TWI787930B - Anti-biofouling plastic particle and manufacture method thereof - Google Patents

Abstract

An anti-biofouling polypropropylene plastic particle is provided in some embodiments of the present disclosure, including a raw plastic material and a zwitterionic polymer distributed between the raw plastic material. A method of manufacturing an anti-biofouling polypropropylene plastic particle is further provided in some embodiments of the present disclosure, including: providing a raw plastic material; providing a zwitterionic polymer; mixing the raw plastic material and the zwitterionic polymer to obtain a mixture; performing a smelting processing step to the mixture at a temperature of 150°C to 280°C to obtain a plastic particle.

Description

Colloidal particles resistant to adhesion of biomolecules and method for producing the same

The present disclosure relates to a plastic granule that resists adhesion of biomolecules and a manufacturing method thereof, in particular to a plastic granule containing polypropylene micelle and a manufacturing method thereof.

Plastisol is a high-molecular polymer (for example, with a molecular weight of at least 10,000 g/mole), which has plasticity during the manufacturing process. Due to the different monomers in high molecular polymers (such as polyethylene, polypropylene, polyvinyl chloride, etc.), it can be formed into plastic particles with different properties. Due to the excellent plasticity, easy processing and easy storage of plastic granules, the finished products made of plastic granules are widely used in daily life.

For example, Polypropylene (PP) particles are formed by the polymerization of propylene. The plastic products made of polypropylene particles have good mechanical properties, high heat distortion temperature, and are not easily affected by inorganic salts and acids. Or alkali corrosion, often used in supplies such as car batteries, toys, cassette casings, pudding boxes, etc.

However, the finished products made of the current plastic granules inevitably have the problem that biomolecules (molecules contained in living things, such as molecules contained in living things such as viruses, bacteria, and molds) are easy to stick, which may cause problems over time. Hygienic problems such as spreading pollution and breeding, causing concerns about long-term use. In addition, conventional processing methods for anti-adhesive plastic pellets (such as coating the surface with an anti-adhesive layer) usually require multiple processing steps in addition to the melting step of the plastic pellets, and additional processing steps are required during the reaction process. The use of organic solutions is not only cumbersome, but also the discharge of waste liquid is not friendly to the environment.

Based on the above, how to provide a kind of plastic pellets that are easy to manufacture, friendly to the environment, and have good anti-sticking effect is a problem to be solved.

Therefore, one aspect of the present disclosure is to provide an anti-adhesive plastic particle, comprising plastic raw materials and diionic polymers distributed among the plastic raw materials.

In some embodiments, the plastic raw material comprises a homopolymer, a copolymer, or a combination thereof, wherein the constituent monomers of the homopolymer or the copolymer comprise vinyl chloride, propylene, styrene, ethylene, urethane, methyl methacrylate , phenylene sulfide, formaldehyde, phenyl ether, urea, butylene terephthalate, ethylene terephthalate, or amide.

In some embodiments, the diionic polymer comprises block copolymers, random copolymers or alternating copolymers of AU _n BU _m , wherein AU represents the structure represented by -CR ¹ R ² -, and BU represents -CH ₂ CR ² R ³ -or -CR ² R ⁴ CH ₂ CR ² R ⁵ - the structure shown, m represents an integer from 5 to 120, n represents an integer from 5 to 120, wherein R ¹ represents a straight chain with 3 to 18 carbons Shaped, branched or cyclic alkyl, ester group, aryl group or heteroaryl group with 5 to 12 carbons, R ² represents a hydrogen atom or a methyl group, R ³ represents -COOR' or -CONR"H, R ⁴ Represents a hydrogen atom or a carboxyl group, and when R ⁴ is a hydrogen atom, R ⁵ is -COOR' or -CONR"H, wherein when R ⁴ is a carboxyl group, R ⁵ is a cationic group, wherein R' and R" respectively represent beet base, sulfobetaine or carboxybetaine.

In some embodiments, if the weight percentage of the plastic micelle is calculated as 100%, the weight percentage of the diionic polymer is between 0.1% and 3%.

In some embodiments, the plastic granules further include additives distributed among the plastic raw materials.

In some embodiments, the additive comprises a plasticizer, a stabilizer, a slip agent, or a combination thereof.

Another aspect of the present disclosure is to provide a method for manufacturing anti-adhesive plastic particles, including: providing plastic raw materials; providing diionic polymers; mixing plastic raw materials and diionic polymers to obtain a mixture; at a temperature of 150 Between °C and 280°C, the mixture is subjected to a kneading process step to obtain plastic pellets.

In some embodiments, the step of mixing the plastic raw material and the diionic polymer comprises: if the weight percentage of the sum of the plastic raw material and the diionic polymer is 100%, the added weight percentage of the diionic polymer is 0.1% to between 3%.

In some embodiments, the step of mixing the plastic material and the diionic polymer comprises: heating the plastic material and the diionic polymer at a temperature lower than 150°C.

In some embodiments, after the step of providing the plastic raw material, it further includes: providing an auxiliary agent; mixing the auxiliary agent with the plastic raw material to obtain a preprocessed product; mixing the preprocessed product and a diionic polymer to obtain a processing mixture; Between 150°C and 280°C, a kneading processing step is performed on the processing mixture to obtain plastic pellets.

It can be understood that different implementations or examples provided in the following content can implement different features of the subject matter of the present disclosure. The examples of specific components and arrangements are used to simplify the present disclosure and not to limit the present disclosure. Of course, these are examples only and are not intended to be limiting. For example, the description below that a first feature is formed on a second feature includes that the two are in direct contact, or that there are other additional features between the two instead of direct contact. In addition, the present disclosure may repeat reference numerals and/or symbols in several embodiments. Such repetition is for simplicity and clarity and does not imply a relationship between the various embodiments and/or configurations discussed.

The terms used in this specification generally have their ordinary meanings in the art and the context in which they are used. The examples used in this specification, including examples of any term discussed herein, are illustrative only and do not limit the scope and meaning of the disclosure or any exemplified term. Likewise, the disclosure is not limited to some of the embodiments provided in this specification.

In addition, relative terms in space, such as "below" and "upper", are used to conveniently describe the relative relationship between one element or feature and other elements or features in the drawings. These spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the drawings. The device may be otherwise positioned (eg, rotated 90 degrees or at other orientations) and the spatially relative descriptions used herein interpreted accordingly.

In this article, "a" and "the" can generally refer to one or more, unless the article is specifically limited in the context. It will be further understood that the terms "comprising", "comprising", "having" and similar words used herein indicate the features, regions, integers, steps, operations, elements and/or components described therein, but do not exclude Other features, regions, integers, steps, operations, elements, components, and/or groups thereof.

All documents cited herein by reference are as if each individual document or patent application were specifically and individually incorporated by reference by reference. If the definition or usage of a term in a cited document is inconsistent with or contrary to the definition of the term herein, the definition of the term herein shall apply.

Several implementations are listed below to describe the touch device of the present invention in more detail, but they are only for illustrative purposes and are not intended to limit the present invention. The scope of protection of the present invention shall prevail as defined by the scope of the appended patent application .

As mentioned above, the present disclosure provides an anti-adhesive plastic granule and a manufacturing method thereof. By mixing the diionic polymer and the plastic raw material (such as polypropylene), the diionic polymer is distributed among the plastic raw materials, It is achieved that only a small amount of diionic polymer is used to make the plastic particles achieve anti-sticking effect, and it is almost non-toxic to the human body, which can be widely used in daily necessities.

Please refer to FIG. 1 , which shows a flowchart of a method 100 for manufacturing plastic pellets according to some embodiments of the present disclosure. First, as shown in step S110, plastic raw materials are provided.

In some embodiments, the plastic raw material comprises a homopolymer, a copolymer, or a combination thereof, wherein the constituent monomers of the homopolymer or the copolymer comprise vinyl chloride, propylene, styrene, ethylene, urethane, methyl methacrylate , phenylene sulfide, formaldehyde, phenyl ether, urea, butylene terephthalate, ethylene terephthalate, or amide.

In some embodiments, the plastic raw material is polypropylene, which is formed by polymerizing and drying propylene monomers. Depending on the position of branch chain atoms, polypropylene can have different three-dimensional structures. In some embodiments, the polypropylene may be gelled polypropylene after heat granulation.

In some embodiments, after the step of providing the plastic raw material, it further includes: providing an auxiliary agent; mixing the auxiliary agent and the plastic raw material to obtain a preprocessed product, and then performing a subsequent process with the preprocessed product. In some embodiments, the auxiliary agent comprises a plasticizer, a stabilizer (such as an organic tin stabilizer, a barium zinc stabilizer, or a combination thereof), a slip agent (such as an internal slip agent (such as stearic alcohol, stearic acid alcohol, etc.) amine, butyl stearate, stearic acid monoglyceride or a combination thereof) or a slip agent (such as paraffin, stearic acid, polyethylene wax, oxidized polyethylene wax or a combination thereof)) etc. contribute to Additional additives to improve the properties of plastic raw materials. That is, according to the manufacturing process and finished product requirements, before mixing plastic raw materials and diionic polymers, under appropriate reaction conditions, the plastic raw materials can be preprocessed by mixing plastic raw materials and additives to obtain preprocessed products, which can be processed in the subsequent In the step, the preprocessed product is directly used, and the processing mixture is obtained through the same or similar steps as the subsequent manufacturing of plastic particles (for example, mixing the preprocessed product and the double ionic polymer; then, at a temperature between 150°C and 280°C , performing a kneading processing step on the processed mixture to obtain plastic granules), thereby obtaining plastic granules with improved properties compared to the use of plastic raw materials.

Next, as shown in step S120, a diionic polymer is provided.

In some embodiments, the form of the diionic polymer is not limited, such as powder. In one embodiment, the diionic polymer comprises a structure as described in Taiwan Patent Publication No. TW I496819 B, that is, the diionic polymer may, for example, comprise AU _n BU described in the following formula (1) or formula (2) _m block copolymers, random copolymers or alternating copolymers.

式(1)

式 (2)

Formula 1)

Formula (2)

AU represents the methylene structure of the divalent substituent represented by -CR ¹ R ² - in the formula (1), and BU represents the divalent methylene structure represented by -CH ₂ CR ² R ³ - in the formula (1). The ethylene group structure of the substituent, or the divalent propylene group structure with substituent shown in -CR ² R ⁴ CH ₂ CR ² R ⁵ - in formula (2), m represents an integer from 5 to 120, n represents an integer of 5 to 120, wherein AU has an anchor group, and BU has a diionic group or a pseudo-diionic group.

In detail, the above-mentioned R ¹ represents a straight chain, branched or cyclic alkyl group or ester group with 3 to 18 carbons (i.e. -COOR ^x , wherein R ^x represents a straight chain, branched or branched group with 3 to 18 carbons). Chain or cyclic alkyl, aryl or heteroaryl with 5 to 12 carbons (heteroaryl), aryl or heteroaryl with 5 to 12 carbons. The above-mentioned R ² represents a hydrogen atom or a methyl group. The above ^R3 represents the structure of -COOR' or -CONR"H, wherein R' and R" independently represent betaine group, sulfobetaine group or carboxybetaine group . The above-mentioned R ⁴ represents a hydrogen atom or a carboxyl group (-COOH), wherein when R ⁴ is a hydrogen atom, R ⁵ is -COOR' or -CONR"H, and when the above-mentioned R ⁴ is a carboxyl group, R ⁵ can be, for example, a cationic group (For example, it can be N,N-dimethylammonio-ethylene-1-amino-vinyl (N,N-dimethylammonio-ethylene-1-amino-vinyl), N,N-dimethylammonio-propylidene-aminovinyl (N,N-dimethylammnio-propylene-1-amino-vinyl), N,N-dimethylammonium butylamino vinyl (N,N-dimethylammnio-butylene-1-amino-vinyl) and N,N -N,N-dimethylammonio-pentylene-1-amino-vinyl.

Next, as shown in step S130, the plastic raw material and the diionic polymer are mixed to obtain a mixture.

In some embodiments, in the step of mixing plastic raw materials and diionic polymers, if the sum of reactants (such as the sum of plastic raw materials and diionic polymers; if additives are added, it is the plastic raw materials, diionic polymers and the sum of additives) weight percentage is based on 100%, then the weight percentage (weight percentage; wt) added by the diionic polymer is between 0.1% and 3% (such as 0.1%, 0.5%, 1%, 1.5% %, 2%, 2.5%, 3%, or any value within the preceding range). In some embodiments, when the weight percentage of the diionic polymer added is at least 0.1%, compared with no added diionic polymer, it can significantly reduce the adhesion of biomolecules (such as proteins), thereby reducing the adhesion of biomolecules (such as cells or bacteria). Specifically, if the relative attachment ratios of bacteria, proteins, and cells were counted as 100% under the condition of no addition of diionic polymers, then the addition of 0.5% of diionic polymers by weight, relative to the ratio of no addition of diionic polymers When using ionic polymers, it can avoid more than 96% of bacterial attachment (relative attachment ratio is less than 4%), avoid more than 66% of protein attachment (relative attachment ratio is less than 34%), and avoid more than 91% of human cells Attached (relative attachment ratio less than 9%). It should be noted that if the weight percentage of the above-mentioned diionic polymer is lower than the lower limit value, the anti-adhesion effect of the plastic particles of the final product made will not be obvious (the "plastic particles" of the plastic particles referred to in this disclosure "Anti-adhesion" refers to the property of preventing non-specific adhesion of biomolecules. If the relative adhesion ratio of the group without diionic polymers is regarded as 100%, the relative adhesion ratio of plastic particles is not greater than 40%), if the weight percentage is higher than the upper limit, it will not only increase the cost, but also the increase of the anti-sticking effect is limited.

In some embodiments, a diionic polymer with a suitable melting point can be selected to match the kneading temperature, for example, the melting point can be 150°C to 280°C, so that the diionic polymer can be uniformly dispersed in the plastic raw material during subsequent mixing In the process, the dispersion uniformity of the diionic polymer in the final product is improved.

In some embodiments, preliminary heating can be performed during the step of mixing plastic raw materials and diionic polymers to improve mixing efficiency. For example, the plastic raw material and the diionic polymer are heated at a temperature lower than 150° C. to improve the mixing efficiency of the plastic raw material and the diionic polymer, so that the diionic polymer is evenly distributed among the diionic polymers. However, the mixing method of the present disclosure is not limited thereto, and other methods (such as stirring conditions) that help to improve the mixing efficiency of plastic raw materials and diionic polymers are also included in the scope of the present disclosure.

In some embodiments, in the step of mixing plastic raw materials and dual ionic polymers, it is also possible to add suitable additives (such as the aforementioned plasticizers, stabilizers, lubricants, etc.) Mixing efficiency, accelerating the speed of subsequent process reactions, or helping to adjust the physical and chemical properties of plastic particles in the final product.

Next, as shown in step S140, when the temperature is between 150°C and 280°C (such as 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C or any value in the aforementioned range), perform a mixing process on the mixture to obtain plastic granules.

In some embodiments, the step of performing the mixing processing step on the mixture at a temperature between 150°C and 280°C comprises homogenizing the mixture at 190°C. Next, the mixture is plasticized and cooled through a twin-screw extruder to produce plastic pellets.

In some embodiments, the shape and size of the plastic pellets are not limited. For example, the plastic pellets can be formed into a strip-shaped test piece with a length of 120 mm, a width of 70 mm, and a thickness of 0.5 mm.

In some implementations, the melting points of additives (if added), plastic raw materials, and diionic polymers can be considered, and the appropriate mixing and processing temperature can be adjusted accordingly to avoid mixing due to the large difference in the melting points of the three uneven. It is also possible to adjust the number of kneading processes (for example, a single kneading process or two or more staged kneading processes, etc.) according to the aforementioned factors, so as to improve the uniformity of kneading. For example, the mixing processing temperature should not be lower than 150°C to avoid incomplete plasticization of the plastic, resulting in uneven mixing of diionic polymers, poor dispersion, and even the appearance of plastic particles in the final product visible to the naked eye. The white point reduces its transparency, affects the visual perception, and limits the application fields of downstream products made of plastic granules. In addition, if the dispersibility of the diionic polymer is not good, the prepared plastic particles may not be able to effectively resist sticking.

In some embodiments, the time of the mixing processing step is not limited, for example, it can be 20 minutes to 30 minutes or longer, so that the additives (if added), plastic raw materials, and diionic polymers are uniformly mixed .

The following uses several embodiments to illustrate the application of the present disclosure, but it is not intended to limit the present disclosure. Those with ordinary knowledge in the technical field of the present disclosure can use it without departing from the spirit and scope of the present disclosure. Various changes and embellishments.

Embodiment 1, preparation polypropylene micelle

First, using polypropylene as the plastic material, the polypropylene and different weight percentages of dual ion materials are pre-mixed in a mixer (Qiaolong Machinery Co., Ltd.) at a speed of not less than 50 rpm (Revolution(s) Per Minute) The rotational speed is high, fully stirred (if the weight percentage of the sum of the diionic polymer and polypropylene is regarded as 100%, the weight percentage of the diionic polymer is respectively 0.5%, 1%, and 2%) to form a mixture. Next, the mixture was put into a twin-screw extruder (Leistritz company, model ZSE27MAXX) for melt kneading processing, the screw speed was 230 rpm, and the action temperature was 190 ^o C to produce polypropylene granules. Finally, the polypropylene granules were molded in a thermocompression molding machine to obtain polypropylene test pieces. The above-mentioned diionic polymers are generally manufactured according to the method disclosed in the above-mentioned Taiwan Patent Publication No. TW I496819 B (provided by Prebo Biotechnology Co., Ltd.). In order to compare whether the polypropylene test piece added with diionic polymers can resist the adhesion of biomolecules and the degree of anti-adhesion, the polypropylene test piece obtained in this example was used to carry out the subsequent examples.

Embodiment 2, the antibacterial adhesion effect of polypropylene test piece

In this example, the Escherichia coli ( Escherichia coli ) adhesion test was used to evaluate the anti-adhesion effect of the polypropylene test piece on bacteria.

First, culture Escherichia coli with LB (Lysogeny Broth) medium to obtain a bacterial solution with an OD value of 1 at a wavelength of 660 nm. Next, cover the polypropylene test piece with 1 ml of bacterial solution, and incubate in an incubator at 37°C and 150 rpm for 24 hours. Next, wash away the unattached Escherichia coli on the polypropylene test piece with phosphate buffered saline (PBS) buffer solution, and then soak the polypropylene test piece in glutaraldehyde for 24 hours to fix the Escherichia coli on the polypropylene test piece . Next, the Escherichia coli attached to the polypropylene test piece was observed with a laser scanning conjugate focal electron microscope, and the amount of Escherichia coli attached per unit area in each group was calculated. Next, convert the adhesion amount of the polypropylene test piece without adding diionic polymers to 100% (that is, the relative adhesion ratio), and use the polypropylene test piece without adding diionic polymers as the relative adhesion ratio At the same time, the adhesion amount of the polypropylene test piece group added with diionic polymers was converted into a relative adhesion ratio, and the comparison results are shown in Figure 2.

In Figure 2, the horizontal axis represents the different addition contents of diionic polymers, and the vertical axis represents the relative attachment ratio of E. coli per unit area.

Figure 2 illustrates that when the weight percentage of diionic polymer is 0.5%, the relative attachment ratio is 3.41%; when the weight percentage of diionic polymer is 1%, the relative attachment ratio is 1.32%; When the weight percentage is 2%, the relative attachment ratio is 0.73%. That is, when the weight percentage of diionic polymer is 0.5%, compared with the group without adding diionic polymer, the amount of bacterial attachment can be reduced by more than 96%, and, as the weight percentage is gradually increased to 2%. , can reduce the amount of bacteria attached by more than 99%. As the amount of diionic polymers increases, the anti-bacterial adhesion effect will increase.

Embodiment 3, the anti-protein sticking effect of polypropylene test piece

In this example, fibrinogen was used as the protein to be tested, and enzyme-linked immunosorbent assay (ELISA) was used to evaluate the anti-adhesion effect of the polypropylene test piece on the protein.

First, soak the polypropylene test piece in PBS buffer for 30 minutes, then blot the liquid on the polypropylene test piece. Next, add a fibrinogen solution with a concentration of 1 mg/ml to the polypropylene test piece, and place the polypropylene test piece in an oven at 37°C for 30 minutes to dry, so that the fibrinogen is attached to the polypropylene test piece. Chip. Next, after washing the polypropylene test piece with PBS buffer solution for 3 times, the liquid on the polypropylene test piece was removed to remove fibrinogen and impurities in the unbound fibrinogen solution.

Then, a blocking (blocking) step was carried out to fill the portion of the polypropylene test piece that did not absorb fibrinogen. The blocking step was to apply 1 ml of fetal bovine serum albumin (bovine serum albmin; BSA) solution, after standing in an oven at 37°C for 30 minutes, the polypropylene test piece was washed 3 times with PBS buffer solution, and then the liquid on the polypropylene test piece was removed.

Next, the primary antibody that can bind to fibrinogen was applied on the polypropylene test piece, and then dried, and the polypropylene test piece was washed with PBS buffer solution for 3 times, and then the liquid on the polypropylene test piece was removed. Then, perform the above-mentioned sealing step again.

Then apply 1 ml of secondary antibody with a concentration of 1 mg/ml on the polypropylene test strip (the second antibody has specificity for the first antibody, and the second antibody is labeled with a group for subsequent color development (such as horseradish) Peroxidase (horseradish peroxidase; HRP), and after drying, the polypropylene test piece was washed 5 times with PBS buffer solution, and the liquid on the polypropylene test piece was removed.

Next, move the polypropylene test piece to a 24-well plate, and apply 0.5 ml of chromogen 3,3',5,5'-tetramethylbenzidine (3,3',5, 5'-Tetramethylbenzidine; TMB), wait for the reaction for 6 minutes, wait for the color to develop, and then apply 0.5 ml of 1 M sulfuric acid to the polypropylene test piece to terminate the color reaction. Finally, pipette 200 microliters (μL) of the reaction solution into a 96-well plate, and then use a microplate absorbance reader to measure the absorbance of the sample solution at a wavelength of 450 nm, so as to push back onto the polypropylene test piece The amount of fibrinogen attached. Next, convert the adhesion amount of the polypropylene test piece without adding diionic polymers to the relative adhesion ratio of 100%, as the conversion basis for the relative adhesion ratio, and then add the polypropylene test piece group with diionic polymers The other adhesion amounts were converted into relative adhesion ratios, and the comparison results of the relative adhesion ratios of each group are shown in Fig. 3 as an example.

In Figure 3, the horizontal axis represents the different addition contents of diionic polymers, and the vertical axis represents the relative attachment ratio of E. coli per unit area.

Figure 3 illustrates that when the weight percentage of the diionic polymer is 0.5%, the relative attachment ratio is 34%; when the weight percentage of the diionic polymer is 1%, the relative attachment ratio is 30%; When the weight percentage is 2%, the relative attachment ratio is 32%. That is, when the weight percentage of the diionic polymer is 0.5%, the amount of protein attachment can be reduced by at least 65% compared with the group without the added diionic polymer.

Embodiment 4, the anti-cell adhesion effect of polypropylene test piece

In this example, human fibrosarcoma cells (HT-1080 cell line, a cell line easily obtained by those skilled in the art) were used to perform a cell attachment test to evaluate the anti-adhesion effect of polypropylene test pieces on cells.

First, place HT-1080 cells in a cell culture dish and culture them in DMEM (Dulbecco's modified Minimal Essential Medium) medium containing 10% fetal bovine serum at 37°C in a cell culture incubator containing 5% CO ₂ Cultured in medium for 7 days, and then removed the medium. Cells were then washed three times with PBS buffer. Then add trypsin, wait for six minutes, pat the cells out of the culture plate, add DMEM culture medium containing 10% fetal bovine serum, mix evenly, centrifuge to remove excess trypsin and pellet the cells, and then suspend the cells Cell suspension at a cell density of 1.0x ¹⁰⁴ cells/ml.

Take 1 ml of cell suspension to cover the surface of the polypropylene test piece, place it in the cell culture incubator for 24 hours, wash the unattached cells on the surface of the polypropylene test piece with PBS buffer, and take pictures of the cells on the plastic with an inverted microscope Attachment to the surface of the sheet. The amount of cell attachment per unit area in each group was calculated. Then, in a similar manner to the aforementioned Example 2, the amount of attachment of the polypropylene test piece without the addition of the diionic polymer was converted into a 100% relative attachment ratio, and the polypropylene test piece group with the addition of the diionic polymer The other adhesion amounts were converted into relative adhesion ratios, and the comparison results of the relative adhesion ratios of each group are shown in Fig. 4 as an example.

Figure 4 illustrates that when the weight percentage of the diionic polymer is 0.5%, the relative attachment ratio is 8.57%; when the weight percentage of the diionic polymer is 1%, the relative attachment ratio is 15.73%; When the weight percentage is 2%, the relative attachment ratio is 1.40%. That is, when the weight percentage of the diionic polymer is 0.5%, the amount of cell attachment can be reduced by more than 91% compared with the group without the added diionic polymer. When the weight percentage of diionic polymer is 2%, compared with the group without diionic polymer, the amount of cell attachment can be reduced by more than 98%.

The cytotoxicity of embodiment 5, polypropylene test piece

In this example, mouse fibroblasts (L929 cell line, a cell line easily obtained by those skilled in the art) were used to perform an in vitro cytotoxicity test to evaluate whether the polypropylene test piece has cytotoxicity.

First, the L929 cell line was cultured in a petri dish, in which the medium was minimal essential medium (minimal essential medium; MEM; hereinafter referred to as MEM medium) containing 10% horse serum, and the L929 cell line was grown at 37°C, 5% CO ₂ for 7 days. Then, the MEM medium was removed, and the cells were washed 3 times with PBS buffer. Next, trypsin was added to the culture dish, and after standing for 6 minutes, the culture dish was patted lightly to make the L929 cell line detach from the culture dish, and then MEM culture solution was added to the culture dish to suspend the L929 cell line in the MEM culture solution. Next, transfer the MEM culture solution to a centrifuge tube for centrifugation to collect the cell pellet. Next, use the MEM culture medium to suspend the cell pellet to obtain the cell liquid, and then adjust the cell liquid with an appropriate amount of MEM culture liquid to the L929 cell line containing 1.0×10 ⁵ cells or 1.5×10 ⁵ cells per milliliter of the cell liquid (1.0× 10 ⁵ cells/ml or 1.5×10 ⁵ cells/ml).

Next, extract the substance in the polypropylene test piece. Specifically, the polypropylene test piece was covered with MEM culture solution, and the extraction was carried out at 37°C and 150 rpm for 24 hours to obtain extracts of each group (experimental group, positive control group, and negative control group). Specifically, the area of the polypropylene test piece: the ratio of the volume of the MEM culture solution is 6 cm2: 1 ml, and the MEM culture solution is used to extract zinc diethyl-dithiocarbamate (ZDEC) and High-density polyethylene (high density polyethylene, HDPE), the two are used as the positive control group and the negative control group in sequence, wherein the ratio of ZDEC mass: MEM culture medium volume is 0.1 g: 1 ml, HDPE mass: MEM culture medium volume The ratio is 0.2 grams: 1 ml.

Next, add 0.1 ml of 1.0×10 ⁵ cells/ml cell solution to the 96-well culture plate, and culture at 37°C, 5% CO ₂ for 24 hours. Then, after removing the culture solution in the culture dish, add 0.1 ml of the experimental group extract, the MEM culture solution, the positive control group extract and the negative control group extract respectively to the 96-well culture dish, at 37 ° C, 5 The culture was continued for 24 hours in % CO ₂ . Next, 0.1 ml of 2,3-bis(2-methoxy-4-nitro-5-sulfophenyl)-2hydro-tetrazole-5-carboxamide inner salt (2,3-bis( 2-methoxy-4-nitro-5-sulfophenyl)-5-[(phenylamino)carbonyl] -2H-tetrazolium hydroxide; hereinafter abbreviated as XTT reagent) into a 96-well culture plate, and kept at 37°C, 5% CO ₂ Incubate for 3 hours. Subsequently, the 96-well culture plate was taken out, and the OD value at a wavelength of 450 nm was detected by a microplate spectrophotometer to obtain the absorbance values of the experimental group, the blank group, the positive control group and the negative control group respectively, and then The cell viability was calculated by the following formula (Equation (3)).

式 (3)

Formula (3)

In order to facilitate the observation of changes in cell appearance, when adding cells to a 96-well plate, take 1.5×10 ⁵ cells/ml of cell fluid into a 12-well plate at the same time, and after 24 hours of cultivation, remove the culture medium and add 1 ml The extracts of the experimental group, the MEM culture solution, the extracts of the positive control group and the extracts of the negative control group were placed in a 12-well culture plate, and they were also cultured for 24 hours for observation.

According to the criteria of the cell change evaluation table in Table 1 below, the cell appearance changes, cell density changes and cytotoxicity grades of each group were evaluated, and the evaluation results of each group were integrated in Table 2 below.

Table 1. Evaluation table of cell change degree grade Level of reaction Toxicity determination Cell culture status monolayer cell density 0 No difference non-cytotoxic Intracellular organelles and other granules are obviously intact; no cell disintegration 100% 1 subtle slight cytotoxicity Less than 20% of the cells are spherical, non-attached, no granules in the cells, and some cells are disintegrated 80% to 100% 2 slight mild cytotoxicity 50% of the cells are spherical without intracellular granules, continuous cell disintegration and intercellular spaces 50% to 80% 3 Moderate moderate cytotoxicity Less than 80% of lamellar growth cells are spherical or disintegrated 30% to 50% 4 serious severe cytotoxicity Cells that should have grown in layers are almost completely destroyed and disintegrated less than 30%

Table 2. Comparison table of cell changes in each group Diionic polymer content in polypropylene test piece (%) cell type Cell density(%) Cell viability (%) Cytotoxicity 0 whole 92.69 94.66 0 0.5 whole 96.09 96.75 0 1 whole 95.59 88.91 1 2 whole 103.54 83.24 1

The results in Table 2 show that the polypropylene test piece with 0.5% by weight of diionic polymer added has a cytotoxicity of 0; and if the weight percentage of diionic polymer in the polypropylene test piece is increased to 1% and 2%, The cytotoxicity is only slightly increased to 1, almost no cytotoxicity, and almost no harm to the human body. Therefore, adding 0.5% to 2% of the diionic polymer polypropylene test piece has almost no harm to the human body and can be widely used in various daily necessities.

It can be seen from the above examples that the anti-adhesion plastic granules and the manufacturing method of the present disclosure, the dual ionic polymer and plastic raw materials are smelted together to form anti-adhesion plastic granules, which not only have excellent anti-adhesion effect, but also double The ionic polymer is dispersed in the plastic particles, which can avoid the peeling risk of the dual ionic polymer layer when the dual ionic polymer is coated on the plastic surface, and can prolong the anti-adhesion effect of the plastic particles, and compared with direct coating Covering method can reduce the usage of diionic polymers. In addition, it can also simplify other cumbersome steps when processing diionic polymers into plastic raw materials (such as surface grafting, surface separation, bionic adhesion or surface coating, etc.), and reduce the application of organic solvents, which is more environmentally friendly. Friendly, with better environmental protection value.

Although the present disclosure has been disclosed above with several specific embodiments, various modifications, changes and substitutions can be made to the foregoing disclosure, and it should be understood that, without departing from the spirit and scope of the present disclosure, some Circumstances will employ certain features of embodiments of the present disclosure but not correspondingly others. Therefore, the spirit of the present disclosure and the scope of claims should not be limited to that described in the above exemplary embodiments.

100: method

S110, S120, S130, S140: steps

In order to make the above and other purposes, features, advantages and embodiments of the present disclosure more obvious and understandable, the detailed descriptions of the attached drawings are as follows: Figure 1 shows plastic particles according to some embodiments of the present disclosure Flowchart of the fabrication method. FIG. 2 shows a comparison chart of relative attachment ratios of E. coli in an E. coli attachment test according to an embodiment of the present disclosure. FIG. 3 is a comparison chart of the relative attachment ratio of fibrinogen in the fibrinogen attachment test according to an embodiment of the present disclosure. FIG. 4 is a graph showing a comparison of relative cell attachment ratios in a cell attachment assay according to an embodiment of the present disclosure.

100: method

S110, S120, S130, S140: steps

Claims (7)

An anti-adhesive plastic particle, comprising: a plastic raw material, the plastic raw material is polypropylene; and a diionic polymer distributed among the plastic raw materials, wherein if the weight percentage of the plastic particle is 100% , then the weight percentage of the diionic polymer is between 0.1% and 2%. The plastic rubber particle as described in claim 1, wherein the diionic polymer comprises a block copolymer, a random copolymer or an alternating copolymer of AU _n BU _m , wherein AU represents the structure shown in -CR ¹ R ² - , BU represents the structure shown by -CH ₂ CR ² R ³ - or -CR ² R ⁴ CH ₂ CR ² R ⁵ -, m represents an integer from 5 to 120, n represents an integer from 5 to 120, wherein R ¹ represents carbon Straight chain, branched or cyclic alkyl, ester, aryl or heteroaryl with 5 to 12 carbons, R2 represents a ^hydrogen atom or a methyl group, ^R3 represents -COOR' or -CONR"H, R ⁴ represents a hydrogen atom or a carboxyl group, and when R ⁴ is a hydrogen atom, R ⁵ is -COOR' or -CONR"H, wherein when R ⁴ is a carboxyl group, R ⁵ is a cationic group, wherein R ' and R" represent betaine, sulphobetaine or carboxybetaine, respectively. The plastic granule as described in Claim 1 further comprises an additive distributed among the plastic raw materials. Plastic granules as described in claim item 3, wherein the auxiliary agent packs Contains a plasticizer, a stabilizer, a slip agent or a combination thereof. A method for manufacturing anti-adhesive plastic particles, comprising: providing a plastic raw material, the plastic raw material is polypropylene; providing a diionic polymer; mixing the plastic raw material and the diionic polymer to obtain a mixture, wherein if The weight percentage of the plastic raw material and the sum of the diionic polymer is calculated as 100%, and the weight percentage of the diionic polymer added is between 0.1% and 2%; when the temperature is between 150°C and 280°C, A kneading processing step is performed on the mixture to obtain the plastic granules. The method as claimed in claim 5, wherein the step of mixing the plastic raw material and the diionic polymer comprises: heating the plastic raw material and the diionic polymer at a temperature lower than 150°C. The method as described in claim 5, wherein after the step of providing the plastic raw material, it further includes: providing an auxiliary agent; mixing the auxiliary agent and the plastic raw material to obtain a preprocessed product; mixing the preprocessed product and the double The ionic polymer is obtained as a processing mixture; at a temperature between 150° C. and 280° C., the mixing processing step is performed on the processing mixture to obtain a plastic colloid.

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