Medical acrylic adhesive as well as preparation method and application thereof
By using anionic reactive emulsifiers and initiators in medical acrylic adhesives for emulsion polymerization, and by combining the anionic reactive emulsifiers of sulfate ammonium salts and sodium sulfonic acid salts, the existing acrylic adhesives have been solved, and a safer and more durable medical adhesives have been achieved.
Patent Information
- Application Number
- CN202510231876.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-28
- Publication Date
- 2025-05-13
AI Technical Summary
Existing acrylic adhesives have high cytotoxicity and poor friction color fastness performance, which cannot meet the requirements of medical adhesives.
The emulsion polymerization reaction is carried out under the combined action of anionic reactive emulsifier and initiator, and the medical acrylic binder is prepared by adjusting the system pH. The specific methods include pre-emulsification, heating mixing and dropwise addition, and compounding using anionic reactive emulsifier of sulfate ammonium salts and sodium sulfonate salts.
It reduces the toxicity of the adhesive to cells, improves the friction color fastness of the adhesive, meets the use requirements of medical acrylic adhesives, and reduces the total amount of emulsifiers and reduces manufacturing costs.
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Figure CN119979067A_ABST
Abstract
Description
Technical Field
[0001] The present application belongs to the technical field of adhesive synthesis, and more specifically, relates to a medical acrylic adhesive, a preparation method and application thereof. Background Art
[0002] As a kind of non-woven fabric, non-woven fabric is rich in colors and has a wide range of applications in many fields such as medical treatment, health, and industry. In order to improve the strength and durability of non-woven fabrics, adhesives are usually used to bond them together. Traditional adhesives are usually prepared from acrylic monomers, initiators, and emulsifier compositions. In order to ensure that the adhesive has excellent emulsion reaction stability and emulsification effect, non-reactive anionic emulsifiers, non-ionic emulsifiers, and other types of emulsifiers are usually selected for compounding. However, the prepared adhesive has a greater effect on cell activity and does not meet the requirements of medical adhesives. In addition, the above-mentioned adhesive has poor color fastness to friction. During use, the color of the non-woven surface will fall off due to friction, or be transferred to the surface of other objects, resulting in color contamination, which not only affects the appearance of the non-woven fabric, but may also contaminate the contacted objects.
[0003] Therefore, it is necessary to provide a medical acrylic adhesive which has good color fastness to rubbing and has a weaker effect on cell activity. Summary of the invention
[0004] In view of the defects of the prior art, the purpose of this application is to provide a medical acrylic adhesive, a preparation method and application thereof, aiming to solve the problems that the existing acrylic adhesives are highly toxic to cells, have poor abrasion resistance and color fastness, and do not meet the requirements of medical adhesives.
[0005] To achieve the above-mentioned purpose, in the first aspect, the present application provides a medical acrylic adhesive, which is prepared by using an acrylic monomer mixture as a raw material, conducting an emulsion polymerization reaction under the joint action of an anionic reactive emulsifier and an initiator, and then adjusting the system pH; The anionic reactive emulsifier includes an anionic reactive emulsifier of ammonium sulfate salt type, and the amount of the anionic reactive emulsifier is 1wt% to 3wt% of the total weight of the acrylic monomer mixture.
[0006] Further preferably, the above-mentioned ammonium sulfate anionic reactive emulsifier includes one or more of fatty alcohol ammonium sulfate anionic reactive emulsifiers, fatty alcohol polyoxyethylene ether sulfate anionic reactive emulsifiers, and allyloxy alcohol ether sulfate anionic reactive emulsifiers.
[0007] Preferably, the above-mentioned anionic reactive emulsifier also includes a sodium sulfonate anionic reactive emulsifier.
[0008] More preferably, the above-mentioned sodium sulfonate anionic reactive emulsifier includes one or more of allyl sulfonate sodium salt anionic reactive emulsifier and allyloxy sulfonate sodium salt anionic reactive emulsifier.
[0009] Preferably, the acrylic monomer mixture comprises soft monomers, hard monomers and functional monomers.
[0010] Preferably, the soft monomer includes one or more of methyl acrylate, ethyl acrylate, butyl acrylate, and isooctyl acrylate.
[0011] Preferably, the hard monomer includes one or more of acrylonitrile, styrene and methyl methacrylate.
[0012] Preferably, the functional monomers include one or more of acrylic acid, acrylamide, and hydroxyethyl acrylate.
[0013] Preferably, the weight ratio of the soft monomer, the hard monomer and the functional monomer is (300-350):(50-70):(10-15).
[0014] Preferably, the initiator is one or more of ammonium persulfate, potassium persulfate, and sodium bisulfite.
[0015] Preferably, the amount of the initiator is 0.3 wt% to 0.8 wt% of the total weight of the acrylic monomer mixture.
[0016] In a second aspect, the present application provides a method for preparing the above-mentioned medical acrylic adhesive, comprising the following steps: S1, mixing the acrylic monomer mixture, part of the anionic reactive emulsifier and part of deionized water for pre-emulsification to obtain a pre-emulsion; S2. Mix part of the above pre-emulsion, part of the initiator and the remaining anionic reactive emulsifier, heat it to a set temperature, and then simultaneously drop the remaining pre-emulsion and the remaining initiator to carry out a polymerization reaction. After cooling, add an acid-base regulator to obtain a medical acrylic adhesive.
[0017] Preferably, in step S1, the mixing speed is 2500 rpm to 3000 rpm, and the mixing time is 20 to 40 min.
[0018] Preferably, step S2 comprises the following steps: Mix part of the above-mentioned pre-emulsion, part of the initiator and the remaining anionic reactive emulsifier at 70°C~75°C, then heat it to 80°C~82°C, and simultaneously drop the remaining pre-emulsion and the remaining initiator to carry out polymerization reaction, and keep the temperature for 1h~2h. After cooling to below 45°C, add an acid-base regulator to adjust the pH of the system to 7~8 to obtain a medical acrylic adhesive.
[0019] Preferably, the above-mentioned partial pre-emulsion is 5% to 15% of the total weight of the above-mentioned pre-emulsion.
[0020] Preferably, the above-mentioned partial initiator is 20% to 30% of the total weight of the above-mentioned initiator.
[0021] In a third aspect, the present application provides a medical nonwoven fabric comprising the above-mentioned medical acrylic adhesive.
[0022] In general, the above technical solutions conceived by this application have the following technical advantages compared with the prior art: (1) The medical acrylic adhesive provided in the present application, without adding a non-reactive anionic emulsifier or a non-ionic emulsifier, is prepared by polymerizing a single type (ammonium sulfate salt) of anionic reactive emulsifier and an acrylic monomer mixture, an initiator and other components, and regulating the amount of the anionic reactive emulsifier. Compared with the acrylic adhesive prepared by using a non-reactive anionic emulsifier or a non-ionic emulsifier, the medical acrylic adhesive can reduce the toxicity of the adhesive to cells, improve the friction color fastness of the adhesive system, and meet the use requirements of the medical acrylic adhesive.
[0023] (2) The medical acrylic adhesive prepared by adding an emulsifier composed of an anionic reactive emulsifier of ammonium sulfate salt and an anionic reactive emulsifier of sodium sulfonate salt in the present application can reduce the toxicity of the medical acrylic adhesive to cells and improve the emulsification performance of the medical acrylic adhesive.
[0024] (3) Compared with the use of a single type of anionic reactive emulsifier, the medical acrylic adhesive prepared by adding an emulsifier compounded with an anionic reactive emulsifier of ammonium sulfate salt and an anionic reactive emulsifier of sodium sulfonate salt can ensure that the medical acrylic adhesive has better emulsification performance while reducing the total amount of emulsifier, and can further reduce the toxicity of the adhesive to cells. In actual production, it will greatly reduce the manufacturing cost of the adhesive. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] Figure 1 It is a schematic flow chart of the preparation method of the medical acrylic adhesive provided by the present application; Figure 2It is a comparison chart of the test results of the color fastness to rubbing of the medical acrylic adhesives prepared in Example 2, Example 5, Comparative Example 1 and Comparative Example 2 of the present application. DETAILED DESCRIPTION
[0026] In order to make the purpose, technical solution and advantages of the present application more clearly understood, the present application is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.
[0027] In the description of this application, it should be understood that the term "and / or" is a description of the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. The symbol " / " herein indicates that the associated objects are in an or relationship, for example, A / B means A or B.
[0028] In the description of the embodiments of the present application, words such as "exemplary" or "for example" are used to indicate examples, illustrations or descriptions. Any embodiment or design described as "exemplary" or "for example" in the embodiments of the present application should not be interpreted as being more preferred or more advantageous than other embodiments or designs. Specifically, the use of words such as "exemplary" or "for example" is intended to present related concepts in a specific way.
[0029] In the description of the embodiments of the present application, unless otherwise specified, “plurality” means two or more than two.
[0030] The present application provides a medical acrylic adhesive, which is prepared by using an acrylic monomer mixture as a raw material, carrying out an emulsion polymerization reaction under the joint action of an anionic reactive emulsifier and an initiator, and then adjusting the system pH; The anionic reactive emulsifier includes an anionic reactive emulsifier of ammonium sulfate salt type, and the amount of the anionic reactive emulsifier is 1wt% to 3wt% of the total weight of the acrylic monomer mixture.
[0031] In a preferred embodiment, the above-mentioned ammonium sulfate anionic reactive emulsifier includes one or more of fatty alcohol ammonium sulfate anionic reactive emulsifiers, fatty alcohol polyoxyethylene ether sulfate anionic reactive emulsifiers, and allyloxy alcohol ether sulfate anionic reactive emulsifiers.
[0032] In some embodiments, the anionic reactive emulsifier further comprises a sodium sulfonate anionic reactive emulsifier.
[0033] In a preferred embodiment, the above-mentioned sodium sulfonate anionic reactive emulsifier includes one or more of allyl sulfonate sodium salt anionic reactive emulsifier and allyloxy sulfonate sodium salt anionic reactive emulsifier.
[0034] In some embodiments, the weight percentage of the ammonium sulfate anionic reactive emulsifier in the anionic reactive emulsifier is 50% to 100%.
[0035] In some embodiments, the acrylic monomer mixture includes a soft monomer, a hard monomer and a functional monomer.
[0036] In some embodiments, the soft monomer includes one or more of methyl acrylate, ethyl acrylate, butyl acrylate, and isooctyl acrylate.
[0037] In some embodiments, the hard monomer includes one or more of acrylonitrile, styrene, and methyl methacrylate.
[0038] In some embodiments, the functional monomers include one or more of acrylic acid, acrylamide, and hydroxyethyl acrylate.
[0039] In some embodiments, the weight ratio of the soft monomer, the hard monomer and the functional monomer is (300-350):(50-70):(10-15).
[0040] In some embodiments, the initiator is one or more of ammonium persulfate, potassium persulfate, and sodium bisulfite.
[0041] In some embodiments, the amount of the initiator is 0.3 wt % to 0.8 wt % of the total weight of the acrylic monomer mixture.
[0042] It is understandable that the emulsion polymerization reaction is carried out in a deionized water environment, wherein the weight percentage of deionized water in the medical acrylic adhesive is 50wt%-70wt%.
[0043] In some embodiments, an acid-base regulator is used to adjust the pH of the system, wherein the acid-base regulator can be one or more of ammonia water, sodium bicarbonate, liquid caustic soda, disodium bicarbonate, or an organic amine acid-base regulator, such as but not limited to diethanolamine, triethanolamine, 2-amino-2-methyl-1-propanol, etc.
[0044] In some embodiments, the amount of the acid-base regulator is 1 wt % to 2 wt % of the total weight of the acrylic acid monomer mixture.
[0045] On the other hand, Figure 1 As shown, the present application provides a method for preparing the above-mentioned medical acrylic adhesive, comprising the following steps: S1, pre-emulsifying the acrylic monomer mixture, part of the anionic reactive emulsifier, and part of the deionized water to obtain a pre-emulsified liquid; S2. Mix part of the pre-emulsion, part of the initiator and the remaining anionic reactive emulsifier, heat to a set temperature, and then simultaneously add the remaining pre-emulsion and the remaining initiator to carry out emulsion polymerization reaction. After cooling, add an acid-base regulator to obtain a medical acrylic adhesive.
[0046] In some embodiments, in step S1, the mixing speed is 2500 rpm to 3000 rpm, and the mixing time is 20 min to 40 min.
[0047] In some embodiments, step S2 includes the following steps: Part of the above pre-emulsion, part of the initiator and the remaining emulsifier are mixed at 70°C~75°C, then the temperature is raised to 80°C~82°C, and the remaining pre-emulsion and the remaining initiator are added simultaneously to carry out polymerization reaction, and the temperature is kept for 1h~2h. After the temperature is lowered to below 45°C, an acid-base regulator is added to adjust the pH of the system to 7~8 to obtain a medical acrylic adhesive.
[0048] In some embodiments, in order to make the polymerization reaction more gentle and fully reacted, the above-mentioned initiator can be first dissolved in deionized water to prepare an initiator aqueous solution, and then part of the initiator aqueous solution is mixed with part of the above-mentioned pre-emulsion and the remaining emulsifier. In some embodiments, the weight percentage of the initiator in the above-mentioned initiator aqueous solution is 1% to 3%.
[0049] In some embodiments, in step S2, the partial pre-emulsion is 5% to 15% of the total weight of the pre-emulsion.
[0050] In some embodiments, in step S2, the partial initiator is 20% to 30% of the total weight of the initiator.
[0051] In some embodiments, in S2, the remaining pre-emulsion and the remaining initiator are added dropwise for 2 to 5 hours. It is understood that those skilled in the art can appropriately extend or shorten the time of the addition according to the dosage of each component in the medical acrylic acid system, which is within the scope of protection of the present application.
[0052] On the other hand, the present application also provides a medical non-woven fabric, which includes the above-mentioned medical acrylic adhesive.
[0053] It should be understood that materials of the same or similar type, model, quality, nature or function as the reagents and instruments used in the following examples can be used to implement the present application. The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.
[0054] The following are examples and comparative examples: Example 1 The medical acrylic adhesive provided in this embodiment is prepared from the following components in parts by weight: 320 parts of soft monomer (including 20 parts of ethyl acrylate and 300 parts of butyl acrylate), 60 parts of hard monomer (including 25 parts of acrylonitrile and 35 parts of styrene), 12 parts of functional monomer (including 10 parts of acrylic acid and 2 parts of acrylamide), 4 parts of anionic reactive emulsifier (4 parts of allyloxy alcohol ether sulfate ammonium salt anionic reactive emulsifier, Japan Aidico SR-10), 2 parts of initiator ammonium persulfate, 5 parts of acid-base regulator ammonia water and 596 parts of deionized water.
[0055] The preparation method of the medical acrylic adhesive provided in this embodiment comprises the following steps: 1) The above-mentioned soft monomer, hard monomer, functional monomer, 3 parts of anionic reactive emulsifier and 200 parts of deionized water are mixed and placed in an emulsification tank for dispersion and emulsification to obtain a pre-emulsion.
[0056] 2) Take 10wt% of the pre-emulsion as the seed emulsion and seal it for later use.
[0057] 3) Mix the above initiator with 96 parts of deionized water to prepare an initiator aqueous solution.
[0058] 4) Mix 1 part of anionic reactive emulsifier and 300 parts of deionized water in a four-necked flask, heat to 75°C in a water bath, add the above seed emulsion and 20 wt% aqueous initiator solution, continue to heat to 80°C, drop the remaining pre-emulsion and the remaining aqueous initiator solution, the dropping time is 3 hours, and after all the dropping is completed, keep warm for 1 hour to obtain a reaction solution.
[0059] 5) After the reaction solution is cooled to 45° C., the acid-base regulator is added to adjust the pH to 7.5, and the material is filtered to obtain a medical acrylic adhesive.
[0060] Example 2 The medical acrylic adhesive provided in this embodiment is prepared from the following components in parts by weight: 320 parts of soft monomer (including 20 parts of ethyl acrylate and 300 parts of butyl acrylate), 60 parts of hard monomer (including 25 parts of acrylonitrile and 35 parts of styrene), 12 parts of functional monomer (including 10 parts of acrylic acid and 2 parts of acrylamide), 10 parts of anionic reactive emulsifier (10 parts of allyloxy alcohol ether sulfate ammonium salt anionic reactive emulsifier, Japan Aidico SR-10), 2 parts of initiator ammonium persulfate, 5 parts of acid-base regulator ammonia water and 596 parts of deionized water.
[0061] The preparation method of the medical acrylic adhesive provided in this embodiment comprises the following steps: 1) The above-mentioned soft monomer, hard monomer, functional monomer, 8 parts of anionic reactive emulsifier and 200 parts of deionized water are mixed and placed in an emulsification tank for dispersion and emulsification to obtain a pre-emulsion.
[0062] 2) Take 10wt% of the pre-emulsion as the seed emulsion and seal it for later use.
[0063] 3) Mix the above initiator with 96 parts of deionized water to prepare an initiator aqueous solution.
[0064] 4) Mix 2 parts of anionic reactive emulsifier and 300 parts of deionized water in a four-necked flask, heat to 75°C in a water bath, add the above seed emulsion and 20 wt% aqueous initiator solution, continue to heat to 80°C, drop the remaining pre-emulsion and the remaining aqueous initiator solution, the dropping time is 3 hours, and after all the dropping is completed, keep warm for 1 hour to obtain a reaction solution.
[0065] 5) After the reaction solution is cooled to 45° C., the acid-base regulator is added to adjust the pH to 7.5, and the material is filtered to obtain a medical acrylic adhesive.
[0066] Example 3 The medical acrylic adhesive provided in this embodiment is prepared from the following components in parts by weight: 320 parts of soft monomer (including 20 parts of ethyl acrylate and 300 parts of butyl acrylate), 60 parts of hard monomer (including 25 parts of acrylonitrile and 35 parts of styrene), 12 parts of functional monomer (including 10 parts of acrylic acid and 2 parts of acrylamide), 15 parts of anionic reactive emulsifier (15 parts of allyloxy alcohol ether sulfate ammonium salt anionic reactive emulsifier, Japan Aidico SR-10), 2 parts of initiator ammonium persulfate, 5 parts of acid-base regulator ammonia water and 596 parts of deionized water.
[0067] The preparation method of the medical acrylic adhesive provided in this embodiment comprises the following steps: 1) The above-mentioned soft monomer, hard monomer, functional monomer, 12 parts of anionic reactive emulsifier and 200 parts of deionized water are mixed and placed in an emulsification tank for dispersion and emulsification to obtain a pre-emulsion.
[0068] 2) Take 10wt% of the pre-emulsion as the seed emulsion and seal it for later use.
[0069] 3) Mix the above initiator with 96 parts of deionized water to prepare an initiator aqueous solution.
[0070] 4) Mix 3 parts of anionic reactive emulsifier and 300 parts of deionized water in a four-necked flask, heat to 75°C in a water bath, add the above seed emulsion and 20 wt% aqueous initiator solution, continue to heat to 80°C, drop the remaining pre-emulsion and the remaining aqueous initiator solution, the dropping time is 3 hours, and after all the dropping is completed, keep warm for 1 hour to obtain a reaction solution.
[0071] 5) After the reaction solution is cooled to 45° C., the acid-base regulator is added to adjust the pH to 7.5, and the material is filtered to obtain a medical acrylic adhesive.
[0072] Example 4 The medical acrylic adhesive provided in this embodiment is prepared from the following components in parts by weight: 320 parts of soft monomer (including 20 parts of ethyl acrylate and 300 parts of butyl acrylate), 60 parts of hard monomer (including 25 parts of acrylonitrile and 35 parts of styrene), 12 parts of functional monomer (including 10 parts of acrylic acid and 2 parts of acrylamide), 10 parts of anionic reactive emulsifier (10 parts of sodium allyloxysulfonic acid salt anionic reactive emulsifier, Sowell COPS-1), 2 parts of initiator ammonium persulfate, 5 parts of acid-base regulator ammonia water and 596 parts of deionized water.
[0073] The preparation method of the medical acrylic adhesive provided in this embodiment is the same as that in Example 2. A large amount of residue appears when filtering out the material, indicating that the emulsification performance of the medical acrylic adhesive is poor.
[0074] Example 5 The medical acrylic adhesive provided in this embodiment is prepared from the following components in parts by weight: 320 parts of soft monomer (including 20 parts of ethyl acrylate and 300 parts of butyl acrylate), 60 parts of hard monomer (including 25 parts of acrylonitrile and 35 parts of styrene), 12 parts of functional monomer (including 10 parts of acrylic acid and 2 parts of acrylamide), 10 parts of anionic reactive emulsifier (8 parts of allyloxy alcohol ether sulfate ammonium salt anionic reactive emulsifier Japan IDICO SR-10, 2 parts of allyloxy sulfonic acid sodium salt anionic reactive emulsifier Sowell COPS-1), 2 parts of initiator ammonium persulfate, 5 parts of acid-base regulator ammonia water and 596 parts of deionized water.
[0075] The preparation method of the medical acrylic adhesive provided in this embodiment is the same as that in Example 2.
[0076] Example 6 The medical acrylic adhesive provided in this embodiment is prepared from the following components in parts by weight: 320 parts of soft monomer (including 20 parts of ethyl acrylate and 300 parts of butyl acrylate), 60 parts of hard monomer (including 25 parts of acrylonitrile and 35 parts of styrene), 12 parts of functional monomer (including 10 parts of acrylic acid and 2 parts of acrylamide), 4 parts of anionic reactive emulsifier (3 parts of allyloxy alcohol ether sulfate ammonium salt anionic reactive emulsifier Japan IDICO SR-10, 1 part of allyloxy sulfonic acid sodium salt anionic reactive emulsifier Sowell COPS-1), 2 parts of initiator ammonium persulfate, 5 parts of acid-base regulator ammonia water and 596 parts of deionized water.
[0077] The preparation method of the medical acrylic adhesive provided in this embodiment is the same as that in Example 1.
[0078] Example 7 The medical acrylic adhesive provided in this embodiment is prepared from the following components in parts by weight: 320 parts of soft monomer (including 20 parts of ethyl acrylate and 300 parts of butyl acrylate), 60 parts of hard monomer (including 25 parts of acrylonitrile and 35 parts of styrene), 12 parts of functional monomer (including 10 parts of acrylic acid and 2 parts of acrylamide), 4 parts of anionic reactive emulsifier (3 parts of allyloxy alcohol ether sulfate ammonium salt anionic reactive emulsifier Japan Aidico SR-10, 1 part of sodium carboxylate anionic reactive emulsifier Greenson IAEC-1307Na), 2 parts of initiator ammonium persulfate, 5 parts of acid-base regulator ammonia water and 596 parts of deionized water.
[0079] The preparation method of the medical acrylic adhesive provided in this embodiment is the same as that in Example 1. A large amount of residue appears when filtering out the material, and the emulsification effect is poor, which does not meet the use requirements.
[0080] Comparative Example 1 In the medical acrylic adhesive provided in this comparative example, the emulsifier is a non-reactive anionic emulsifier sodium dodecyl sulfate, and the rest is the same as in Example 1.
[0081] Comparative Example 2 In the medical acrylic adhesive provided in this comparative example, the emulsifier is nonionic emulsifier O-25 Pingjia, and the rest is the same as in Example 1.
[0082] Comparative Example 3 In the medical acrylic adhesive provided in this comparative example, the amount of the allyloxy alcohol ether sulfate ammonium salt anionic reactive emulsifier (Japan Aidico SR-10) is 2 parts, and the rest is the same as in Example 1.
[0083] The preparation method of the medical acrylic adhesive provided in this comparative example is the same as that in Example 1. During the preparation process, it was found that the pre-emulsion was stratified. This may be because the amount of anionic reactive emulsifier used was too low, resulting in poor emulsion reaction stability and emulsification effect.
[0084] The properties of the acrylic adhesives prepared in the examples and comparative examples were tested using the following test methods: 1) Emulsification performance: The prepared pre-emulsion was allowed to stand in the flask for 1 hour and observed to see whether stratification occurred, so as to evaluate the emulsification performance of the pre-emulsion.
[0085] In the later stage of the preparation process, an acid-base regulator is added to adjust the pH of the system and then the material is filtered out to observe whether there is residue, so as to preliminarily evaluate the emulsification effect of the acrylic adhesive system.
[0086] A particle size analyzer was used to measure the particle size and distribution of dispersed particles in the medical acrylic adhesive sample to evaluate the emulsification performance, and the particle size was limited to 100nm~250nm to meet the use requirements.
[0087] 2) Cytotoxicity: Tested in accordance with standard ISO 10993-5:2009.
[0088] 3) Color fastness to rubbing: Different medical acrylic adhesives were used to carry out sizing tests on the test cloths, and blue color paste was added to obtain blue cloth samples treated with different adhesives.
[0089] Dry rubbing color fastness: Refer to standard ISO105-X12 to test the dry rubbing color fastness of fabric samples and assess the color fastness grade. The dry rubbing color fastness grade is divided into 1 to 5 levels. The larger the value, the better the dry rubbing color fastness.
[0090] Wet rubbing color fastness: The reference standard GBT3920-2008 tests the dry rubbing color fastness of fabric samples. It means that under certain humidity conditions, the wet rubbing color fastness level is divided into 1 to 5 levels. The larger the value, the better the wet rubbing color fastness.
[0091] The test results are shown in Table 1.
[0092] Table 1 Color fastness to rubbing and cytotoxicity of acrylic adhesives prepared in Examples and Comparative Examples
[0093] Figure 1This is a comparison chart of the test results of the color fastness to rubbing of the medical acrylic adhesives prepared in Example 2, Example 5, Comparative Example 1, and Comparative Example 2. It can be seen that the fabrics treated with the medical acrylic adhesives prepared in Example 2 and Example 5 have weaker staining after dry friction / wet friction treatment, and have excellent color fastness to rubbing. In practical applications, the durability of non-woven fabrics can be improved.
[0094] By comparing the examples and comparative examples 1-2, it can be seen that the acrylic adhesive prepared by using a non-reactive anionic emulsifier (ie, comparative example 1) or a nonionic emulsifier (comparative example 2) is highly toxic to cells and does not meet the requirements of medical adhesives.
[0095] Examples 1 to 3 are medical acrylic adhesives to which a single type (ammonium sulfate salt) anionic reactive emulsifier is added, Example 4 is a medical acrylic adhesive to which a single type (sodium sulfonate salt) anionic reactive emulsifier is added, and Examples 5 to 7 are medical acrylic adhesives to which two types of anionic reactive emulsifiers are added. Compared with Comparative Examples 1 to 2, the addition of ammonium sulfate salt anionic reactive emulsifiers in Examples 1 to 2 can reduce the toxicity of medical acrylic adhesives to cells, and at the same time, the emulsification effect of the adhesive system is better and the stability is good. In Example 3, the amount of ammonium sulfate salt anionic reactive emulsifier is increased, so that the stability of the adhesive is improved, but the cytotoxicity is increased, which does not meet the requirements. The reason for the analysis may be that the amount of anionic reactive emulsifier is too high, resulting in part of the emulsifier not participating in the reaction and remaining in the adhesive system in a free form, thereby increasing the toxicity of the adhesive to cells.
[0096] Compared with Examples 2 and 4, when the total amount of anionic reactive emulsifiers used is the same, the medical acrylic adhesive in Example 5, in which two types (ammonium sulfate salts + sodium sulfonate salts) of anionic reactive emulsifiers are added, has significantly better emulsification performance and cell survival rate than Examples 2 and 4, and even better than the sum of the technical effects of Examples 2 and 4. This indicates that the ammonium sulfate salt and the sodium sulfonate salt anionic reactive emulsifiers have a synergistic effect after compounding, which can reduce the toxicity of the adhesive to cells and improve the emulsification performance of the adhesive.
[0097] Compared with Example 2, in Example 6 and Example 7, when the total amount of anionic reactive emulsifier is reduced, the medical acrylic adhesive compounded with two types (ammonium sulfate salts + sodium sulfonate salts) of anionic reactive emulsifiers in Example 6 has a significantly higher cell survival rate than that in Example 2, and its emulsification performance is slightly lower than that in Example 2, but still at a relatively good level. This shows that the medical acrylic adhesive compounded with ammonium sulfate salts and sodium sulfonate salts of anionic reactive emulsifiers in Example 6 can ensure that the adhesive has a relatively good emulsification performance while reducing the total amount of emulsifiers, and can further reduce the toxicity of the adhesive to cells. In actual production, the manufacturing cost of the adhesive will be greatly reduced. However, in Example 7, the medical acrylic emulsifier compounded with two types (ammonium sulfate salts + sodium carboxylate salts) of anionic reactive emulsifiers has poor emulsification performance and does not meet the use requirements. Therefore, its cytotoxicity and rubbing color fastness were not tested, and " / " was used to indicate it.
[0098] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application shall be included in the scope of protection of the present application.
Claims
1. A medical acrylic adhesive, characterized in that: The medical acrylic adhesive is prepared by using an acrylic monomer mixture as a raw material, carrying out an emulsion polymerization reaction under the joint action of an anionic reactive emulsifier and an initiator, and then adjusting the pH of the system; The anionic reactive emulsifier includes an anionic reactive emulsifier of ammonium sulfate salt type, and the amount of the anionic reactive emulsifier used is 1wt% to 3wt% of the total weight of the acrylic monomer mixture.
2. The medical acrylic adhesive according to claim 1, characterized in that: The anionic reactive emulsifier also includes sodium sulfonate anionic reactive emulsifiers.
3. The medical acrylic adhesive according to claim 1 or 2, characterized in that: The ammonium sulfate anionic reactive emulsifier includes one or more of an ammonium sulfate anionic reactive emulsifiers of fatty alcohol, an ammonium sulfate anionic reactive emulsifiers of fatty alcohol polyoxyethylene ether, and an ammonium sulfate anionic reactive emulsifiers of allyloxy alcohol ether; The sodium sulfonate salt anionic reactive emulsifier includes one or more of an allyl sulfonate sodium salt anionic reactive emulsifier and an allyloxy sulfonate sodium salt anionic reactive emulsifier.
4. The medical acrylic adhesive according to claim 1, characterized in that: The acrylic monomer mixture includes soft monomers, hard monomers and functional monomers; Wherein, the soft monomer includes one or more of methyl acrylate, ethyl acrylate, butyl acrylate, and isooctyl acrylate; The hard monomer includes one or more of acrylonitrile, styrene, and methyl methacrylate; The functional monomers include one or more of acrylic acid, acrylamide, and hydroxyethyl acrylate.
5. The medical acrylic adhesive according to claim 1, characterized in that: The initiator is one or more of ammonium persulfate, potassium persulfate, and sodium bisulfite; Preferably, the amount of the initiator used is 0.3 wt% to 0.8 wt% of the total weight of the acrylic monomer mixture.
6. A method for preparing the medical acrylic adhesive according to any one of claims 1 to 5, characterized in that: The steps include: S1, mixing the acrylic monomer mixture, part of the anionic reactive emulsifier, and part of deionized water for pre-emulsification to obtain a pre-emulsion; S2, mixing part of the pre-emulsion, part of the initiator and the remaining anionic reactive emulsifier, heating to a set temperature, and simultaneously dropping the remaining pre-emulsion and the remaining initiator to carry out a polymerization reaction, and adding an acid-base regulator after cooling to obtain a medical acrylic adhesive.
7. The preparation method according to claim 6, characterized in that: In step S1, the mixing speed is 2500 rpm to 3000 rpm, and the mixing time is 20 to 40 minutes.
8. The preparation method according to claim 6, characterized in that: Step S2 includes the following steps: Part of the pre-emulsion, part of the initiator and the remaining anionic reactive emulsifier are mixed at 70°C~75°C, then the temperature is raised to 80°C~82°C, the remaining pre-emulsion and the remaining initiator are simultaneously added dropwise to carry out a polymerization reaction, and the temperature is kept for 1h~2h. After the temperature is lowered to below 45°C, an acid-base regulator is added to adjust the pH of the system to 7~8 to obtain a medical acrylic adhesive.
9. The preparation method according to claim 8, characterized in that: The partial pre-emulsion is 5% to 15% of the total weight of the pre-emulsion; The partial initiator is 20% to 30% of the total weight of the initiator.
10. A medical nonwoven fabric, characterized in that: It comprises the medical acrylic adhesive according to any one of claims 1 to 5.