A PMMA composite material, its preparation method and application

Abstract

The present invention discloses a PMMA composite material, a preparation method and an application thereof, belonging to the technical field of polymer materials; the PMMA composite material provided by the present invention comprises the following components in parts by mass: 40-80 parts of PMMA, 20-60 parts of polyvinylpyrrolidone-vinyl acetate copolymer, and 0.2-3 parts of surfactant. The PMMA composite material provided by the present invention has high transparency and excellent blood compatibility; moreover, the preparation method of the PMMA composite material provided by the present invention is simple, which is beneficial to actual production, and then it is applied to the automated rapid detection of blood in medical or livestock industries.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and in particular relates to a PMMA composite material and a preparation method and application thereof. Background Art

[0002] Polymethyl methacrylate (PMMA), a high-molecular-weight polymer also known as acrylic or organic glass, offers advantages such as high transparency, low price, and ease of machining, making it a commonly used glass alternative. PMMA has also found widespread application in the medical industry, particularly in the emerging field of automated blood testing. Its high transparency, comparable to glass, and superior toughness have led to its increasing adoption. However, as a polymer material, PMMA lacks hemotropism. While ensuring sample visibility during blood sampling, this slows sampling, significantly impacting efficiency and urgently requires improvement. Summary of the Invention

[0003] The purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and to provide a PMMA composite material with high transparency and good hemophilicity, as well as a preparation method and application thereof.

[0004] To achieve the above object, in a first aspect of the present invention, the present invention provides a PMMA composite material, comprising the following components in parts by mass: 40-80 parts of PMMA, 20-60 parts of polyvinyl pyrrolidone-vinyl acetate copolymer, and 0.2-3 parts of a surfactant;

[0005] The number average molecular weight of the polyvinyl pyrrolidone-vinyl acetate copolymer is 5×10 3 -2×10 5 ;

[0006] In the polyvinyl pyrrolidone-vinyl acetate copolymer, the molar ratio of vinyl pyrrolidone to vinyl acetate is vinyl pyrrolidone:vinyl acetate=(70-90):(10-30).

[0007] The PMMA composite material provided by the present invention is characterized by introducing a polyvinyl pyrrolidone-vinyl acetate copolymer (PVP-VAC) of appropriate mass and a surfactant, and further limiting the number average molecular weight of the polyvinyl pyrrolidone-vinyl acetate copolymer and the molar ratio of vinyl pyrrolidone to vinyl acetate in the polyvinyl pyrrolidone-vinyl acetate copolymer. This ensures that the PMMA composite material has excellent hemophilicity while maintaining high transparency.

[0008] Hemophilicity in the present invention is similar to hydrophilicity and refers to the ability of blood to wet a material.

[0009] The preparation method of the polyvinylpyrrolidone-vinyl acetate copolymer in this invention is as follows: Under an inert gas atmosphere, using anhydrous ethanol as a solvent, weigh a certain amount of vinylpyrrolidone monomer and vinyl acetate monomer. First, add part of the vinylpyrrolidone monomer and vinyl acetate monomer to the reactor according to a molar ratio of 1:1. After heating to 50 - 80 °C, add azobisisobutyronitrile as an initiator for polymerization reaction. While reacting, add the remaining part of the vinylpyrrolidone monomer. After reacting for 2 - 4 h, stop the reaction, and purify and dry to obtain a powdery product.

[0010] The method for measuring the molar ratio of vinylpyrrolidone and vinyl acetate in the polyvinylpyrrolidone-vinyl acetate copolymer is as follows: Refer to the Kjeldahl method for testing. First, measure the weight content of nitrogen element by elemental analysis, and then divide the weight content of nitrogen element by the molecular weight of nitrogen element (14) to obtain the molar content N1 of vinylpyrrolidone. Then multiply the molar content N1 of vinylpyrrolidone by the molecular weight of vinylpyrrolidone (111) to obtain the weight content W1 of vinylpyrrolidone. Subsequently, calculate the weight content W2 of vinyl acetate, W2 = 1 - W1. Divide W2 by the molecular weight of vinyl acetate (86) to obtain the molar content N2 of ethyl acetate. Then calculate the molar ratio of the two, that is, vinylpyrrolidone:vinyl acetate = N1:N2.

[0011] The method for testing the number-average molecular weight of the polyvinylpyrrolidone-vinyl acetate copolymer is as follows: Use GPC to test the molecular weight of the reaction product.

[0012] As a preferred embodiment of the PMMA composite material described in this invention, the PMMA composite material comprises the following components in parts by mass: 50 - 60 parts of PMMA, 40 - 50 parts of polyvinylpyrrolidone-vinyl acetate copolymer, and 0.5 - 1.5 parts of surfactant.

[0013] The inventors' research found that when further selecting the mass parts of the components within the above range, the comprehensive effect of the obtained product is better; the addition of surfactant can cooperate with the polyvinylpyrrolidone-vinyl acetate copolymer to further improve the hemocompatibility of the composite material to a certain extent. However, an excessive amount of surfactant will reduce the transparency of the composite material while improving the hemocompatibility. Therefore, the preferred amount of surfactant is 0.5 - 1.5 parts; similarly, the selection of the mass parts of the polyvinylpyrrolidone-vinyl acetate copolymer and PMMA also takes into account the synergistic effect between the components, so as to achieve excellent comprehensive properties of the composite material.

[0014] As a preferred embodiment of the PMMA composite material described in this invention, the number-average molecular weight of the polyvinylpyrrolidone-vinyl acetate copolymer is 8×10 3 -5×10 4 ;

[0015] And / or, in the polyvinylpyrrolidone-vinyl acetate copolymer, the molar ratio of vinylpyrrolidone to vinyl acetate is vinylpyrrolidone:vinyl acetate = (75 - 85):(15 - 25).

[0016] The inventors' research found that when the molar ratio of vinylpyrrolidone to vinyl acetate in the polyvinylpyrrolidone-vinyl acetate copolymer is further preferably (75 - 85):(15 - 25), the transparency of the product can be further improved, and at the same time, better hemocompatibility can be achieved; when the number-average molecular weight of the polyvinylpyrrolidone-vinyl acetate copolymer is further preferably 8×10 3 - 5×10 4 , it can also ensure excellent overall compatibility of the composite material, and thus ensure that the composite material has excellent transparency and hemocompatibility.

[0017] Preferably, the number-average molecular weight of the polyvinylpyrrolidone-vinyl acetate copolymer is 1×10 4 , and in the polyvinylpyrrolidone-vinyl acetate copolymer, the molar ratio of vinylpyrrolidone to vinyl acetate is vinylpyrrolidone:vinyl acetate = 80:20.

[0018] When the number-average molecular weight of the polyvinylpyrrolidone-vinyl acetate copolymer and the molar ratio of vinylpyrrolidone to vinyl acetate in the polyvinylpyrrolidone-vinyl acetate copolymer are further preferably the above point values, the comprehensive performance of the obtained composite material is optimal.

[0019] As a preferred embodiment of the PMMA composite material of the present invention, the surfactant is an ionic surfactant.

[0020] Preferably, the surfactant is an anionic surfactant.

[0021] Exemplarily, the anionic surfactant includes at least one of carboxylate anionic surfactants, sulfonate anionic surfactants, sulfate ester salt anionic surfactants, and phosphate ester salt anionic surfactants.

[0022] More preferably, the surfactant is a sulfonate surfactant.

[0023] Exemplarily, the sulfonate surfactant may be at least one of sodium monooleamide sulfosuccinate, linear sodium dodecylbenzenesulfonate, sodium dodecyl diphenyl ether disulfonate, sodium allyloxyhydroxypropanesulfonate, sodium 2-hydroxypropyl methacrylate sulfonate, sodium 2-acrylamido-2-methylpropanesulfonate, sodium allyloxysulfonate, and sodium vinylsulfonate.

[0024] The inventors' research found that when the surfactant is an ionic surfactant, especially an anionic surfactant, better comprehensive effects can be achieved.

[0025] As a preferred embodiment of the PMMA composite material described in the present invention, the number-average molecular weight of the PMMA is 5×10 4 -1.5×10 5 .

[0026] The test method for the number-average molecular weight of PMMA is to use GPC for testing.

[0027] The inventors' research found that when the number-average molecular weight of PMMA is within the above range, it is more conducive to processing; within the scope of the present invention, the selection of the number-average molecular weight of PMMA has no significant impact on transparency and blood compatibility, and excellent comprehensive effects can be achieved; exemplarily, the number-average molecular weight of PMMA can be 5×10 4 , 5.5×10 4 , 6×10 4 , 6.5×10 4 , 7×10 4 , 7.5×10 4 , 8×10 4 , 8.5×10 4 , 9×10 4 , 9.5×10 4 , 1×10 5 , 1.5×10 5 .

[0028] As a preferred embodiment of the PMMA composite material described in the present invention, the PMMA composite material further comprises 0-1 part of antioxidant and 0-1 part of lubricant.

[0029] Preferably, the antioxidant is at least one of hindered phenol antioxidants, phosphite antioxidants, metal alkyl thiophosphate antioxidants, carbamate antioxidants, and organic sulfur antioxidants; more preferably, the antioxidant is a phosphite antioxidant.

[0030] Preferably, the lubricant is at least one of amides, polysiloxanes, stearates, PE wax, and PP wax.

[0031] In the second aspect of the present invention, the present invention provides a method for preparing a PMMA composite material, the preparation method comprising the following steps: mixing the components evenly and then melt-extruding to obtain the PMMA composite material.

[0032] As a preferred embodiment of the preparation method described in the present invention, the temperature of the melt-extrusion is 120-210°C.

[0033] Preferably, the temperature of the twin-screw extruder is divided into ten zones. The temperature of the first to second zones is 120 - 170 °C, the temperature of the third to fifth zones is 190 - 210 °C, and the temperature of the sixth to tenth zones is 170 - 190 °C.

[0034] In the third aspect of the present invention, the present invention provides an application of the PMMA composite material in the automated rapid detection of blood.

[0035] As a preferred embodiment of the application of the present invention, the automated rapid detection of blood includes detection in the medical field or the livestock industry.

[0036] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0037] In a PMMA composite material provided by the present invention, by introducing a suitable mass of polyvinylpyrrolidone-vinyl acetate copolymer and a surfactant, and further defining the molecular weight of the polyvinylpyrrolidone-vinyl acetate copolymer and the molar ratio of vinylpyrrolidone to vinyl acetate in the polyvinylpyrrolidone-vinyl acetate copolymer, it is possible to achieve excellent hemocompatibility while ensuring high transparency of the PMMA composite material; specifically, the transparency of the obtained PMMA composite material is above 70.5%, and the time required to fill a specific volume blood collection tube (10 μL) for the reaction material with hemocompatibility is less than 2.9 s; moreover, the preparation method of the PMMA composite material provided by the present invention is simple, which is beneficial to actual production, and then it can be applied to the automated rapid detection of blood in the medical or livestock industry. Detailed implementation manners

[0038] To better illustrate the purpose, technical solution and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0039] Unless otherwise specified, the raw materials used in the present invention are conventional commercially available raw materials, and the raw materials used in the parallel embodiments or comparative examples in the present invention are the same.

[0040] PMMA1: Molecular weight is 8×10 4 , LG Sumitomo Chemical;

[0041] PMMA2: Molecular weight is 1.2×10 5 , CM-205, Chi Mei;

[0042] PVP-VAC1: Molecular weight is 1×10 4 , the molar ratio of vinylpyrrolidone to vinyl acetate in PVP-VAC is 80:20, Hubei Baidu Chemical;

[0043] PVP-VAC2: Molecular weight is 8×10 3, the molar ratio of vinyl pyrrolidone to vinyl acetate in PVP-VAC is 75:25, Hubei Baidu Chemical Industry;

[0044] PVP-VAC3: The molecular weight is 5×10 4 , the molar ratio of vinyl pyrrolidone to vinyl acetate in PVP-VAC is 85:15, Hubei Baidu Chemical Industry;

[0045] PVP-VAC4: The molecular weight is 5×10 3 , the molar ratio of vinyl pyrrolidone to vinyl acetate in PVP-VAC is 70:30, Hubei Baidu Chemical Industry;

[0046] PVP-VAC5: The molecular weight is 2×10 5 , the molar ratio of vinyl pyrrolidone to vinyl acetate in PVP-VAC is 90:10, Hubei Baidu Chemical Industry;

[0047] PVP-VAC6: The molecular weight is 1×10 4 , the molar ratio of vinyl pyrrolidone to vinyl acetate in PVP-VAC is 95:5, Hubei Baidu Chemical Industry;

[0048] PVP-VAC7: The molecular weight is 1×10 4 , the molar ratio of vinyl pyrrolidone to vinyl acetate in PVP-VAC is 65:35, Hubei Baidu Chemical Industry;

[0049] PVP-VAC8: The molecular weight is 1×10 3 , the molar ratio of vinyl pyrrolidone to vinyl acetate in PVP-VAC is 80:20, Hubei Baidu Chemical Industry;

[0050] PVP-VAC9: The molecular weight is 4×10 5 , the molar ratio of vinyl pyrrolidone to vinyl acetate in PVP-VAC is 80:20, Hubei Baidu Chemical Industry;

[0051] Surfactant 1: Sodium alkyl sulfonate, HS1, Clariant;

[0052] Surfactant 2: Sodium 2-acrylamido-2-methylpropanesulfonate, Zhongshan Dixin Chemical Co., Ltd.;

[0053] Surfactant 3: Allyloxy nonylphenol polyoxyethylene (10) ether monophosphate, commercially available;

[0054] Surfactant 4: Polyquaternium-16, commercially available;

[0055] Surfactant 5: Tween-80, commercially available;

[0056] Antioxidants: A mixture of RIANOX 1010 and RIANOX 168 in a mass ratio of 1:1, commercially available;

[0057] Lubricant: Vinyl bisstearamide, commercially available.

[0058] Examples 1-15 and Comparative Examples 1-8

[0059] Examples 1-15 of the present invention and Comparative Examples 1-8 provide a PMMA composite material, and the components (parts by mass) of the composite material are shown in Tables 1-2;

[0060] Table 1

[0061]

[0062] Table 2

[0063]

[0064] The preparation method of the PMMA composite materials provided in Examples 1-15 and Comparative Examples 1-8 is as follows: Mix evenly according to the parts by mass of the components in Tables 1-2 and then melt and extrude to obtain the PMMA composite material; the temperature of the twin-screw extruder is divided into ten zones, and the temperatures of the first to tenth zones are 120 °C, 180 °C, 220 °C, 220 °C, 220 °C, 220 °C, 220 °C, 220 °C, 220 °C, and 210 °C respectively.

[0065] Effect Examples

[0066] The effect examples of the present invention verify the properties of the PMMA composite materials prepared in Examples 1-15 and Comparative Examples 1-8, including the following two aspects:

[0067] 1. Light transmittance: Inject the PMMA composite material into a square plate with a thickness of 1.0 mm, and test it according to GB2140-1980 using a light transmittance-haze tester;

[0068] 2. Hemocompatibility: Inject the PMMA composite material into a cylindrical blood collection tube with a diameter of 1 mm, and test the time required to fill the blood in a specific volume of the blood collection tube (10 μL). The stronger the wetting ability of the blood to the material, that is, the higher the affinity between the two, the smaller the contact angle and the more obvious the capillary effect. Under the same environmental conditions, the climbing speed of the blood in the capillary is faster. Therefore, the hemocompatibility of the material can be evaluated by the time;

[0069] The test results are shown in Table 3;

[0070] Table 3

[0071]

[0072] As can be seen from Table 3, when the technical solution of the present invention is adopted, the comprehensive performance of the obtained product is excellent. The transparency of the obtained composite material is above 70.5%, and the time required to fill a specific volume of blood-taking vessel (10 μL) reflecting the hemocompatibility of the reaction material is below 2.9 s;

[0073] As can be seen from Examples 1-5 and Comparative Examples 3-4, the mass parts of the components of the composite material will affect the comprehensive performance of the product. When PMMA is further preferably 50-60 parts, polyvinylpyrrolidone-vinyl acetate copolymer is 40-50 parts, and surfactant is 0.2-1.5 parts, the comprehensive performance of the obtained product is better. The transparency is above 84.5%, and the time required to fill a specific volume of blood-taking vessel (10 μL) reflecting the hemocompatibility of the reaction material is below 1 s; When the addition amount of PVP-VAC in Comparative Example 3 is too much, the transparency of the obtained product decreases, and the blood-filling time is greatly prolonged. When the addition amount of surfactant in Comparative Example 4 is too much, the transparency of the obtained product decreases significantly, and the blood-taking time also increases compared with the examples;

[0074] As can be seen from Example 1 and Comparative Examples 1-2, PVP-VAC and surfactant are both indispensable for achieving high transparency and high hemocompatibility of the product; When PVP-VAC is not added in Comparative Example 1, the hemocompatibility of the obtained product decreases significantly, and the blood-taking time > 20 s, that is, the blood vessel cannot be filled, and the transparency of the product also shows a downward trend; When surfactant is not added in Comparative Example 2, although the effect on light transmittance is not significant, the blood-taking time increases significantly, which is 14 times longer than that in Example 1;

[0075] As can be seen from Example 1, Examples 8-11 and Comparative Examples 5-8, the molecular weight of PVP-VAC and the molar ratio of vinylpyrrolidone to vinyl acetate in PVP-VAC will both affect the performance of the product; When the molecular weight of PVP-VAC is further preferably 8×10 3 -5×10 4 and the molar ratio of vinylpyrrolidone to vinyl acetate in PVP-VAC is (75-85):(15-25), the comprehensive performance of the obtained product is more excellent. The transparency is above 84.4%, and the time required to fill a specific volume of blood-taking vessel (10 μL) reflecting the hemocompatibility of the reaction material is below 1.1 s;

[0076] As can also be seen from Example 1 and Examples 12-15, the selection of surfactant type will also affect the comprehensive performance of the product. Among them, when sulfonate surfactants are selected, the best comprehensive effect is obtained.

[0077] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A PMMA composite material, characterized in that: The PMMA composite material comprises the following components in parts by mass: 40-80 parts of PMMA, 20-60 parts of polyvinyl pyrrolidone-vinyl acetate copolymer, and 0.2-3 parts of surfactant; The number average molecular weight of the polyvinyl pyrrolidone-vinyl acetate copolymer is 5×10 3 -2×10 5 ; In the polyvinyl pyrrolidone-vinyl acetate copolymer, the molar ratio of vinyl pyrrolidone to vinyl acetate is vinyl pyrrolidone:vinyl acetate=(70-90):(10-30).

2. The PMMA composite material according to claim 1, characterized in that The PMMA composite material comprises the following components in parts by mass: 50-60 parts of PMMA, 40-50 parts of polyvinyl pyrrolidone-vinyl acetate copolymer, and 0.5-1.5 parts of a surfactant.

3. The PMMA composite material according to claim 1, characterized in that The number average molecular weight of the polyvinyl pyrrolidone-vinyl acetate copolymer is 8×10 3 -5×10 4 ; And / or, in the polyvinyl pyrrolidone-vinyl acetate copolymer, the molar ratio of vinyl pyrrolidone to vinyl acetate is vinyl pyrrolidone:vinyl acetate=(75-85):(15-25).

4. The PMMA composite material according to claim 1, characterized in that The surfactant is an ionic surfactant.

5. The PMMA composite material according to claim 1, characterized in that The molecular weight of the PMMA is 5×10 4 -1.5×10 5 .

6. The PMMA composite material according to claim 1, characterized in that The PMMA composite material further comprises 0-1 part of an antioxidant and 0-1 part of a lubricant.

7. The method for preparing the PMMA composite material according to any one of claims 1 to 6, wherein: The preparation method comprises the following steps: mixing the components uniformly and then melting and extruding them to obtain a PMMA composite material.

8. The preparation method according to claim 7, characterized in that The temperature of the melt extrusion is 120-210°C.

9. Use of the PMMA composite material according to any one of claims 1 to 6 in automated rapid detection of blood.

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