 h to obtain matured polyisoprene latex;
[0078] S2: Clean the mold and dry it at 80 °C for 5 minutes;
[0079] S3: Immerse in a coagulant (20 wt% aqueous solution of calcium nitrate), and dry the coagulant at 90 °C for 5 minutes;
[0080] S4: Immerse in the matured polyisoprene latex, and dry the latex at 80 °C for 5 minutes;
[0081] S5: Leach at 60 ± 5 °C and perform a curling process;
[0082] S6: Perform a drying and vulcanization treatment on the curled latex, and dry and vulcanize at 110 °C for 25 min;
[0083] S7: Demold, wash with 60 °C hot water, leach, and perform post-treatment to obtain the airbag.
[0084] Raw materials used in the embodiments and comparative examples of this application: The nano-silica suspension is of the SS-S10WJ type produced by Hangzhou Jikang New Materials Co., Ltd., with a silica particle size of 8-15 nm and a concentration of 30 wt%; the polyisoprene latex is the IR-550 polyisoprene latex produced by Puyang Lin's Chemical New Materials Co., Ltd., with a solid content of 50 wt%; the sulfur is the special sulfur powder of the S-80 type produced by Qingdao Luchuan Chemical Co., Ltd., mesh number: 400 mesh; the conductive graphite is the 1000-mesh graphite powder produced by Qingdao Dongkai Graphite Co., Ltd.
[0085] The anesthesia storage airbags of Examples 4-6 and Comparative Examples 1-5 of this application were subjected to performance tests in accordance with YY / T0978-2016 and ASTM D412-16 (2021), and resistance tests were carried out in accordance with the requirements of 39.3b in GB9706.1-2007. The test results are shown in Table 1.
[0086] Aging test: The anesthesia storage airbags of Examples 4-6 and Comparative Examples 1-5 of this application were placed in a hot air aging oven and aged at 100 °C for 5 days, and then relevant performance tests were carried out. The test results are shown in Table 1.
[0087] Migration resistance aging test: The anesthesia storage airbags of Examples 4-6 and Comparative Examples 1-5 of this application were placed in methanol and soaked statically at a constant temperature of 70 °C for 48 hours. After taking them out and drying the methanol, they were aged in a hot air aging oven at 100 °C for 5 days and then relevant performance tests were carried out. The test results are shown in Table 1.
[0088] Table 1 Test data table of the mechanical properties and resistance values of the storage airbag
[0089]
[0090] It can be seen from Examples 4, 5, and 6 in Table 1 that the anesthesia storage airbag of the present invention has excellent mechanical properties (tensile strength of the test piece, elongation at break of the test piece), antistatic properties (resistance value), and migration resistance properties (migration resistance aging experiment).
[0091] Comparative Example 1 is a comparative example different from Example 5. The difference is that a mixture of equal mass of N-phenyl-1,3-phenylenediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid in a mass ratio of 1:1.5 was used to prepare the storage airbag. It can be seen from the data in Table 1 that the tensile strength of the test piece after aging is 13.7 MPa, and the tensile strength of the test piece after migration resistance aging is 9.8 MPa. Its migration resistance aging ability is worse than that of Examples 4-6. The possible reason is that the molecular weights of N-phenyl-1,3-phenylenediamine and 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid are smaller, the diffusion resistance is lower, and the migration resistance performance is poor, resulting in the loss of antioxidant and poor anti-aging performance.
[0092] Comparative Example 2 and Comparative Example 3 are air bags for storage prepared by using allyl glycerol ether and 3-(2-allylphenoxy)propane-1,2-diol to replace glycerol 1-ether-d5 in the synthesis of antioxidants. From the data in Table 1, it can be seen that the tensile strengths of the test pieces after aging are 15.2 and 15.6 MPa respectively, and the elongation at break of the test pieces are 368% and 436% respectively. Their anti-migration and anti-aging capabilities are poorer than those of Examples 4-6. The reason may be that: the alkyl chains of allyl glycerol ether and 3-(2-allylphenoxy)propane-1,2-diol, compared with 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with a long-chain structure, have better compatibility with the rubber matrix, enabling the antioxidant to be evenly dispersed in the material, which can reduce problems such as excessive local concentration or precipitation; the alkyl chains can form steric hindrance through their volume effect to protect the active groups (such as phenolic hydroxyl or amine groups) in the antioxidant molecules from being attacked by free radicals and delay their own oxidation and failure.
[0093] Comparative Example 4 is an air bag for storage prepared by using Intermediate 1 of Example 2 as an antioxidant. From the data in Table 1, it can be seen that the tensile strength of the test piece of the air bag in Comparative Example 4 after aging is 14.3 MPa, and the elongation at break of the test piece is lower than 479%. Its anti-migration and anti-aging performance is significantly inferior to that of the anesthesia air bags in Examples 4-6. The main reason is the lack of the process of inhibiting chain reaction by the N-H structure in N-phenyl-1,3-phenylenediamine, resulting in poor anti-aging ability.
[0094] Comparative Example 5 is an air bag for storage prepared by using the modified antioxidant prepared in Example 2 of the Chinese invention patent with the publication number CN118165385A. From the data in Table 1, it can be seen that the tensile strength of the test piece of the air bag in Comparative Example 5 after anti-migration aging is 12.8 MPa, and its anti-migration aging performance is significantly inferior to that of the anesthesia air bags in Examples 4-6. The main reason may be the small molecular weight, resulting in poor anti-migration performance.
[0095] In summary, as can be seen from the data of the comparative examples and the examples in Table 1, the antistatic polyisoprene rubber anesthetic reservoir prepared by the present invention has good migration resistance, excellent tensile strength and elongation at break, and still maintains relatively good tensile strength and elongation at break after aging. The reason why the polyisoprene rubber anesthetic reservoir prepared by the present invention has excellent antioxidant and anti-aging effects is as follows: The antioxidant prepared by the present invention introduces 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and N-phenyl-1,3-phenylenediamine on glycerol 1-ether-d5, increasing the molecular weight of the antioxidant, improving the extraction resistance of the antioxidant, and reducing the loss of the antioxidant. Among them, the long-chain alkyl structure of glycerol 1-ether-d5 has good compatibility with the rubber, enabling the antioxidant to have good migration resistance; 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid provides a hindered phenol antioxidant with two hindered phenol units, and the substituents on both sides of the -OH on the benzene ring can form strong intermolecular forces with the molecules in the matrix material, which can effectively restrict the movement of the antioxidant molecules, thereby improving its migration resistance; the introduced N-phenyl-1,3-phenylenediamine functional group increases the conjugation effect of δ-π (N-benzene ring), the hydrogen of N-H falls off to form a free radical, and the fallen hydrogen will quickly react with the free radicals and peroxy free radicals on the polyisoprene carbon chain, making them lose their activity, achieving the process of inhibiting the chain reaction, and further improving its anti-aging ability.
[0096] The above is only the preferred embodiment of the present invention and is not used to limit the present invention; however, for those of ordinary skill in the art, without departing from the scope of the technical solution of the present invention, some equivalent changes such as slight modifications, evolutions made by using the technical content disclosed above are all equivalent embodiments of the present invention; at the same time, any equivalent changes, modifications and evolutions made to the above embodiments based on the essence of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims
1. An antistatic polyisoprene rubber anesthesia air storage bag, characterized in that: The invention comprises the following raw materials in parts by weight: Polyisoprene latex: 100 parts; Stabilizer: 0.5-2 parts; Sodium p-styrene sulfonate aqueous solution: 1-2 parts; Nano-silicon dioxide suspension dispersion: 3-6 parts; Anti-aging agent: 1-2 parts; Conductive graphite: 0.8-2 parts; Curing package: 3-6 parts; Wherein: the vulcanization package includes the following raw materials in parts by weight: sulfur: 5-10 parts; zinc oxide: 4-8 parts; accelerator: 5-10 parts; antioxidant 1010: 5-8 parts; peregal O-20: 3-6 parts; The antioxidant is firstly prepared by reacting 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and glycerol 1-oleyl ether-d5 to generate an esterification product, which is then epoxidized with hydrogen peroxide and formic acid and then reacted with N-phenyl-1,3-phenylenediamine.
2. The antistatic polyisoprene rubber anesthesia air storage bag according to claim 1, characterized in that: The antioxidant is prepared by the following method: S1: Toluene, 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 1-oleyl glycerol-d5, and p-toluenesulfonic acid are placed in a reaction bottle in sequence, stirred, heated to 110-120°C, reacted for 6-8h, removed the generated water during the reaction, cooled to room temperature, and post-treated to obtain intermediate 1; S2: DMF, intermediate 1 and strong acid cation exchange resin are added into the reactor, stirred and heated to 60-80°C; then formic acid and 30wt% H2O2 are mixed evenly and slowly dripped into the reaction bottle, and the reaction is continued for 6-8h, and intermediate 2 is obtained after post-treatment; S3: Under nitrogen protection, tetrahydrofuran, intermediate 2, N-phenyl-1,3-phenylenediamine and triethylamine were placed in a reaction bottle in sequence, stirred, and the temperature was raised to 70-75°C for reaction for 9-10 hours, then cooled to room temperature, and post-treated to obtain an antioxidant.
3. The antistatic polyisoprene rubber anesthesia air storage bag according to claim 2, characterized in that: In step S1, the molar ratio of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 1-oleyl glycerol-d5, and p-toluenesulfonic acid is 2:(1.1-1.5):(0.05-0.1).
4. The antistatic polyisoprene rubber anesthesia air storage bag according to claim 2, characterized in that: In step S2, the feed mass ratio of intermediate 1, strong acid cation exchange resin, formic acid and 30wt% H2O2 is 10:(0.5-2):(1.5-3):(6-8).
5. The antistatic polyisoprene rubber anesthesia air storage bag according to claim 2, characterized in that: In step S3, the molar ratio of the intermediate 2, N-phenyl-1,3-phenylenediamine and triethylamine is 1:(1.2-1.5):(1-2).
6. The antistatic polyisoprene rubber anesthesia air storage bag according to claim 1, characterized in that: The stabilizer is a 10-25wt% potassium hydroxide aqueous solution.
7. The antistatic polyisoprene rubber anesthesia air storage bag according to claim 1, characterized in that: The accelerator is one of accelerator TMTD and accelerator BZ.
8. The antistatic polyisoprene rubber anesthesia air storage bag according to claim 1, characterized in that: The mass concentration of the sodium p-styrene sulfonate aqueous solution is 25-30wt%.
9. The antistatic polyisoprene rubber anesthesia air storage bag according to claim 1, characterized in that: The sulfur, zinc oxide, accelerator, antioxidant 1010 and conductive graphite are all in the form of a water dispersion with a total solid content of 50 wt %. The water dispersion is ground with a nano-abrasive machine until the dispersion D90 is no more than 3 microns, and 0.4-0.8 wt % of disodium methylene dinaphthalene sulfonate is added to the ground water dispersion as a surfactant.
Citation Information
Patent Citations
Composite rubber anti-aging agent and preparation process thereof
CN113620988A
Polyisoprene rubber anesthesia air storage bag
CN118165385A