A raw rubber masterbatch, a fungicide adhesive and its preparation method

Abstract

This invention relates to the field of antimicrobial materials technology, and discloses a raw rubber masterbatch, an antimicrobial adhesive, and their preparation methods. The raw rubber masterbatch of this invention is prepared by combining polyether, porous inorganic nanoparticles, and raw rubber. The prepared raw rubber masterbatch exhibits good stability, does not show solid-liquid separation even after long-term storage, and has good uniformity, making it easier to transport and store, and more conducive to commercial production and application. The antimicrobial adhesive of this invention is prepared in two stages. A semi-stable mixture formed by mixing liquid polyether additives and porous inorganic nanoparticles is gradually incorporated into already-refined raw rubber through a mixing process to obtain the raw rubber masterbatch. The raw rubber masterbatch is then mixed with a base polymer and cured to obtain the antimicrobial adhesive. The antimicrobial adhesive of this invention, prepared using the above method, exhibits good stability and uniformity, and demonstrates excellent application performance.

Description

Technical Field

[0001] This invention relates to the field of antimicrobial materials technology, specifically to a raw rubber masterbatch, an antimicrobial adhesive, and a method for preparing the same. Background Technology

[0002] Antibacterial adhesives can be used to manufacture plastic products with antibacterial properties, including medical plastic products, plastic packaging products, and containers, achieving good antibacterial effects. Antibacterial adhesives use rubber and other basic polymers as a carrier, with functional additives added to enhance their chemical properties.

[0003] However, adding non-solid compounds, especially liquid, oily, or low-viscosity compounds, to basic polymers such as rubber can easily cause machine slippage during manufacturing, making mixing difficult and leading to additive loss. To reduce slippage after adding additives, the additives can be mixed with dry, solid excipients to form a masterbatch, thereby improving processability.

[0004] Since the additives are not removed during production, selecting additives that do not affect material properties is a crucial prerequisite. Porous inorganic nanoparticles, especially silica, are a good option as they are compatible with silicone rubber and possess excellent liquid absorption properties. Existing technologies, such as patent application CN109843988A, disclose a method of achieving the aforementioned effect by combining specific silica with a high-molecular-weight sulfide compound to form a masterbatch. This involves mixing silica with a suitable surface area and the sulfide compound using equipment such as a homogenizer. The resulting masterbatch can then be compounded with uncured rubber to form the final product. If the sulfide compound is synthesized on-site, impurities or byproducts must be removed as much as possible during the masterbatch mixing process.

[0005] However, using porous inorganic nanoparticles combined with silicone rubber to form masterbatches has the following drawbacks: First, porous inorganic nanoparticles themselves are not polymers and are hygroscopic; therefore, masterbatches based solely on porous inorganic nanoparticles are not stable in the long term. Over time, the solid properties of the masterbatch will gradually decrease, eventually potentially becoming a gel-like mixture. Second, when finely powdered porous inorganic nanoparticles are mixed with liquid additives, it is common for the masterbatch particles to be of varying sizes, which is expected in heterogeneous mixing. The masterbatch may also be partially powdery, partially viscous semi-solid, or exhibit water-oil separation, with the masterbatch adhering to the homogenization equipment. If the masterbatch production and the subsequent silicone rubber compounding process are not carried out immediately, transportation and handling will become difficult. Summary of the Invention

[0006] The purpose of this invention is to solve the problem of difficult mixing when using liquid additives in the production of antimicrobial adhesives, and to provide a method for preparing raw rubber masterbatch. This method uses polyether, porous inorganic nanoparticles, and raw rubber to prepare the raw rubber masterbatch. The prepared raw rubber masterbatch has good stability, is convenient for transportation and storage, and is more conducive to commercial production and application.

[0007] Another objective of this invention is to provide a raw rubber masterbatch prepared by the above method.

[0008] Another objective of this invention is to provide a method for preparing an antimicrobial adhesive. This method employs a two-stage preparation process. First, a semi-stable mixture is formed by mixing a liquid polyether additive with porous inorganic nanoparticles. Then, this mixture is batch-mixed into already-refined raw rubber to obtain the raw rubber masterbatch. Finally, the raw rubber masterbatch is mixed with a base polymer and cured to obtain the antimicrobial adhesive.

[0009] In addition, the present invention aims to provide a bacteriostatic adhesive prepared by the above method.

[0010] In a first aspect, the present invention provides a method for preparing raw rubber masterbatch, comprising:

[0011] Polyethers are combined with porous inorganic nanoparticles to form a mixture;

[0012] The mixture is combined with raw rubber to form raw rubber masterbatch.

[0013] In a preferred embodiment, the polyether comprises grafted silicone-modified polyether, functionalized polyether, or unmodified polyether.

[0014] More preferably, the grafted organosilicon polyether is a polymethylsiloxane grafted onto one or more polyethers.

[0015] More preferably, the grafted organosilicon polyether comprises one or more polyethers selected from the following: fatty alcohol polyoxyalkylene ethers grafted onto poly(C1-C6)alkylsiloxanes, polyoxyalkylene fatty acids, polyoxyalkylene sorbitan, polyoxyalkylene sorbitan fatty acid esters, polyalkylene diols, and combinations thereof.

[0016] More preferably, the polyether is selected from polyethylene glycol, polypropylene glycol or copolymers thereof, and the number average molecular weight of each polyether is 300-50000 Da.

[0017] In some preferred embodiments, the polyether is a vinyl-terminated polyether selected from vinyl-terminated polyethylene glycol, vinyl-terminated polypropylene glycol, or copolymers thereof.

[0018] In some preferred embodiments, the polyether is polyethylene glycol.

[0019] In a preferred embodiment, the porous inorganic nanoparticles are selected from silica, alumina, carbon black, zinc oxide, ferrous oxide, and mixtures thereof.

[0020] In a preferred embodiment, the specific surface area of ​​the porous inorganic nanoparticles is 50-500 m². 2 / g.

[0021] In some preferred embodiments, the porous inorganic nanoparticles are silicon dioxide.

[0022] In a preferred embodiment, the raw rubber is selected from silicone rubber, thermosetting rubber, and combinations thereof.

[0023] In some preferred embodiments, the raw rubber is methyl vinyl silicone rubber.

[0024] In some specific preferred embodiments, the polyether is polyethylene glycol, the porous inorganic nanoparticles are silicon dioxide, and the raw rubber is methyl vinyl silicone rubber.

[0025] In a preferred embodiment, the mass ratio of the polyether, porous inorganic nanoparticles, and raw rubber is 6:3:11 to 8:3:9.

[0026] In a preferred embodiment, the base polymer is selected from thermoplastic polyurethane (TPU), styrene-ethylene-butene-styrene (SEBS), polyolefin elastomer (POE), thermoplastic polyester elastomer (TPEE), thermoplastic vulcanizate (TPV), polyethylene (PE), polypropylene (PP), polystyrene (PS), styrene-acrylonitrile resin (SAN), acrylonitrile butadiene styrene (ABS), polyethylene terephthalate-1,4-cyclohexanediethanolamine (PCTG), polylactic acid (PLA), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polycarbonate (PC), polymethylpentene (PMP), polyamide (PA), polyvinyl chloride (PVC), ethylene-vinyl acetate (EVA), methyl methacrylate butadiene styrene (MBS), silicone rubber, and blends and copolymers thereof.

[0027] In a preferred embodiment, after the raw rubber is mixed evenly, the mixture is added to the raw rubber in batches and mixed together with the raw rubber.

[0028] More preferably, the mixture is added in 5 to 15 batches, and each batch is mixed for 3 to 15 minutes.

[0029] In some preferred embodiments, the mixture is added in 10 batches, with each batch being mixed for 3 minutes.

[0030] The raw rubber masterbatch provided by the present invention is prepared by any of the preparation methods described above.

[0031] Secondly, the present invention provides a method for preparing antimicrobial adhesives, which uses the above-mentioned raw rubber masterbatch for preparation, including:

[0032] The raw rubber masterbatch is combined with the base polymer to form an uncured antibacterial adhesive.

[0033] The uncured antibacterial adhesive is cured to form the antibacterial adhesive.

[0034] In some preferred embodiments, the base polymer is silicone rubber.

[0035] In some preferred embodiments, the base polymer is selected from liquid silicone rubber (LSR) or thermosetting rubber (HCR).

[0036] In a preferred embodiment, the mass ratio of the raw rubber masterbatch to the base polymer is 1:6 to 1:13.

[0037] In a preferred embodiment, the polyether is present at a weight ratio of 3.0 to 5.0% relative to the weight of the antibacterial adhesive.

[0038] In a preferred embodiment, the curing is performed by directly heating and curing the uncured antibacterial adhesive at a temperature of 120°C to 220°C, or by incorporating a curing agent into the uncured antibacterial adhesive and then heating and curing it at a temperature of 120°C to 220°C.

[0039] The antibacterial adhesive provided by the present invention is an antibacterial adhesive prepared by any of the methods described above.

[0040] The antibacterial adhesive of the present invention has antibacterial function and can be used to prepare antibacterial plastic products.

[0041] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0042] The raw rubber masterbatch of this invention is prepared by combining polyether, porous inorganic nanoparticles, and raw rubber. Because raw rubber molecules are relatively large and do not absorb water, using raw rubber as the carrier substrate of the masterbatch effectively improves the problems of water absorption and liquefaction of silica itself. The resulting raw rubber masterbatch exhibits good stability and uniformity, and does not show solid-liquid separation even after long-term storage. This makes the raw rubber masterbatch easier to transport and store, and more conducive to commercial production and application.

[0043] The method for preparing the antimicrobial adhesive of the present invention adopts a two-stage preparation process. First, liquid polyether additives are mixed with porous inorganic nanoparticles to form a semi-stable mixture. Then, the mixture is mixed into raw rubber that has been kneaded in batches to obtain raw rubber masterbatch. The antimicrobial adhesive is obtained by mixing the raw rubber masterbatch with the base polymer and curing it.

[0044] Moreover, since the raw rubber is a solid, it is a homogeneous mixture when mixed with porous inorganic nanoparticles that have absorbed polyether additives. The two-stage production of the antimicrobial adhesive solves the problem of uniformity in heterogeneous mixing of polyether additives, resulting in an antimicrobial adhesive with good uniformity. This not only makes it convenient to use but also improves the application effect of the antimicrobial adhesive. Attached Figure Description

[0045] Figure 1 This is an observation diagram of the raw rubber masterbatch prepared in Example 1.

[0046] Figure 2 This is an observation diagram of the raw rubber masterbatch prepared in Example 2.

[0047] Figure 3 This is an observation diagram of the raw rubber masterbatch prepared in Example 3.

[0048] Figure 4 This is an observation diagram of the raw rubber masterbatch prepared in Comparative Example 1.

[0049] Figure 5 This is an observation diagram of the raw rubber masterbatch prepared in Comparative Example 2. Detailed Implementation

[0050] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. However, the scope of protection and implementation of the present invention are not limited thereto. Any changes or modifications that do not depart from the spirit and essence of the present invention will be within the scope of protection of the present invention.

[0051] In this specification, references to "an embodiment," "an implementation," or "an exemplary embodiment" indicate that the described embodiment may include specific features, structures, or characteristics, but not every embodiment may include such specific features, structures, or characteristics. Furthermore, these phrases do not necessarily refer to the same embodiment. Additionally, when a specific feature, structure, or characteristic is described in connection with an embodiment, whether or not it is explicitly described, it is assumed that the effect of applying that feature, structure, or characteristic to other embodiments is within the knowledge of those skilled in the art.

[0052] Values ​​expressed as ranges should be interpreted flexibly, including not only the values ​​explicitly listed as limits of the range, but also all individual values ​​or subranges included within the range, as if each value and subrange were explicitly specified. For example, a concentration range of “about 0.1% to about 5%” should be interpreted as including not only the explicitly listed about 0.1% to about 5% by weight, but also individual concentrations within the specified range (e.g., 1%, 2%, 3%, and 4%) and subranges (e.g., 0.1% to 0.5%, 1.1% to 2.2%, and 3.3% to 4.4%).

[0053] As stated herein, unless otherwise specified, the terms "a" or "an" are used to include one or more species, and the term "or" is used to indicate a non-exclusive "or". Furthermore, when terms are used herein without further definition, they should be understood as descriptive for purposes other than limitation. Additionally, all publications, patents, and patent documents mentioned in the specification are incorporated herein by reference in their entirety as if individually incorporated by reference. If there is any inconsistency between the usage in this document and those documents incorporated by reference, the usage in the cited references shall be considered supplementary to this document. In the event of irreconcilable inconsistencies, the usage herein shall prevail.

[0054] In the manufacturing method described in the specification, the steps may be performed in any order without departing from the principles of the invention, except where the timing or sequence of operations is explicitly stated. The claims state that a step is performed first, followed by several other steps. It should be understood that the first step is performed before any other step, and other steps may be performed within any other step unless the order is further specified in that step. For example, a claim stating "step A, step B, step C, step D, and step E" should be interpreted as meaning that step A is performed first, step E is performed last, and steps B, C, and D are performed within steps A and E. They may be performed in any order, and such order still falls within the literal scope of the process claimed in the claims. Similarly, a given step or sub-step may be repeated.

[0055] Furthermore, unless the claims explicitly state that they are performed separately, the specified steps may be performed simultaneously. For example, the steps required to perform X and the steps required to perform Y may be performed simultaneously in a single operation, and such process should fall within the literal scope of the claimed process.

[0056] Unless the context clearly indicates otherwise, the singular forms “a”, “an”, and “the” may include plural indicators.

[0057] The term "about" can allow for a range of values ​​or a degree of variation within a certain range, such as within 10% or 5% of a specified value or range.

[0058] Unless the context clearly indicates otherwise, the term "independently selected" means that the mentioned groups are the same, different, or a mixture thereof. Therefore, under this definition, "X1, X2, and X3 are independently selected from an inert gas" should include, for example, when X1, X2, and X3 are all the same, when X1, X2, and X3 are completely different, wherein X1 and X2 are the same but X3 is different, and other similar permutations.

[0059] As used herein, "alkyl" refers to a straight-chain or branched saturated hydrocarbon group. Examples of alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl), pentyl (e.g., 1-methylbutyl, 2-methylbutyl, isopentyl, tert-pentyl, 1,2-dimethylpropyl, neopentyl, and 1-ethylpropyl), hexyl, etc. In various embodiments, the alkyl group may have 1-40 carbon atoms (i.e., C1-40 alkyl), for example, 1-30 carbon atoms (i.e., C1-30 alkyl). In some embodiments, the alkyl group may have 1-6 carbon atoms and may be referred to as a "lower alkyl group". Examples of lower alkyl groups include methyl, ethyl, propyl (e.g., n-propyl and isopropyl), and butyl (e.g., n-butyl, isobutyl, sec-butyl, tert-butyl). In some embodiments, as described herein, the alkyl group may optionally be substituted. The alkyl group is generally not substituted by another alkyl, alkenyl, or ynyl group.

[0060] As used herein, a "polymeric compound" (or "polymer") refers to a molecule comprising one or more repeating units linked by covalent chemical bonds. Polymeric compounds can be represented by general formula I:

[0061] *-(-(Ma)x—(Mb)y—)z*

[0062] General Formula I

[0063] Ma and Mb are each a repeating unit or monomer. A polymeric compound may have only one type of repeating unit or two or more different types of repeating units. When a polymeric compound has only one repeating unit, it can be called a homopolymer. When a polymeric compound has two or more different types of repeating units, the terms "copolymer" or "copolymer compound" can be used instead. For example, a copolymer compound may include repeating units where Ma and Mb represent two different repeating units.

[0064] Unless otherwise specified, the assembly of repeating units in a copolymer can be head-to-tail, head-to-head, or tail-to-tail. Additionally, unless otherwise specified, the copolymer can be a random copolymer, an alternating copolymer, or a block copolymer. For example, general formula I can be used to represent a copolymer of Ma and Mb, wherein the molar fraction of Ma is x and the molar fraction of Mb is y, wherein the repeating of comonomers Ma and Mb can be alternating, random, regio-random, regio-regular, or block, with a maximum of z comonomers. In addition to composition, polymeric compounds are characterized by their degree of polymerization (n) and molar mass (e.g., number-average molecular weight (M) and / or weight-average molecular weight (Mw)), depending on the measurement technique(s). The polymers described herein can exist in a variety of stereochemical configurations, such as isotactic, syndiotactic, random, or combinations thereof.

[0065] The method for preparing raw rubber masterbatch provided by the present invention includes: combining polyether with porous inorganic nanoparticles to form a mixture; and combining the mixture with raw rubber to form raw rubber masterbatch.

[0066] The polyethers used include grafted silicone-modified polyethers or unmodified polyethers.

[0067] In a preferred embodiment, the grafted organosilicon-modified polyether is a polymethylsiloxane grafted onto one or more polyethers, and is a polymer comprising repeating units of Formula 1:

[0068]

[0069] Formula 1

[0070] For each case, R 1 Each is independently a C1-C6 alkyl group or of the formula -(CH2)mR 2 The polyether portion shown is an integer selected from m = 0-4; R 2 The grafted silicone polyether is end-capped with one or more portions selected from C1-C6 alkyl, hydroxy, C1-C6 alkoxy, or polyether. In a particular preferred embodiment, the grafted silicone polyether comprising the repeating unit of Formula 1 comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more polyether portions.

[0071] Grafted silicone-modified polyethers can be block, alternating, random, regio-random, or regio-regular polymers. Grafted silicone-modified polyethers can be isotactic polymers, syndiotactic polymers, atactic polymers, or combinations thereof.

[0072] In a preferred embodiment, m is 0, 2-4, or 2-3. When m is 0, the polyether can be covalently bonded to the silicon-based repeating unit of Formula 1 via a silicon-oxygen covalent bond.

[0073] In which R1 In the case of C1-C6 alkyl groups, R 1 It can be a straight-chain or branched C1-C5 alkyl, C1-C4 alkyl, C1-C3 alkyl, or C1-C2 alkyl. In some embodiments, R 1 It is a methyl group.

[0074] In a preferred embodiment, the polyether is selected from fatty alcohol polyoxyalkylene ethers, polyoxyalkylene fatty acids, polyoxyalkylene sorbitan, polyoxyalkylene sorbitan fatty acid esters, polyalkylene glycols, and combinations thereof.

[0075] In a preferred embodiment, the polyether is selected from polyethylene glycol, polyoxyethylene sorbitan hexaoleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene lauryl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene hexadecyl / octadecyl ether, polyoxyethylene acrylate, silane-terminated polyoxyethylene, polyoxyethylene ethylene ether, polyoxyethylene grafted polymethylsiloxane, polypropylene glycol, polyoxypropylene glycol, polyoxypropyleneamine, polyoxypropylene acrylate, polyoxypropylene methacrylate, polyoxypropylene glycerol ether, and combinations thereof.

[0076] In some preferred embodiments, the polyether is selected from polyethylene glycol, ceteareth-20, poly(ethylene glycol) sorbitan hexaoleate, polysorbate 80, PEG-40 hydrogenated castor oil, and combinations thereof.

[0077] In some preferred embodiments, the polyether is selected from vinyl-terminated polyethers, such as vinyl-terminated polyethylene glycol, vinyl-terminated polypropylene glycol, or copolymers thereof.

[0078] In some preferred embodiments, the polyether is polyethylene glycol.

[0079] In a preferred embodiment, the number average molecular weight of each polyether is 300-50000 Da.

[0080] The number average molecular weight of grafted organosilicon polyethers can be 500-1,000,000 Da, 500-900,000 Da, 500-800,000 Da, 500-700,000 Da, 500-600,000 Da, 500-500,000 Da, 500-400,000 Da, 500-300,000 Da, 500-200,000 Da, 500-100,000 Da, 500-100,000 Da, or 500-90,000 Da. 500-90000Da, 500-80000Da, 500-70000Da, 500-60000Da, 300-50000Da, 500-40000Da, 500-30000Da, 10000-30000Da, 500-20000Da, 10000-20000Da, 500-10000Da or 1000-10000Da.

[0081] In another preferred embodiment, the polyether portion is represented by the following formula: -(CH2)mR 2 Where m is 2 or 3; R 2 It is polyethylene glycol.

[0082] In another preferred embodiment, the grafted silicone polyether has Formula 2:

[0083]

[0084] Formula 2

[0085] Where n is an integer between 1 and 100000, 1000-100000, 10000-100000, 1-10000, 1-1000, 100-1000, or 1-100; for each case, R 1 All are independently C1-C6 alkyl, methyl, or of the formula -(CH2)mR 2 The polyether portion shown is an integer selected from m = 0-4; for each case, R 3 All are independently hydroxyl, methoxy, C1-C6 alkoxy, C1-C6 alkyl, methyl, or of the formula -(CH2)mR 2 The polyether portion shown, wherein the grafted silicone polyether comprises at least one polyether portion.

[0086] In some preferred embodiments, the grafted silicone polyether containing the repeating unit of Formula 2 comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or more polyether portions.

[0087] In another preferred embodiment, the grafted silicone polyether is a polymer comprising repeating units of formula 3:

[0088]

[0089] Formula 3

[0090] Where n is an integer between 1 and 100000, 1000 and 100000, 10000 and 1 and 10000; for each case, R 3 All are independently hydroxyl, methoxy, or of the formula -(CH2)mR 2 The polyether portion shown, wherein m is an integer selected from m = 0-4, and wherein at least one R 2 It is the polyether portion.

[0091] The functionalized polyethers are selected from dialkylhydrosilane-terminated polyethers, allyl-terminated polyethers, and vinyl-terminated polyethers.

[0092] When the functionalized polyether is a dialkylhydrosilane-terminated polyether, the base polymer contains at least a supplementary reactive functional group, such as an olefin, capable of reacting with the dialkylhydrosilane-terminated polyether in the presence of a crosslinking agent. Therefore, in a preferred embodiment, the base polymer contains one or more olefin moieties, such as vinylsilane, allylsilane, or allyloxysilane.

[0093] In some preferred embodiments, the functionalized polyether has Formula 4:

[0094]

[0095] Formula 4

[0096] Where n is an integer between 1 and 100000, 1000-100000, 10000-100000, 1-10000, 1-1000, 100-1000, or 1-100; for each case, R 1 Each is independently methyl, vinyl, or allyl; for each case, R 3 All are independently hydroxy, methoxy, methyl, vinyl, or allyl, wherein the grafted silicone polyether comprises at least one polyether moiety. In some particularly preferred embodiments, the functionalized polyether of Formula 4 comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more vinyl and / or allyl moiety.

[0097] When the functionalized polyether is an allyl-terminated polyether, the base polymer may contain supplemental reactive functional groups, such as dialkylhydrosilanes, capable of reacting with the dialkylhydrosilane-terminated polyether in the presence of a crosslinking agent. Therefore, in a preferred embodiment, the base polymer comprises one or more hydrosilane moieties, such as dialkylhydrosilanes or dimethylhydrosilanes.

[0098] In some embodiments, the functionalized polyether has Formula 5:

[0099]

[0100] General Formula 5

[0101] Where n is an integer between 1 and 100000, 1000-100000, 10000-100000, 1-10000, 1-1000, 100-1000, or 1-100; for each case, R 1 All are independently C1-C6 alkyl, methyl, or hydrogen; for each case, R 3 Each is independently hydroxyl, C1-C6 alkoxy, methoxy, or hydrogen, wherein the grafted organosilicon polyether comprises at least one polyether moiety. In some particularly preferred embodiments, the functionalized polyether of Formula 5 comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more hydrogen moieties.

[0102] In a preferred embodiment, the porous inorganic nanoparticles may be selected from silica, alumina, carbon black, zinc oxide, titanium dioxide, zirconium oxide, ferrous oxide, and mixtures thereof. In some particularly preferred embodiments, the porous inorganic nanoparticles are silica.

[0103] In some preferred embodiments, the nanoscale size range of the porous inorganic nanoparticles is, for example, about 1 nm to about 900 nm, about 1 nm to about 500 nm, about 1 nm to about 100 nm, about 5 nm to about 100 nm, or about 5 nm to about 50 nm.

[0104] In some preferred embodiments, the specific surface area of ​​the porous inorganic nanoparticles is about 50-500 m². 2 / g, approximately 100-50m 2 / g, approximately 200-500m 2 / g, approximately 300-500m 2 / g or approximately 400-500m 2 / g.

[0105] In a preferred embodiment, the raw rubber is selected from silicone rubber, thermosetting rubber, and combinations thereof.

[0106] In some preferred embodiments, the silicone rubber can be liquid silicone rubber, thermosetting silicone rubber, or room temperature vulcanizing silicone rubber. In some particularly preferred embodiments, the raw rubber is methyl vinyl silicone rubber.

[0107] The mass ratio of polyether, porous inorganic nanoparticles, and raw rubber depends on the properties of the selected polyether and porous inorganic nanoparticles. In a preferred embodiment, the mass ratio of polyether, porous inorganic nanoparticles, and raw rubber is 6:3:11–8:3:9, 6:3:11–6.5:3:9, 6:3:11–7:3:9, 6:3:11–7.5:3:9, 6:3:10–6.5:3:9, 6:3:9.5–6.5:3:9, 6.5:3:11–7.5:3:9, 6.5:3:10–8:3:9, 6.5:3:9.5–7.5:3:9, or 6.5:3:10–7.5:3:9.

[0108] The raw rubber masterbatch of the present invention can also be prepared by the following methods:

[0109] Polyether and porous inorganic nanoparticles are combined to form a mixture; after the raw rubber is mixed evenly, the mixture is added to the raw rubber in batches and mixed together to form raw rubber masterbatch.

[0110] In a preferred embodiment, the mixture is added in 5 to 15 batches, such as in 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 batches.

[0111] In a preferred embodiment, the mixture is mixed for 3 to 15 minutes per batch, such as 3 minutes, 3.5 minutes, 4 minutes, 4.5 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes or 10 minutes.

[0112] In some preferred embodiments, the mixture is added in 10 batches, with each batch being mixed for 3 minutes.

[0113] There are no particular limitations on the method of combining polyether with porous inorganic nanoparticles, or on combining raw rubber masterbatch with the base polymer; mixing can be carried out in any manner known to those skilled in the art. Mixtures can be prepared by blending or mixing the basic components and other optional components as uniformly as possible using any conventional mixing method. Commonly used mixing equipment includes drum mixers, high-speed mixers; blenders, such as V-type, belt, or cone mixers; and mixers, such as jet mixers, planetary mixers, or Banbury mixers. The mixture can be preheated during the mixing process. Mixing can also be carried out in a portion of an extruder.

[0114] The combination of polyether and porous inorganic nanoparticles with raw rubber requires the use of a mixing machine or other machines used for processing silicone rubber.

[0115] The method for preparing the antimicrobial adhesive of the present invention includes: combining polyether with porous inorganic nanoparticles to form a mixture; combining the mixture with raw rubber to form a raw rubber masterbatch; combining the raw rubber masterbatch with a base polymer to form an uncured antimicrobial adhesive; and curing the uncured antimicrobial adhesive to form the antimicrobial adhesive.

[0116] In a preferred embodiment, the base polymer may be selected from thermoplastic polyurethane (TPU), styrene-ethylene-butene-styrene (SEBS), polyolefin elastomer (POE), thermoplastic polyester elastomer (TPEE), thermoplastic vulcanizate (TPV), polyethylene (PE), polypropylene (PP), polystyrene (PS), styrene-acrylonitrile resin (SAN), acrylonitrile butadiene styrene (ABS), polyethylene terephthalate-1,4-cyclohexanediethanolamine (PCTG), polylactic acid (PLA), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polycarbonate (PC), polymethylpentene (PMP), polyamide (PA), polyvinyl chloride (PVC), ethylene-vinyl acetate (EVA), methyl methacrylate butadiene styrene (MBS), silicone rubber, and blends and copolymers thereof.

[0117] In some preferred embodiments, the base polymer is silicone rubber. This silicone rubber can be liquid silicone rubber (LSR), thermosetting silicone rubber (HCR), or room temperature vulcanizing silicone rubber.

[0118] In a preferred embodiment, the mass ratio of raw rubber masterbatch to base polymer is 1:6 to 1:13, 1:6.5 to 1:13, 1:7 to 1:13, 1:8 to 1:13, 1:9 to 1:13, 1:7 to 1:12, 1:8 to 1:12, 1:8 to 1:10, 1:8.5 to 1:10, or 1:9 to 1:10.

[0119] In a preferred embodiment, the polyether is present at a weight ratio of 3.0–5.0%, 3.5–5.0%, 4.0–5.0%, 4.5–5.0%, 3.5–4.5%, 3.0–4.0%, or 3.5–4.0% relative to the weight of the antimicrobial adhesive, such as 3.0%, 3.5%, 4.0%, 4.5%, or 5.0%.

[0120] In the combination of polyether and porous inorganic nanoparticles, in the combination of mixture and raw rubber to form raw rubber masterbatch, and in the combination of raw rubber masterbatch and base polymer to form antimicrobial adhesive, at least one additive selected from the following may be included: antioxidant, whitening agent, nucleating agent, release agent, color stabilizer, UV stabilizer (ultraviolet stabilizer), filler, plasticizer, impact modifier, colorant, lubricant, antistatic agent, flame retardant and anti-esterification agent.

[0121] Relative to the weight of the antimicrobial adhesive and additives, the content of additives in the antimicrobial adhesive by weight may be approximately 1-10%, approximately 1-9%, approximately 1-8%, approximately 1-7%, approximately 1-6%, or approximately 1-5%.

[0122] The step of curing uncured antimicrobial adhesive may include heating the uncured polymer composite material at temperatures of 120°C-220°C, 120°C-210°C, 120°C-200°C, 120°C-200°C, 130°C-200°C, or 140°C-200°C. The step of curing uncured antimicrobial adhesive may include heating the uncured antimicrobial adhesive for 60-600 seconds, 100-600 seconds, 150-600 seconds, 150-550 seconds, 150-500 seconds, or 180-550 seconds.

[0123] In a preferred embodiment, the step of curing the uncured antimicrobial adhesive may include heating the uncured antimicrobial adhesive at a temperature of 120°C-200°C, 120°C-190°C, 130°C-190°C, or 130°C-180°C; and then post-curing the antimicrobial adhesive at a temperature of 180°C-220°C, 180°C-210°C, 190°C-210°C, 195°C-205°C, or 200°C.

[0124] The step of curing uncured antimicrobial adhesive may include heating the uncured antimicrobial adhesive for 60-600 seconds, 100-600 seconds, 150-600 seconds, 150-550 seconds, 150-500 seconds, or 180-550 seconds. The step of post-curing antimicrobial adhesive may include heating the uncured antimicrobial adhesive for 1-6 hours, 1-5 hours, 2-5 hours, or 2-4 hours.

[0125] In another preferred embodiment, the method for preparing the antimicrobial compound further includes combining a crosslinking agent with a raw rubber masterbatch and a base polymer to form an uncured antimicrobial compound containing the crosslinking agent; and curing the uncured antimicrobial compound to form a crosslinked antimicrobial compound.

[0126] Any crosslinking agent known in the art can be used in the methods described herein. In preferred embodiments, the crosslinking agent is an organic peroxide, such as a dialkyl peroxide or a diaryl peroxide, or a hydrosilylation catalyst, such as a platinum catalyst or a rhodium catalyst. In some particularly preferred embodiments, the crosslinking agent is bis-(2,4-dichlorobenzoyl)-peroxide, dicumyl peroxide, or a combination thereof. In other preferred embodiments, the crosslinking agent is a Karstedt catalyst or Cp*Ru(MeCN)3]PF6.

[0127] The antibacterial adhesive of the present invention can also be prepared by the following methods:

[0128] Polyether is combined with porous inorganic nanoparticles to form a mixture; after the raw rubber is mixed evenly, the mixture is added to the raw rubber in batches and mixed together to form a raw rubber masterbatch; the raw rubber masterbatch is combined with the base polymer to form an uncured antimicrobial adhesive; the uncured antimicrobial adhesive is cured to form an antimicrobial adhesive.

[0129] In a preferred embodiment, the mixture is added in 5 to 15 batches, such as in 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 batches.

[0130] In a preferred embodiment, the mixture is mixed for 3 to 15 minutes per batch, such as 3 minutes, 3.5 minutes, 4 minutes, 4.5 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes or 10 minutes.

[0131] In some preferred embodiments, the mixture is added in 10 batches, with each batch being mixed for 3 minutes.

[0132] There are no particular limitations on the method of combining polyether with porous inorganic nanoparticles, or on combining raw rubber masterbatch with the base polymer; mixing can be carried out in any manner known to those skilled in the art. Mixtures can be prepared by blending or mixing the basic components and other optional components as uniformly as possible using any conventional mixing method. Commonly used mixing equipment includes drum mixers, high-speed mixers; blenders, such as V-type, belt, or cone mixers; and mixers, such as jet mixers, planetary mixers, or Banbury mixers. The mixture can be preheated during the mixing process. Mixing can also be carried out in a portion of an extruder.

[0133] The combination of polyether and porous inorganic nanoparticles with raw rubber requires the use of a mixing machine or other machines used for processing silicone rubber.

[0134] Additionally, antimicrobial compounds can be molded into shapes such as small balls, but they can also be molded into semi-finished or finished products. Suitable examples of methods for shaping antimicrobial compounds include blow molding, injection molding, compression molding, thermoforming, blow molding, casting, and extrusion compression molding. Blow molding is widely used in the production of films. Injection molding and blow molding are widely used in the production of products such as bottles, boxes, and containers. Extrusion is widely used in the production of products such as rods, sheets, and tubes.

[0135] The present invention also provides a bacteriostatic adhesive, specifically a bacteriostatic adhesive prepared by any of the methods described above.

[0136] The antibacterial adhesive of the present invention has antibacterial function and can be used to prepare antibacterial plastic products.

[0137] The antimicrobial adhesive described herein can be used to prepare plastic articles with antimicrobial properties. This invention also relates to the use of the antimicrobial adhesive in the preparation of articles. These articles may be used for storing or transporting food or beverages.

[0138] In some preferred embodiments, the article is a conduit for transporting fluids. The fluids can be beverages, such as water, and, for example, soft drinks, wine, beer, or milk.

[0139] In some preferred embodiments, the article is a flexible package. Suitable examples are films, sheets, plastic bags, containers, bottles, boxes, and drums. In other preferred embodiments, the antimicrobial adhesive is used for pharmaceutical packaging, for example, for primary packaging that comes into direct contact with the active pharmaceutical ingredient and includes blister packs, liquid bags, pouches, bottles, vials, and ampoules.

[0140] In some preferred embodiments, the article is used for medical applications. Medical applications include, for example, closures, rigid bottles and ampoules, needle sheaths, plunger rods for disposable syringes, moldings for containing diagnostic equipment, foldable tube shoulders, blow-fill sealing products, foldable tube bodies, films for primary and secondary medical and pharmaceutical packaging, disposable syringes, actuator bodies, sample cups, moldings for containing diagnostic equipment, centrifuge tubes, porous microtiter plates, trays, pipettes, and caps and closures.

[0141] The embodiments provided below can be used to better understand the implementation of this disclosure. The invention is not limited to the embodiments given herein.

[0142] Example 1

[0143] The preparation steps of the antibacterial adhesive in this embodiment are as follows:

[0144] 70g of silica (Evonik Aerosil 200, with a specific surface area of ​​175-225m²) was added. 2 175g of polyethylene glycol (number average molecular weight 600 Da) and 1 / g of raw rubber (methyl vinyl silicone rubber / 110 raw rubber) are placed in a container and mixed at low speed (40 rpm) with a stirrer until no obvious liquid residue remains. 255g of raw rubber (methyl vinyl silicone rubber / 110 raw rubber) is then mixed in a mixer for approximately 5 minutes until homogeneous. The aforementioned mixture is added to the raw rubber in batches, 10 times, mixing for 3 minutes each time, avoiding exceeding the vulcanization temperature. After 30 minutes, an uncured raw rubber masterbatch is obtained. The obtained uncured raw rubber masterbatch is as follows: Figure 1 As shown, the polyethylene glycol was completely absorbed, there was no oil leakage, and the mixture was uniform.

[0145] 34g of the obtained uncured raw rubber masterbatch was mixed with 366g of silicone rubber (Elastosil R406 / 70CN) and curing agent (platinum vulcanizing agent, including component A and component B, with component A added at 0.55% and component B added at 2.0% relative to the weight of the antimicrobial compound and silicone rubber, Shenzhen Longlifeng Materials Co., Ltd.) for 15 minutes (processing temperature <40℃), cured at 175℃ for 10 minutes, and then cured at 200℃ for 4 hours to obtain the antimicrobial compound.

[0146] Antimicrobial activity test: According to the test standard ASTM E3371, the antimicrobial adhesive obtained in this embodiment was made into a sheet for testing. Compared with polyethylene terephthalate (PET) sheets that meet the standard requirements, the antimicrobial adhesive achieved 99.92% antimicrobial activity.

[0147] Tensile properties: According to the test standard ISO 527-1:2012, the antibacterial compound obtained in this embodiment was made into silicone dumbbell plates for mechanical tensile testing, and compared with silicone without masterbatch and directly added antibacterial agent as a control group.

[0148] The silicone prepared from the antibacterial adhesive obtained in this embodiment has an average tensile strength of 3.7 (MPa), an average maximum force of 42.3 (N), an average elongation at break of 195.3 (%), and an average Young's modulus of elasticity of 14.4 (MPa).

[0149] The control group of silica gel with direct addition of antibacterial agent had an average tensile strength of 7.2 (MPa), an average maximum force of 108.5 (N), an average elongation at break of 486.4 (%), and an average Young's modulus of elasticity of 9.0 (MPa).

[0150] Example 2

[0151] The preparation steps of the antibacterial adhesive in this embodiment are as follows:

[0152] 60g of silica (Evonik Aerosil 200, with a specific surface area of ​​175-225m²) was added. 2 In a container, combine 150g of polyethylene glycol (number average molecular weight 600 Da) and 1g of raw rubber (methyl vinyl silicone rubber / 110 raw rubber). Mix at low speed (40 rpm) with a stirrer until no significant liquid residue remains. Then, mix 190g of raw rubber (methyl vinyl silicone rubber / 110 raw rubber) in a mixer for approximately 5 minutes until homogeneous. Add the mixture to the raw rubber in batches, 8 times, mixing for 3 minutes each time, avoiding exceeding the vulcanization temperature. After 30 minutes, obtain an uncured raw rubber masterbatch. The obtained uncured raw rubber masterbatch is shown below. Figure 2 As shown, the polyethylene glycol was completely absorbed, there was no oil leakage, and the mixture was uniform.

[0153] 32g of the obtained uncured raw rubber masterbatch was mixed with 368g of silicone rubber (Elastosil R406 / 70CN) and curing agent (platinum vulcanizing agent, including component A and component B, with component A added at 0.55% and component B added at 2.0% relative to the weight of the antimicrobial compound and silicone rubber, Shenzhen Longlifeng Materials Co., Ltd.) for 15 minutes (processing temperature <40℃), cured at 175℃ for 10 minutes, and then cured at 200℃ for 4 hours to obtain the antimicrobial compound.

[0154] Antimicrobial resistance test: According to the test standard ASTM E3371, the obtained antimicrobial adhesive was made into a sheet for testing. Compared with polyethylene terephthalate (PET) sheets that meet the standard requirements, the antimicrobial adhesive achieved 99.91% antimicrobial performance.

[0155] Tensile properties: According to the test standard ISO 527-1:2012, the antibacterial compound obtained in this embodiment was made into silicone dumbbell plates for mechanical tensile testing, and compared with silicone without masterbatch and directly added antibacterial agent as a control group.

[0156] The silicone prepared from the antibacterial adhesive obtained in this embodiment has an average tensile strength of 3.0 (MPa), an average maximum force of 40.4 (N), an average elongation at break of 195.1 (%), and an average Young's modulus of elasticity of 12.6 (MPa).

[0157] The control group of silica gel with direct addition of antibacterial agent had an average tensile strength of 7.2 (MPa), an average maximum force of 108.5 (N), an average elongation at break of 486.4 (%), and an average Young's modulus of elasticity of 9.0 (MPa).

[0158] Example 3

[0159] The preparation steps of the antibacterial adhesive in this embodiment are as follows:

[0160] 60g of silica (Evonik Aerosil 200, with a specific surface area of ​​175-225m²) was added. 2 In a container, combine 150g of polyethylene glycol (number average molecular weight 600 Da) and 1g of raw rubber (methyl vinyl silicone rubber / 110 raw rubber). Mix at low speed (40 rpm) with a stirrer until no significant liquid residue remains. Then, mix 165g of raw rubber (methyl vinyl silicone rubber / 110 raw rubber) in a mixer for approximately 5 minutes until homogeneous. Add the mixture to the raw rubber in batches, adding in 7 batches and mixing for 3 minutes each time, avoiding exceeding the vulcanization temperature. After 30 minutes, an uncured raw rubber masterbatch is obtained. The obtained uncured raw rubber masterbatch is as follows: Figure 3 As shown, the polyethylene glycol was completely absorbed, there was no oil leakage, and the mixture was uniform.

[0161] 30g of the obtained uncured raw rubber masterbatch was mixed with 370g of silicone rubber (trade name Elastosil R406 / 70CN) and curing agent (platinum vulcanizing agent, including component A and component B, with component A added at 0.55% and component B added at 2.0% relative to the weight of the antimicrobial compound and silicone rubber, Shenzhen Longlifeng Materials Co., Ltd.) for 15 minutes (processing temperature <40℃), cured at 175℃ for 10 minutes, and then cured at 200℃ for 4 hours to obtain the antimicrobial compound.

[0162] Antimicrobial activity test: According to the test standard ASTM E3371, the obtained antimicrobial adhesive was made into a sheet for testing. Compared with polyethylene terephthalate (PET) sheets that meet the standard requirements, it can be seen that the antimicrobial adhesive achieves 99.99% antimicrobial performance.

[0163] Tensile properties: According to the test standard ISO 527-1:2012, the antibacterial compound obtained in this embodiment was made into silicone dumbbell plates for mechanical tensile testing, and compared with silicone without masterbatch and directly added antibacterial agent as a control group.

[0164] The silicone prepared with antibacterial adhesive has an average tensile strength of 3.1 MPa, an average maximum force of 44.1 N, an average elongation at break of 198.3%, and an average Young's modulus of elasticity of 12.7 MPa.

[0165] The control group of silica gel with direct addition of antibacterial agent had an average tensile strength of 7.2 (MPa), an average maximum force of 108.5 (N), an average elongation at break of 486.4 (%), and an average Young's modulus of elasticity of 9.0 (MPa).

[0166] Comparative Example 1

[0167] The preparation steps of the antibacterial adhesive in this comparative example are as follows:

[0168] 45g of silicon dioxide (Evonik Aerosil 200, with a specific surface area of ​​175-225m²) was added. 2 Mix 250g of raw rubber (methyl vinyl silicone rubber / 110 raw rubber) with 250g of polyethylene glycol (number average molecular weight 600 Da) in a container and stir at low speed (40 rpm) until no obvious liquid residue remains. Mix 250g of raw rubber (methyl vinyl silicone rubber / 110 raw rubber) in a mixer for approximately 5 minutes until homogeneous. Add the mixture to the raw rubber in batches, 15 times, mixing for 3 minutes each time, avoiding exceeding the vulcanization temperature. After 45 minutes, obtain the uncured raw rubber masterbatch.

[0169] The uncured raw rubber masterbatch obtained in this comparative example is as follows: Figure 4 As shown, there was obvious uneven mixing, the polyethylene glycol could not be completely absorbed by the mixture, and oil leakage occurred.

[0170] Furthermore, the uncured raw rubber masterbatch obtained in this comparative example experienced oil leakage, causing the mixer to slip and making it impossible to uniformly mix the raw rubber masterbatch and silicone rubber. Therefore, it could not be used to prepare antimicrobial compounds of production significance.

[0171] Comparative Example 2

[0172] 50g of silica (Evonik Aerosil 200, with a specific surface area of ​​175-225m²) was added. 2 Mix 167g of polyethylene glycol (number average molecular weight 600 Da) with 1g of raw rubber (methyl vinyl silicone rubber / 110 raw rubber) in a container and stir at low speed (40 rpm) until no obvious liquid residue remains. Mix 200g of raw rubber (methyl vinyl silicone rubber / 110 raw rubber) in a mixer for about 5 minutes until homogeneous. Add the mixture to the raw rubber in batches, 15 times, mixing for 3 minutes each time, avoiding exceeding the vulcanization temperature. After 45 minutes, obtain the uncured raw rubber masterbatch.

[0173] The uncured raw rubber masterbatch obtained in this comparative example is as follows: Figure 5 As shown, there was obvious uneven mixing, the polyethylene glycol could not be completely absorbed by the mixture, and oil leakage occurred.

[0174] Furthermore, the uncured raw rubber masterbatch obtained in this comparative example experienced oil leakage, causing the mixer to slip and making it impossible to uniformly mix the raw rubber masterbatch and silicone rubber. Therefore, it was impossible to prepare a biodegradable rubber compound.

[0175] Based on the above description, further discussion regarding the use and operation of the present invention should be obvious. Therefore, no further discussion relating to the use and operation will be provided.

[0176] Then, regarding the above description, it should be understood that the optimal dimensional relationships of the components of the present invention, including variations in size, material, shape, form, function and operation, assembly and use, are all considered to be within the scope of the expertise of those skilled in the art, and all equivalent structural variations and relationships that are equivalent to the structures described in the specification are covered by the present invention.

[0177] Therefore, the foregoing is merely an explanation of the principles of the present invention. Furthermore, since many modifications and alterations will readily occur to those skilled in the art, it is not intended to limit the invention to the exact constructions and operations shown and described. Therefore, all suitable modifications and equivalents are possible and fall within the scope of the invention.

Claims

1. A method for preparing raw rubber masterbatch, characterized in that, include: Polyethers are combined with porous inorganic nanoparticles to form a mixture; The mixture is combined with raw rubber to form raw rubber masterbatch; The raw rubber is silicone rubber; Specifically, the step of combining the mixture with the raw rubber involves adding the mixture to the raw rubber in batches after the raw rubber has been mixed evenly, and then mixing and combining the mixture with the raw rubber. The polyether is polyethylene glycol, with a number-average molecular weight of 600 Da; The mass ratio of the polyether, porous inorganic nanoparticles, and raw rubber is 6:3:9.5, 6:3:10, 6:3:11, 6.5:3:9, 6.5:3:9.5, 6.5:3:10, 6.5:3:11, 7:3:9, 7.5:3:9, or 8:3:

9.

2. The method for preparing raw rubber masterbatch according to claim 1, characterized in that, The porous inorganic nanoparticles are selected from silicon dioxide, aluminum oxide, carbon black, zinc oxide, ferrous oxide and mixtures thereof.

3. The method for preparing raw rubber masterbatch according to claim 1, characterized in that, The specific surface area of ​​the porous inorganic nanoparticles is 50-500 m². 2 / g.

4. The method for preparing raw rubber masterbatch according to claim 1, characterized in that, The porous inorganic nanoparticles are silicon dioxide, and the raw rubber is methyl vinyl silicone rubber.

5. The method for preparing raw rubber masterbatch according to claim 1, characterized in that, The mixture is added in 5 to 15 batches, and each batch is mixed for 3 to 15 minutes.

6. A raw rubber masterbatch, characterized in that, It is prepared by the method described in any one of claims 1-5.

7. A method for preparing an antibacterial adhesive, characterized in that, include: The raw rubber masterbatch is combined with the base polymer to form an uncured antibacterial adhesive, wherein the raw rubber masterbatch is the raw rubber masterbatch as described in claim 6; The uncured antibacterial adhesive is cured to form the antibacterial adhesive.

8. The method for preparing the antibacterial adhesive according to claim 7, characterized in that, The base polymer is silicone rubber.

9. The method for preparing the antibacterial adhesive according to claim 7, characterized in that, The mass ratio of the raw rubber masterbatch to the base polymer is 1:6 to 1:

13.

10. The method for preparing the antibacterial adhesive according to claim 7, characterized in that, The curing process involves directly heating and curing the uncured antibacterial adhesive at a temperature of 120℃ to 220℃, or incorporating a curing agent into the uncured antibacterial adhesive and then heating and curing it at a temperature of 120℃ to 220℃.

11. A bacteriostatic adhesive, characterized in that, It is prepared by the method described in any one of claims 7-10.

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