CN113913048A - High-thermal-conductivity PCR reaction tube and preparation process thereof - Google Patents
High-thermal-conductivity PCR reaction tube and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a high thermal conductivity PCR reaction tube and a preparation process thereof; the preparation method comprises the following steps: the process 1 comprises the following steps: carrying out plasma pretreatment on the PCR reaction tube to obtain a pretreated PCR reaction tube; and (2) a process: and (3) soaking the pretreated PCR reaction tube in a heat conduction material for surface treatment to obtain the high-thermal-conductivity PCR reaction tube. The heat conduction material comprises modified graphene, an organic polymer, a solvent and a chemical auxiliary agent; the modified graphene is prepared from neohesperidin modified graphene oxide; the prepared PCR reaction tube has high thermal conductivity and excellent water resistance, biological pollution resistance and wear resistance.
Description
Technical Field
The invention belongs to the technical field of reaction tubes, and particularly relates to a high-thermal-conductivity PCR reaction tube and a preparation process thereof.
Background
At present, the variety of high thermal conductive materials studied is various, and the materials can be classified into the following three categories according to the material variety, respectively: polymer-based thermally conductive materials, metal-based thermally conductive materials, and ceramic thermally conductive materials. The heat-conducting polymer material mainly replaces metal materials and is applied to environments needing good heat conductivity and excellent anti-corrosion performance, such as heat exchangers, heat-conducting pipes, solar water heaters, coolers of storage batteries and the like. One of the largest and most important applications of thermally conductive plastics is the manufacture of heat exchangers instead of metals and metal alloys, which have the disadvantage of not being corrosion resistant, which have the disadvantage of expensive alloy materials, which can be overcome by thermally conductive plastics.
With the development of science and technology, domestic instrument detection equipment is also continuously developed, such as the application of a PCR instrument in the field of medical detection; the tube cover and the tube body of the reaction tube used by the PCR instrument are integrally connected, so that the closing tightness is good, the pollution can be prevented, and the cover is easy to open; the tube wall of the PCR reaction tube needs to ensure the effectiveness and the uniformity of indirect heat conduction of the sample; therefore, the development of a high thermal conductivity reaction tube is a hot spot of many researchers.
Disclosure of Invention
The invention aims to provide a PCR reaction tube with high thermal conductivity, excellent water resistance, anti-biological pollution performance and wear resistance.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a preparation process of a high-thermal-conductivity PCR reaction tube comprises the following steps:
the process 1 comprises the following steps: carrying out plasma pretreatment on the PCR reaction tube to obtain a pretreated PCR reaction tube;
and (2) a process: soaking the pretreated PCR reaction tube in a heat conduction material for surface treatment to obtain a high-thermal-conductivity PCR reaction tube;
the heat conduction material comprises modified graphene, an organic polymer, a solvent and a chemical auxiliary agent;
the modified graphene is prepared from neohesperidin modified graphene oxide.
According to the preparation method, neohesperidin is adopted to modify graphene oxide to obtain modified graphene; the modified graphene has excellent dispersion stability in a solvent to prevent coagulation, is compounded with other components to obtain a heat conduction material, and is coated on the surface of a PCR reaction tube to obtain the PCR reaction tube with excellent heat conductivity and wear resistance and better biological pollution resistance, so that the PCR reaction tube has less protein loss rate when detecting protein substances; the reason may be that the neohesperidin reacts with oxygen-containing groups in the graphene oxide, and the neohesperidin has a large molecular structure, so that the interlayer spacing of the graphene is increased, steric hindrance is formed between layers, the dispersion stability of the modified graphene is improved, and the physical and chemical properties of the graphene oxide are further improved; and the reaction tube is compounded with other components to obtain a heat conduction material, the heat conduction material possibly contains more active groups, the surface treatment is carried out on the reaction tube to obtain the reaction tube with higher heat conductivity, so that the good heat transfer efficiency is realized, the effectiveness and the uniformity of heat conduction among samples are ensured, and meanwhile, the PCR reaction tube has excellent wear resistance and better biological pollution resistance.
Preferably, the preparation method of the modified graphene is as follows:
dispersing 1-5 parts of graphene oxide in 25-45 parts of DMF (dimethyl formamide), and then adding 120-180 parts of thionyl chloride to treat for 8-12 hours at 70-85 ℃; after the reaction is finished, washing a reaction product by using dichloromethane, and drying at 45-55 ℃ to obtain functionalized graphene oxide; and then adding 1-3 parts of functionalized graphene oxide, 20-30 parts of neohesperidin, 2.5-3.5 parts of triethylamine, 20-40 parts of toluene and 7-14 parts of DMF (dimethyl formamide) into a round-bottom flask provided with a magnetic stirrer and a reflux condenser, stirring for 1-2 hours at 75-85 ℃, refluxing for 80-120 hours, cooling, washing and drying at 45-55 ℃ to obtain the modified graphene.
Preferably, in the heat conduction material, by weight, 7-15 parts of modified graphene, 10-25 parts of organic polymer, 40-80 parts of solvent and 0.5-5 parts of chemical auxiliary agent.
Preferably, the organic polymer is one or a combination of several of polyvinylpyrrolidone, urea resin, polymethyl acrylate and polyethylene glycol.
Preferably, the solvent is one of methyl formamide, methanol, toluene, dichloromethane and n-butanol.
Preferably, the chemical adjuvant comprises a coupling agent; the coupling agent is one of silane coupling agent or titanate coupling agent.
More preferably, the coupling agent is one or a combination of KH-560, KH-570, NDZ-201 and HY-109.
Preferably, the chemical auxiliary further comprises 1, 3-dibutoxy-2-propanol acetate.
Preferably, a method of preparing a thermally conductive material is as follows:
dissolving 10-25 parts by weight of organic polymer in 20-40 parts by weight of solvent, and uniformly mixing to obtain a polymerization solution;
adding 7-15 parts of modified graphene into 20-40 parts of solvent, and performing ultrasonic dispersion for 2-3 hours to obtain a modified graphene dispersion liquid;
and adding 0.5-5 parts of chemical auxiliary agent into the polymerization solution, then adding into the modified graphene dispersion solution, and uniformly mixing with ultrasonic dispersion through high-speed stirring, wherein the stirring speed is 800-1000 r/min, the stirring time is 15-30 min, the ultrasonic power is 150-250W, and the ultrasonic time is 10-20 min, so as to obtain the heat conduction material.
The invention adopts the plasma technology to pretreat the PCR reaction tube, possibly changes the internal structure of the reaction tube material to a certain degree, and then the reaction tube material is soaked in the heat conduction material, and the reaction tube material and active groups in the heat conduction material can generate some physical and chemical reactions, so that the heat conduction material is better adhered and combined on the surface of the PCR reaction tube, and further the physical and chemical properties of the PCR reaction tube are improved.
Preferably, in the process 1, the plasma pretreatment conditions are as follows: the background vacuum degree is 0.5-1.0 Pa, the argon flow is 60-70 sccm, and the ventilation time is 5-15 min; the discharge vacuum degree is 20-30 Pa, the output power is 60-150W, and the discharge time is 10-20 min.
Preferably, in the process 2, the soaking time is 5-10 h.
The invention also discloses application of the modified graphene in improving the biological pollution resistance of the PCR reaction tube.
The invention also discloses application of the modified graphene in improving the wear resistance of the PCR reaction tube.
According to the invention, the neohesperidin is adopted to modify the graphene oxide to obtain modified graphene; the modified graphene has excellent dispersion stability in a solvent to prevent coagulation, is compounded with other components to obtain a heat conduction material, and is coated on the surface of a PCR reaction tube to obtain the PCR reaction tube, so that the modified graphene has the following beneficial effects: the PCR reaction tube has excellent thermal conductivity and water resistance, better biological pollution resistance, excellent thermal conductivity and wear resistance, and better biological pollution resistance; the obtained modified graphene has excellent dispersion stability in a solvent, is used as a component of a heat conduction material and is compounded with other components to obtain the heat conduction material, the heat conduction material possibly contains more active groups, the surface treatment is carried out on the reaction tube to obtain the reaction tube with higher heat conductivity, so that the good heat transfer efficiency is realized, the effectiveness and the uniformity of heat conduction among samples are ensured, and meanwhile, the PCR reaction tube has excellent wear resistance and better biological pollution resistance.
Drawings
Fig. 1 is an infrared spectrum of modified graphene in example 2;
FIG. 2 shows the thermal conductivity of the PCR reaction tube;
FIG. 3 shows the amount of protein adsorbed on the surface of a PCR reaction tube;
FIG. 4 shows water absorption of PCR reaction tubes;
FIG. 5 shows the wear rate of the PCR reaction tube.
Detailed Description
The PCR reaction tubes used in the embodiment of the invention are all commercially available and made of polypropylene materials.
In order to further improve the heat conductivity and wear resistance of the PCR reaction tube and simultaneously enable the PCR reaction tube to have excellent water resistance, the preferable measures further comprise:
adding 0.1-0.5 part by weight of 1, 3-dibutoxy-2-propanol acetate into a chemical auxiliary agent, compounding the chemical auxiliary agent and modified graphene together with a coupling agent to prepare a heat conduction material, and carrying out surface treatment on a PCR reaction tube, so that the heat conductivity and the wear resistance of the PCR reaction tube are further improved, and the PCR reaction tube has excellent water resistance; probably because the 1, 3-dibutoxy-2-propanol acetic ester and the coupling agent can generate certain physical and chemical crosslinking and then react with active groups contained in the modified graphene, the dispersity of the heat conduction material is improved, the heat conduction material can be uniformly coated on the surface of the PCR reaction tube, the heat conduction performance and the wear resistance of the PCR reaction tube are further improved, and meanwhile, the PCR reaction tube has excellent water resistance.
The technical solution of the present invention is further described in detail below with reference to the following detailed description and the accompanying drawings:
example 1
A preparation method of a heat conduction material comprises the following steps:
s1: preparation of modified graphene
Dispersing 2.5 parts by weight of graphene oxide in 35 parts by weight of DMF (dimethyl formamide), and then adding 130 parts by weight of thionyl chloride to treat for 8 hours at 75 ℃; after the reaction is finished, washing a reaction product by using dichloromethane, and drying at 45 ℃ to obtain functionalized graphene oxide; then adding 1.5 parts by weight of the functionalized graphene oxide, 24 parts by weight of neohesperidin, 2.5 parts by weight of triethylamine, 25 parts by weight of toluene and 8 parts by weight of DMF (dimethyl formamide) into a round-bottomed flask provided with a magnetic stirrer and a reflux condenser, stirring at 75 ℃ for 1h, refluxing for 80h, cooling to room temperature, washing with ethanol, and drying at 45 ℃ to obtain modified graphene;
s2: preparation of heat conductive material
Dissolving 10 parts by weight of polyvinylpyrrolidone in 30 parts by weight of methyl formamide, and uniformly mixing to obtain a polymerization solution;
adding 8 parts by weight of the modified graphene into 30 parts by weight of methyl formamide, and performing ultrasonic dispersion for 2 hours to obtain a modified graphene dispersion liquid;
adding 1.8 parts by weight of KH-560 into the polymerization solution, then adding into the modified graphene dispersion solution, and uniformly mixing with ultrasonic dispersion through high-speed stirring, wherein the stirring speed is 800r/min, the stirring time is 30min, the ultrasonic power is 150W, and the ultrasonic time is 20min to obtain the heat conduction material.
Example 2
A preparation method of a heat conduction material comprises the following steps:
s1: preparation of modified graphene
Dispersing 4 parts by weight of graphene oxide in 45 parts by weight of DMF, and then adding 160 parts by weight of thionyl chloride to treat for 12 hours at 80 ℃; after the reaction is finished, washing a reaction product by using dichloromethane, and drying at 45 ℃ to obtain functionalized graphene oxide; then adding 2.5 parts by weight of the functionalized graphene oxide, 30 parts by weight of neohesperidin, 3.5 parts by weight of triethylamine, 30 parts by weight of toluene and 11 parts by weight of DMF (dimethyl formamide) into a round-bottom flask provided with a magnetic stirrer and a reflux condenser, stirring at 85 ℃ for 1h, refluxing for 100h, cooling to room temperature, washing with ethanol, and drying at 50 ℃ to obtain modified graphene;
s2: preparation of heat conductive material
Dissolving 20 parts by weight of polymethyl acrylate in 40 parts by weight of methylformamide, and uniformly mixing to obtain a polymerization solution;
adding 12 parts by weight of the modified graphene into 40 parts by weight of methyl formamide, and performing ultrasonic dispersion for 2.5 hours to obtain a modified graphene dispersion liquid;
adding 2.5 parts by weight of NDZ-201 into the polymerization solution, then adding into the modified graphene dispersion solution, and uniformly mixing with ultrasonic dispersion through high-speed stirring, wherein the stirring speed is 1000r/min, the stirring time is 20min, the ultrasonic power is 200W, and the ultrasonic time is 15min to obtain the heat conduction material.
Example 3
A preparation method of a heat conduction material comprises the following steps:
s1: preparation of modified graphene
Dispersing 5 parts by weight of graphene oxide in 40 parts by weight of DMF, and then adding 180 parts by weight of thionyl chloride to treat for 12 hours at 85 ℃; after the reaction is finished, washing a reaction product by using dichloromethane, and drying at 55 ℃ to obtain functionalized graphene oxide; then adding 1 part by weight of the functionalized graphene oxide, 20 parts by weight of neohesperidin, 2.5 parts by weight of triethylamine, 25 parts by weight of toluene and 14 parts by weight of DMF (dimethyl formamide) into a round-bottomed flask provided with a magnetic stirrer and a reflux condenser, stirring at 75 ℃ for 1h, refluxing for 120h, cooling to room temperature, washing with ethanol, and drying at 50 ℃ to obtain modified graphene;
step S2 is the same as in example 2.
Example 4
A preparation method of a heat conduction material comprises the following steps:
step S1 is the same as in example 2;
s2: preparation of heat conductive material
Dissolving 25 parts by weight of polyethylene glycol in 40 parts by weight of toluene, and uniformly mixing to obtain a polymerization solution;
adding 15 parts by weight of the modified graphene into 40 parts by weight of toluene, and performing ultrasonic dispersion for 3 hours to obtain a modified graphene dispersion liquid;
adding 5 parts by weight of NDZ-201 into the polymerization solution, then adding into the modified graphene dispersion solution, and uniformly mixing with ultrasonic dispersion through high-speed stirring, wherein the stirring speed is 1000r/min, the stirring time is 20min, the ultrasonic power is 250W, and the ultrasonic time is 15min to obtain the heat conduction material.
Example 5
A preparation method of a heat conduction material comprises the following steps:
step S1 is the same as in example 2;
s2: preparation of heat conductive material
Dissolving 20 parts by weight of polymethyl acrylate in 40 parts by weight of methylformamide, and uniformly mixing to obtain a polymerization solution;
adding 12 parts by weight of the modified graphene into 40 parts by weight of methyl formamide, and performing ultrasonic dispersion for 2.5 hours to obtain a modified graphene dispersion liquid;
adding 2.5 parts by weight of NDZ-201 and 0.25 part by weight of 1, 3-dibutoxy-2-propanol acetate into the polymerization solution, then adding into the modified graphene dispersion solution, and uniformly mixing with ultrasonic dispersion through high-speed stirring, wherein the stirring speed is 1000r/min, the stirring time is 20min, the ultrasonic power is 200W, and the ultrasonic time is 15min, so as to obtain the heat conduction material.
Example 6
A preparation method of a heat conduction material comprises the following steps:
dissolving 20 parts by weight of polymethyl acrylate in 40 parts by weight of methylformamide, and uniformly mixing to obtain a polymerization solution;
adding 12 parts by weight of graphene oxide into 40 parts by weight of methyl formamide, and performing ultrasonic dispersion for 2.5 hours to obtain a graphene dispersion liquid;
adding 2.5 parts by weight of NDZ-201 and 0.25 part by weight of 1, 3-dibutoxy-2-propanol acetate into the polymerization solution, then adding into the graphene dispersion solution, and uniformly mixing with ultrasonic dispersion through high-speed stirring, wherein the stirring speed is 1000r/min, the stirring time is 20min, the ultrasonic power is 200W, and the ultrasonic time is 15min, so as to obtain the heat conduction material.
Example 7
A preparation process of a high-thermal-conductivity PCR reaction tube comprises the following steps:
the process 1 comprises the following steps: placing a sample of the PCR reaction tube in a plasma treatment instrument for plasma pretreatment, wherein the plasma pretreatment conditions are as follows: background vacuum degree of 0.8Pa, argon flow of 70sccm, and ventilation time of 10 min; filling argon into the whole vacuum chamber; closing the thermocouple vacuum gauge, opening a radio frequency power source and a radio frequency matcher, wherein the discharge vacuum degree is 25Pa, the output power is 90W, and the discharge time is 10min to obtain a pretreated PCR reaction tube;
and (2) a process: and (3) soaking the pretreated PCR reaction tube in the heat conduction material in the embodiment 1 for 10h for surface treatment, and drying to obtain the high-heat-conductivity PCR reaction tube.
Example 8
A preparation process of a high-thermal-conductivity PCR reaction tube comprises the following steps:
the process 1 comprises the following steps: placing a sample of the PCR reaction tube in a plasma treatment instrument for plasma pretreatment, wherein the plasma pretreatment conditions are as follows: background vacuum degree of 1.0Pa, argon flow of 60sccm, and ventilation time of 15 min; filling argon into the whole vacuum chamber; closing the thermocouple vacuum gauge, opening a radio frequency power source and a radio frequency matcher, wherein the discharge vacuum degree is 30Pa, the output power is 150W, and the discharge time is 15min to obtain a pretreated PCR reaction tube;
and (2) a process: and (3) soaking the pretreated PCR reaction tube in the heat conduction material in the embodiment 1 for 10h for surface treatment, and drying to obtain the high-heat-conductivity PCR reaction tube.
Example 9
The preparation process of high heat conductivity PCR reaction tube is the same as that in example 7 except that:
and (2) a process: and (3) soaking the pretreated PCR reaction tube in the heat conduction material in the embodiment 2 for 10h for surface treatment, and drying to obtain the high-heat-conductivity PCR reaction tube.
Example 10
The preparation process of high heat conductivity PCR reaction tube is the same as that in example 7 except that:
and (2) a process: and (3) soaking the pretreated PCR reaction tube in the heat conduction material in the embodiment 3 for 10h for surface treatment, and drying to obtain the high-heat-conductivity PCR reaction tube.
Example 11
The preparation process of high heat conductivity PCR reaction tube is the same as that in example 7 except that:
and (2) a process: and (3) soaking the pretreated PCR reaction tube in the heat conduction material in the embodiment 4 for 10h for surface treatment, and drying to obtain the high-heat-conductivity PCR reaction tube.
Example 12
The preparation process of high heat conductivity PCR reaction tube is the same as that in example 7 except that:
and (2) a process: and (3) soaking the pretreated PCR reaction tube in the heat conduction material in the embodiment 5 for 10h for surface treatment, and drying to obtain the high-heat-conductivity PCR reaction tube.
Example 13
The preparation process of high heat conductivity PCR reaction tube is the same as that in example 7 except that:
and (2) a process: and (3) soaking the pretreated PCR reaction tube in the heat conduction material in the embodiment 6 for 10h for surface treatment, and drying to obtain the high-heat-conductivity PCR reaction tube.
Comparative example 1
A preparation method of a heat conduction material comprises the following steps:
dissolving 20 parts by weight of polymethyl acrylate in 40 parts by weight of methylformamide, and uniformly mixing to obtain a polymerization solution;
adding 12 parts by weight of graphene oxide into 40 parts by weight of methyl formamide, and performing ultrasonic dispersion for 2.5 hours to obtain a graphene dispersion liquid;
adding 2.5 parts by weight of NDZ-201 into the polymerization solution, then adding into the graphene dispersion solution, and uniformly mixing with ultrasonic dispersion through high-speed stirring, wherein the stirring speed is 1000r/min, the stirring time is 20min, the ultrasonic power is 200W, and the ultrasonic time is 15min to obtain the heat conduction material.
Comparative example 2
The preparation process of high heat conductivity PCR reaction tube is the same as that in example 7 except that:
and (2) a process: and (3) soaking the pretreated PCR reaction tube in the heat conduction material in the comparative example 1 for 10h for surface treatment, and drying to obtain the high-heat-conductivity PCR reaction tube.
Comparative example 3
A PCR reaction tube without surface treatment was used as comparative example 3.
Test example 1
1. Determination of infrared spectrum of modified graphene
The test adopts a Bruker Optics VERTEX-70/70v Fourier external spectrometer to characterize the sample, and the measurement range is 4000--1。
Fig. 1 is an infrared spectrum of the modified graphene in example 2. As can be seen from FIG. 1, the infrared spectrum of the modified graphene is 3628cm relative to that of the unmodified graphene oxide-1A strong characteristic absorption peak appears nearby, which is the stretching vibration of phenolic hydroxyl in neohesperidin; at 2985cm-1The nearby characteristic absorption peak is the telescopic vibration of the alkane; at 1759cm-1The strong characteristic absorption peak appearing nearby is the stretching vibration of the ester bond; at 1718cm-1The characteristic absorption peak appearing nearby is stretching vibration of carbonyl; at 974cm-1The characteristic absorption peak appearing nearby is the stretching vibration of ester cyclic ether; therefore, the modified graphene is obtained by modifying the graphene oxide with neohesperidin.
2. Determination of dispersion stability of modified graphene
The phase change cycle test is adopted in the test to determine the dispersion stability of the graphene oxide before and after modification; and dispersing the graphene oxide before and after modification in DMF, and observing whether the test sample is agglomerated or not after 30 phase change cycles, wherein unmodified graphene oxide is used as a control group.
As can be seen from table 1, the control group and examples 1 to 3 all have good dispersibility in the DMF solvent at 0 phase change cycle, and after 10 phase change cycles, the control group slightly agglomerated, while the modified graphene in examples 1 to 3 all had good dispersibility; after 30 phase change cycles, no obvious agglomeration or sedimentation phenomenon occurs in the modified graphene in the examples 1 to 3, the modified graphene in the example 2 has good dispersibility, and the control group has serious obvious agglomeration or sedimentation phenomenon, so that the modified graphene obtained by modifying the graphene oxide with neohesperidin has excellent dispersion stability.
Test example 2
1. Measurement of Heat conductivity of PCR reaction tube
The test adopts a steady state method, and the test temperature is measured to be 80 ℃ by a YBF-3 type (Hangzhou Dahua instrument manufacturing Co., Ltd.) flat plate heat conductivity coefficient tester.
FIG. 2 shows the thermal conductivity of the PCR reaction tube. As can be seen from FIG. 2, the thermal conductivity of the PCR reaction tubes of examples 7-11 was higher than 1.75W/(m.K), and compared to comparative example 3, the thermal conductivity of the PCR reaction tube surface-treated with the heat conductive material was increased by 11 times; comparing example 9 with comparative example 2, and example 12 with example 13, the thermal conductivity of example 9 is much higher than that of comparative example 2, and the thermal conductivity of example 12 is higher than that of example 13, which shows that the modified graphene is obtained by modifying graphene oxide with neohesperidin, and the modified graphene is used as a component of a thermal conductive material and coated on the surface of a PCR reaction tube, so that the thermal conductivity of the PCR reaction tube is improved; comparing example 9 with example 12, example 13 with comparative example 2, example 12 has a higher thermal conductivity than example 9, and example 13 has a higher thermal conductivity than comparative example 2, which shows that the addition of 1, 3-dibutoxy-2-propanol acetate to the thermal conductive material further improves the thermal conductivity of the PCR reaction tube, which results in higher thermal conductivity of the PCR reaction tube, and the addition of modified graphene and 1, 3-dibutoxy-2-propanol acetate at the same time significantly improves the thermal conductivity of the PCR reaction tube.
2. Determination of anti-biocontamination Properties of PCR reaction tubes
This experiment was performed on a BIACORE3000(Sweden BIACORE AB) instrument. Bovine Serum Albumin (BSA) was dissolved in PBS buffer (137mM NaCl, 2.7mM KCl, 2mM KH)2PO4And 10mM Na2HPO4pH7.4) was prepared for protein adsorption experimental analysis. At the beginning of the experiment, the channel was washed with PBS at a flow rate of 0.05mL/min, after the baseline was stabilized, BSA solution (1mg/mL) was passed through the corresponding channel, and after 10min, the channel was washed with PBS, and the amount of protein adsorbed on the surface of the PCR reaction tube was calculated from the change in refractive index (RU) before and after protein adsorption. A variation of about 1000 RU generally indicates a PCR reaction tube surface of 100ng/cm2The mass of the protein changes.
FIG. 3 shows the amount of protein adsorbed on the surface of a PCR reaction tube. The test groups corresponding to the curves a, b, c, d, e, f are example 7, example 9, example 12, example 13, comparative example 2 and comparative example 3, respectively, and it can be seen from FIG. 3 that the adsorption amount of BSA on the surface of the PCR reaction tube increases and then decreases with the increase of time in example 7, example 9 and example 12, in contrast, the decrease of the adsorption amount of BSA on the surfaces of the PCR reaction tubes in example 13, comparative example 2 and comparative example 3 was not significant, comparing example 9 with comparative example 2, and example 12 with example 13, the adsorption amount of BSA in example 9 was lower than that in comparative example 2, the adsorption amount of BSA in example 12 was lower than that in example 13 with the increase of time, the method shows that the neohesperidin is adopted to modify the graphene oxide to obtain the modified graphene, and the modified graphene is used as a component of a heat conduction material and coated on the surface of the PCR reaction tube, so that the biological pollution resistance of the PCR reaction tube is improved; comparing example 9 with example 12, example 13 with comparative example 2, the BSA adsorption amount of example 12 is not much different from example 9 and slightly decreases, and the BSA adsorption amount of example 13 is not significantly different from comparative example 2 and slightly decreases, which shows that the addition of 1, 3-dibutoxy-2-propanol acetate in the heat conductive material has little effect on the anti-bio-contamination performance of the PCR reaction tube; comparing example 7, example 9, example 12, example 13 and comparative example 3, the adsorption amount of BSA in examples 7, 9, 12 and 13 was lower than that in comparative example 3 with the increase of time, which shows that the anti-bio-contamination performance of the PCR reaction tube is improved by treating the surface of the PCR reaction tube with the heat conductive material prepared by the present invention.
3. Determination of adhesion between PCR reaction tube and heat conducting material
The invention tests the adhesion between the PCR reaction tube and the heat conducting material according to ISO 2409 and 2007 cross-cut method.
It can be seen from table 2 that the adhesion grades of examples 7-13 are all 0 grade, and all have good adhesion, that is, the thermal conductive material is coated on the surface of the PCR reaction tube by using plasma and immersion technology, so that the thermal conductive material and the PCR reaction tube have good binding ability, and the PCR reaction tube has excellent physicochemical properties.
4. Determination of water resistance of PCR reaction tube
In the test, the mass changes of samples with different soaking times are measured according to HG/T3344-2012, and the water absorption rate calculation formula is as follows:
W=(m1-m0)/(m0)×100%
in the formula: m is0Mass (g) of the sample before immersion; m is1The mass (g) of the sample after immersion.
FIG. 4 shows water absorption of PCR reaction tubes. As can be seen from fig. 4, the water absorption rates of example 7, example 9 and comparative example 2 have gradually increasing trends with increasing soaking time, but the trend is slower than that of comparative example 3; the increasing trend of the water absorption of the embodiment 12 and the embodiment 13 is not obvious; after soaking for 80h, the water absorption of examples 12 and 13 is lower than 0.22%; comparing example 9 with comparative example 2, and example 12 with example 13, the change trend of the water absorption of example 9 is not significantly different from that of comparative example 2, and the change trend of example 12 is not significantly different from that of example 13, which shows that the modified graphene obtained by modifying graphene oxide with neohesperidin has little influence on the water absorption of the PCR reaction tube when the modified graphene is used as a component of the heat conductive material and coated on the surface of the PCR reaction tube; comparing example 9 with example 12, example 13 with comparative example 2, the water absorption of example 12 has a lower trend than example 9, and the water absorption of example 13 has a lower trend than comparative example 2, which shows that the addition of 1, 3-dibutoxy-2-propanol acetate in the heat conductive material can make the PCR reaction tube have better water-resistant effect, i.e. better barrier property to water molecules, so as to prolong the service life of the PCR reaction tube; comparing example 12 with comparative example 3, the water absorption of example 12 is much lower than that of comparative example 3, which shows that the water resistance of the PCR reaction tube is improved by using the heat conductive material to perform surface treatment on the PCR reaction tube.
5. Determination of abrasion resistance of PCR reaction tube
In the test, an HSR-2M high-speed reciprocating friction and wear testing machine is used for testing the tribological performance of the prepared sample; during the test, a GCrl5 bearing steel ball with the diameter of 6mm is used as a pair grinding pair, and the test parameters are as follows: reciprocating distance Smm, friction frequency 4.2Hz, loading load SN, test time 30min, and 5 groups of parallel experiments. The wear rate calculation formula is as follows:
V=(m1-m2)/t
in the formula: v is the wear rate (g/min) of the sample; m is1Mass (g) of the sample before rubbing; m is2Mass (g) of the sample after rubbing; t is rubbing time (min).
FIG. 5 shows the wear rate of the PCR reaction tube. As can be seen from FIG. 5, the wear rates of examples 7-11 were less than 7.2X 10-5g/min which is far higher than that of a comparative example 3, comparing example 9 with that of a comparative example 2, and comparing example 12 with that of an example 13, wherein the wear rate of the example 9 is lower than that of the comparative example 2, and the wear rate of the example 12 is lower than that of the example 13, which shows that the modified graphene is obtained by modifying the graphene oxide with the neohesperidin and is coated on the surface of the PCR reaction tube as a component of a heat conduction material, so that the wear resistance of the PCR reaction tube is improved; comparing example 9 with example 12, example 13 with comparative example 2, the wear rate of example 12 is lower than that of example 9, and the wear rate of example 13 is lower than that of comparative example 2, which shows that the addition of 1, 3-dibutoxy-2-propanol acetate in the heat conductive material has a further improvement in the wear resistance of the PCR reaction tube; comparing example 12 with comparative example 3, the wear rate of example 12 is much lower than that of comparative example 3The proportion 3 shows that the modified graphene and the 1, 3-dibutoxy-2-propanol acetate are added into the heat conduction material at the same time, and the surface treatment is carried out on the PCR reaction tube, so that the wear resistance of the PCR reaction tube is obviously improved.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (9)
1. A preparation process of a high-thermal-conductivity PCR reaction tube comprises the following steps:
the process 1 comprises the following steps: carrying out plasma pretreatment on the PCR reaction tube to obtain a pretreated PCR reaction tube;
and (2) a process: soaking the pretreated PCR reaction tube in a heat conduction material for surface treatment to obtain a high-thermal-conductivity PCR reaction tube;
the heat conduction material comprises modified graphene, an organic polymer, a solvent and a chemical auxiliary agent;
the modified graphene is prepared from neohesperidin modified graphene oxide.
2. The process according to claim 1, wherein the thermal conductivity of the PCR reaction tube is as follows: in the heat conduction material, by weight, 7-15 parts of modified graphene, 10-25 parts of organic polymer, 40-80 parts of solvent and 0.5-5 parts of chemical auxiliary agent are added.
3. The process according to claim 1, wherein the thermal conductivity of the PCR reaction tube is as follows: the organic polymer is one or a combination of a plurality of polyvinylpyrrolidone, urea resin, polymethyl acrylate and polyethylene glycol.
4. The process according to claim 1, wherein the thermal conductivity of the PCR reaction tube is as follows: the solvent is one of methyl formamide, methanol, toluene, dichloromethane and n-butanol.
5. The process according to claim 1, wherein the thermal conductivity of the PCR reaction tube is as follows: the chemical auxiliary agent comprises a coupling agent; the coupling agent is one of silane coupling agent or titanate coupling agent.
6. The process according to claim 1, wherein the thermal conductivity of the PCR reaction tube is as follows: the chemical auxiliary agent also comprises 1, 3-dibutoxy-2-propanol acetate.
7. The process according to claim 1, wherein the thermal conductivity of the PCR reaction tube is as follows: in the process 2, the soaking time is 5-10 hours.
8. Use of the modified graphene as claimed in claim 1 for improving the anti-biocontamination performance of a PCR reaction tube.
9. Use of the modified graphene as claimed in claim 1 for improving wear resistance of a PCR reaction tube.
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