Graphene self-adhesive glue, cold adhesive tape containing graphene self-adhesive glue and preparation method of cold adhesive tape

Abstract

The invention relates to the technical field of analytical chemistry, and particularly discloses graphene self-adhesive glue, a cold adhesive tape containing the graphene self-adhesive glue and a preparation method of the cold adhesive tape. The graphene self-adhesive is specifically prepared from the following components in parts by weight: 48 to 58 parts of resin, 12 to 18 parts of graphene, 4 to 8 parts of a plasticizer, 3 to 7 parts of an aluminate coupling agent, 1 to 5 parts of filler and 0.4 to 1.2 parts of an auxiliary agent, the auxiliary agent is any one or two of a maleic anhydride-acrylic acid copolymer and a styrene-maleic anhydride copolymer. The graphene self-adhesive glue prepared according to the raw material formula provided by the invention is used for preparing the cold adhesive tape, and the cold adhesive tape has excellent mechanical properties, heat resistance and corrosion and aging resistance.

Description

Technical Field

[0001] The present application relates to the technical field of analytical chemistry, and in particular to a graphene self-adhesive, a cold adhesive tape containing the graphene self-adhesive, and a preparation method thereof. Background Art

[0002] At present, more than 100 million tons of metal are scrapped due to corrosion every year in the world, and the loss of metal structures, equipment and materials caused by corrosion is approximately equivalent to 20%-40% of the metal production in that year. In order to solve the above problems, people use various technologies to slow down the speed of corrosion. For example, anti-corrosion paint is applied on the metal surface to form a protective layer, or cold adhesive tape is used to wrap metal pipes. Among them, cold adhesive tape refers to adhesive tape used for anti-corrosion wrapping. Wrapping metal pipes with cold adhesive tape is suitable for the anti-corrosion and repair of related parts in various fields such as petroleum, natural gas, chemical industry, water supply and drainage pipelines, construction bridges, etc.

[0003] Common cold adhesive tape materials include polypropylene fiber, glass fiber, etc. Among them, polypropylene fiber has relatively stable chemical properties, and although glass fiber has strong heat resistance, good corrosion resistance and high mechanical strength, it is brittle and has poor wear resistance. Most of the existing anti-corrosion cold adhesive tapes simply stick these materials together, and have defects in wear resistance, adhesion and corrosion resistance. Although they can meet certain anti-corrosion requirements in the initial stage of use, the anti-corrosion ability will decrease as the use time increases. Summary of the invention

[0004] In order to improve the anti-corrosion and anti-aging performance of cold adhesive tape materials, the present application provides a graphene self-adhesive, a cold adhesive tape containing the graphene self-adhesive, and a preparation method thereof.

[0005] The present application provides a graphene self-adhesive, which specifically comprises the following components in parts by weight: 48-58 parts of resin, 12-18 parts of graphene, 4-8 parts of plasticizer, 3-7 parts of aluminate coupling agent, 1-5 parts of filler, and 0.4-1.2 parts of auxiliary agent; the auxiliary agent is any one or two of maleic anhydride acrylic acid copolymer and styrene maleic anhydride copolymer.

[0006] The present application utilizes the above technical solution to prepare a graphene self-adhesive prepared with resin, graphene, plasticizer, aluminate coupling agent, filler and additive as raw material formula for preparing a cold adhesive tape, which has excellent mechanical properties, heat resistance and anti-corrosion and anti-aging properties.

[0007] The highly saturated structure of graphene self-adhesive and the high stability of graphene are used in combination with other raw materials to make it have high chemical invariance, which greatly avoids the diffusion of corrosive media in graphene self-adhesive, making the material have excellent corrosion resistance to most inorganic acids and organic acids, and resistant to alkaline solutions, giving it excellent anti-corrosion and anti-aging properties.

[0008] Preferably, the graphene self-adhesive specifically comprises the following components in parts by weight: 52-58 parts of resin, 15-18 parts of graphene, 4-6 parts of plasticizer, 5-7 parts of coupling agent, 1-2 parts of filler, and 0.4-0.8 parts of additive.

[0009] Preferably, the resin is one or more of coumarone resin, terpene resin and rosin resin.

[0010] Preferably, the resin is coumarone resin and rosin resin in a weight ratio of 11:(1-5).

[0011] In a specific embodiment, the weight ratio of the coumarone resin to the rosin resin may be 11:1, 11:3, or 11:5.

[0012] In some specific embodiments, the weight ratio of the coumarone resin to the rosin resin may also be 11:(1-3) or 11:(3-5).

[0013] Through experimental analysis, it can be known that the present application uses the above-mentioned weight ratio of coumarone resin and rosin resin as the resin raw materials in the graphene self-adhesive, which further improves the mechanical properties, heat resistance and anti-corrosion and anti-aging properties of the cold adhesive tape.

[0014] Preferably, the plasticizer is aromatic oil and dimethyl phthalate in a weight ratio of 9:(1-7).

[0015] Preferably, the plasticizer is aromatic oil and dimethyl phthalate in a weight ratio of 9:(3-5).

[0016] In a specific embodiment, the weight ratio of the aromatic oil to dimethyl phthalate can be 9:1, 9:3, 9:4, 9:5, or 9:7.

[0017] In some specific embodiments, the weight ratio of the aromatic oil to dimethyl phthalate can also be 9:(1-3), 9:(1-4), 9:(1-5), 9:(3-4), 9:(3-7), 9:(4-5), 9:(4-7), 9:(5-7).

[0018] Through experimental analysis, it can be known that the aromatic oil and dimethyl phthalate in the above weight ratio of the present application are used as plasticizers in the graphene self-adhesive, which further improves the mechanical properties, heat resistance and anti-corrosion and anti-aging properties of the cold adhesive tape.

[0019] Preferably, the filler is selected from one of calcium carbonate, titanium dioxide, zinc oxide, zinc sulfide, lithopone, barium sulfate and silicon dioxide.

[0020] In a second aspect, the present application provides a cold adhesive tape, which includes, from top to bottom, a PVDF fluoroalloy film layer, the above-mentioned graphene self-adhesive layer, and a PET peelable film layer.

[0021] Preferably, the PVDF fluoroalloy membrane consists of a layer A with a thickness of 0.028-0.032 mm and a layer B with a thickness of 0.068-0.072 mm, and the layer A consists of the following components in parts by weight: 65-74 parts of a thermoplastic fluoropolymer and 26-35 parts of an acrylic polymer; the layer B consists of the following components: 12-28 parts of a thermoplastic fluoropolymer, 4-28 parts of an acrylic polymer, 32-49 parts of polyethylene and an ethylene-methyl acrylate blend, and 10-28 parts of a mineral pigment.

[0022] In a third aspect, the present application provides a method for preparing the above-mentioned cold adhesive tape, characterized in that the method specifically comprises the following steps: stirring and mixing the resin and the plasticizer at 180-220° C., after swelling and stirring evenly, adding the aluminate coupling agent, the graphene, the filler, and the auxiliary agent, stirring evenly, cooling to 165-170° C., and obtaining the graphene self-adhesive for standby use; The materials of the two layers A and B in the PVDF fluorine alloy membrane are mixed separately, and then the two layers are co-extruded to obtain the PVDF fluorine alloy membrane; The graphene self-adhesive layer and the PVDF fluorine alloy film layer with a thickness of 0.28-0.32 mm are sequentially coated on the surface of the PET peelable film layer by coating and thermal compounding.

[0023] In summary, the technical solution of this application has the following effects: The graphene self-adhesive prepared by the present application using resin, graphene, plasticizer, aluminate coupling agent, filler and additive as raw material formula is used to prepare cold adhesive tape, and the cold adhesive tape has excellent mechanical properties, heat resistance and anti-corrosion and anti-aging properties.

[0024] This application further improves the mechanical properties, heat resistance, and anti-corrosion and anti-aging properties of the material by screening and optimizing the types of raw materials such as resins and plasticizers. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a schematic diagram of the cold adhesive tape structure in Example 1 of the present application.

[0026] Figure 2 This is a picture of the finished product of the cold adhesive tape in Example 1 of the present application. DETAILED DESCRIPTION

[0027] The raw materials used in this application, coumarone resin (CAS: 2011-09), terpene resin (CAS: 9003-74-1), and rosin resin (CAS: 18-4212-8512), were purchased from Shanghai Sanlian Industrial Co., Ltd.; graphene was purchased from Nangong Longjian Alloy Material Co., Ltd.; cycloalkane oil and aromatic oil were purchased from Shandong Taichang Petrochemical Technology Co., Ltd.; maleic anhydride acrylic acid copolymer and styrene maleic anhydride copolymer were purchased from Shanghai Gaoming Chemical; aluminate coupling agent was purchased from Kangjin Chemical; PET film layer peelable film layer-PET140 was purchased from BASF, Germany; the remaining raw materials and reagents can be obtained through commercial purchase.

[0028] The present application is further described in detail below in conjunction with examples, comparative examples and performance testing experiments. These examples should not be construed as limiting the scope of protection claimed in the present application. Example

[0029] Examples 1-3 Embodiments 1-3 each provide a cold adhesive tape.

[0030] The difference between the above embodiments is that the usage of each raw material component in the graphene self-adhesive in the cold adhesive tape is different, as shown in Table 1.

[0031] The structure of the cold adhesive tape in the above embodiment is shown as follows Figure 1 As shown, from top to bottom, it includes a PVDF fluoroalloy film layer, the above-mentioned graphene self-adhesive layer, and a PET peelable film layer.

[0032] The specific preparation process of the cold adhesive tape in the above embodiment is as follows: (1) Preparation of graphene self-adhesive According to the weight of each raw material in Table 1, the resin (composed of coumarone resin and rosin resin in a weight ratio of 11:3) and the plasticizer (composed of aromatic oil TC-5 and dimethyl phthalate in a weight ratio of 9:4) were stirred at 200°C for 2h. After swelling and stirring, aluminate coupling agent, graphene, calcium carbonate filler with a particle size of 600 mesh, and maleic anhydride acrylic acid copolymer additive were added and stirred to obtain a uniform and stable viscous self-adhesive liquid, which was cooled to 165-170°C for standby use.

[0033] (2) Composite of PET film and graphene self-adhesive The graphene self-adhesive in step (1) is evenly coated on the surface of the PET 140 film (peelable film layer) by an automatic glue coating machine, and dried in a drying oven. The thickness of the self-adhesive layer is 0.30 mm. The coating equipment is a device that can melt the solid hot melt adhesive and transport the melted liquid adhesive to a specific component through a pressurizing device for coating the substrate, and has the function of automatically controlling and automatically tracking the production line speed.

[0034] (3) Composite with PVDF fluorine membrane The thermoplastic fluorine-containing polymer (vinylidene fluoride-trifluoroethylene copolymer) and acrylic polymer (polymethyl methacrylate) are added into a high-speed mixer to be uniformly mixed; then, they are added into a twin-screw extruder for mixing, and extruded, cooled, and pelletized at a temperature of 240°C and a rotation speed of 350rpm to obtain a composite film A layer; Thermoplastic fluorine-containing polymer (vinylidene fluoride-trifluoroethylene copolymer), acrylic polymer (polymethyl methacrylate), PE / EMA blend and titanium dioxide mineral pigment are added to a twin-screw extruder for mixing, and extruded, cooled and pelletized at a temperature of 240°C and a rotation speed of 450rpm to obtain the material of layer B of the composite film; the A / B two-layer material is co-extruded into a 0.09-0.11mm thick PVDF fluorine film using a T-type die; The PVDF fluoroalloy film is placed in a screw extruder at a temperature of 150°C, and the raw materials are melted into a fluid state, and then transported to a coating die through a high-precision metering pump. After the coating die, it is evenly compounded on the PET film-graphene self-adhesive substrate in step (2) according to the preset material thickness (gram weight). After compounding, it passes through a cooling roller and a release film to a compounding pressure roller, and the tension is adjusted by a tension system. At the same time, the winding speed is controlled to synchronize it with the compounding speed, and the winding device is used for neat winding. The coating and compounding process is required to be carried out in a clean workshop, wherein the cleanliness level of the coating and compounding unit is 10,000, and the cleanliness level of the compounding unit is 100,000.

[0035] like Figure 2 Shown is a finished product image of the cold adhesive tape in Example 2 of the present application.

[0036] Table 1 Amount of each raw material component in graphene self-adhesive Embodiment 4-8 Embodiments 4-8 each provide a cold adhesive tape.

[0037] The difference between the above embodiment and embodiment 2 is that the type of resin in the cold adhesive tape is different, as shown below.

[0038] In Example 4: the resin is coumarone resin.

[0039] In Example 5: the resin is composed of terpene resin and rosin resin in a weight ratio of 11:3.

[0040] In Example 6: the resin is composed of coumarone resin and rosin resin in a weight ratio of 11:7.

[0041] In Example 7: the resin is composed of coumarone resin and rosin resin in a weight ratio of 11:1.

[0042] In Example 8: the resin is composed of coumarone resin and rosin resin in a weight ratio of 11:5.

[0043] The remaining components, the amounts of the components and the preparation method of the cold adhesive tape in the above embodiment are the same as those in Example 2.

[0044] Examples 9-13 Embodiments 9-13 each provide a cold adhesive tape.

[0045] The difference between the above embodiment and embodiment 2 is that the types of plasticizers in the cold adhesive tape are different, as shown below.

[0046] In Example 9: the plasticizer is aromatic oil TC-5.

[0047] In Example 10: the plasticizer is composed of cyclohexane oil (Xinjiang Karamay 4006) and dimethyl phthalate in a weight ratio of 9:4.

[0048] In Example 11: the plasticizer is composed of aromatic oil TC-5 and dimethyl phthalate in a weight ratio of 9:8.

[0049] In Example 12: the plasticizer is composed of aromatic oil TC-5 and dimethyl phthalate in a weight ratio of 9:1.

[0050] In Example 13: the plasticizer is composed of aromatic oil TC-5 and dimethyl phthalate in a weight ratio of 9:7.

[0051] The remaining components, the amounts of the components and the preparation method of the cold adhesive tape in the above embodiment are the same as those in Example 2.

[0052] Comparative Example Comparative Example 1-2 This comparative example provides a kind of cold adhesive tape respectively.

[0053] The difference between the comparative example and Example 2 is that the amounts of the raw material components in the graphene self-adhesive in the cold adhesive tape are different, as shown in Table 1.

[0054] The types of components and the preparation method of the cold adhesive tape in the above comparative example are the same as those in Example 2.

[0055] Performance testing (1) Tensile strength: Based on GB / T 1040 as the reference standard, the longitudinal tensile strength of the cold adhesive tape specimen (25 mm × 15 mm) was tested.

[0056] (2) Peel strength: According to GB / T 2792-2014, the peel strength of the cold adhesive tape sample was tested.

[0057] (3) Heat resistance: A cold adhesive tape sample (25 mm × 15 mm) was placed in an oven at 80°C for 60 min. The size of the sample was tested and its shrinkage was calculated: shrinkage = (length of the sample after heat treatment - 25 mm) / 15 mm × 100%.

[0058] (4) Acid resistance test: The cold adhesive tape sample was immersed in a 0.005 mol / L sulfuric acid solution for 360 h, and the peel strength loss of the sample before and after the test was calculated to evaluate the acid resistance of the sample.

[0059] (5) Alkali resistance test: The cold adhesive tape sample was immersed in a 0.01 mol / L sodium hydroxide solution for 360 h, and the peel strength loss of the sample before and after the test was calculated to evaluate the alkali resistance of the sample.

[0060] (6) Salt water resistance test: The cold adhesive tape sample was immersed in a 3% sodium chloride solution for 720 hours, and the peel strength loss of the sample before and after the test was calculated to evaluate the salt water resistance of the sample.

[0061] Test results: as shown in Table 2.

[0062] Table 2 Performance test results of cold adhesive tape in Examples 1-13 and Comparative Examples 1-2 Combined with the test results of Table 2, by comparing the test results of Examples 1-13 with Comparative Examples 1-2, this application uses 48-58 parts of resin, 12-18 parts of graphene, 4-8 parts of plasticizer, 3-7 parts of aluminate coupling agent, 1-5 parts of filler, and 0.4-1.2 parts of auxiliary agent as the raw material components of graphene self-adhesive, and the prepared cold adhesive tape has a tensile strength of ≥48MPa, a peel strength of ≥6.52N / mm, a heat shrinkage rate of ≤7.6%, and strong acid resistance, alkali resistance, and salt water resistance. The above test results show that the graphene self-adhesive prepared using the raw material formula provided by the application is used to prepare a cold adhesive tape, which has excellent mechanical properties, heat resistance, and anti-corrosion and anti-aging properties, so that the cold adhesive tape has a longer service life and better use effect.

[0063] By comparing the test results of Examples 1-3 with those of Comparative Examples 1-2, it can be seen that the amount of raw material components in the graphene self-adhesive has a great influence on the performance of the cold adhesive tape. The present application obtains a cold adhesive tape with excellent mechanical properties, heat resistance, and anti-corrosion and anti-aging properties by reasonably controlling the amount of each raw material component.

[0064] By comparing the test results of Examples 2 and 4-8, the present application uses coumarone resin and rosin resin in a weight ratio of 11:(1-5) as the resin raw materials in the graphene self-adhesive, which further improves the mechanical properties, heat resistance and anti-corrosion and anti-aging properties of the cold adhesive tape.

[0065] By comparing the test results of Examples 2 and 4-8, the present application uses aromatic oil and dimethyl phthalate in a weight ratio of 9:(3-5) as plasticizers in the graphene self-adhesive, which further improves the mechanical properties, heat resistance, and anti-corrosion and anti-aging properties of the cold adhesive tape.

[0066] Although the present invention has been described in detail above with general descriptions and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements may be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A graphene self-adhesive, characterized in that: Specifically, the composition comprises the following components in parts by weight: 48-58 parts of resin, 12-18 parts of graphene, 4-8 parts of plasticizer, 3-7 parts of aluminate coupling agent, 1-5 parts of filler, and 0.4-1.2 parts of auxiliary agent; the auxiliary agent is any one or two of maleic anhydride acrylic acid copolymer and styrene maleic anhydride copolymer.

2. The graphene self-adhesive according to claim 1, characterized in that: Specifically, the composition comprises the following components in parts by weight: 52-58 parts of resin, 15-18 parts of graphene, 4-6 parts of plasticizer, 5-7 parts of coupling agent, 1-2 parts of filler and 0.4-0.8 parts of auxiliary agent.

3. The graphene self-adhesive according to claim 1, characterized in that: The resin is one or more of coumarone resin, terpene resin and rosin resin.

4. The graphene self-adhesive according to claim 1, characterized in that: The resin is coumarone resin and rosin resin in a weight ratio of 11:(1-5).

5. The graphene self-adhesive according to claim 1, characterized in that: The plasticizer is aromatic oil and dimethyl phthalate in a weight ratio of 9:(1-7).

6. The graphene self-adhesive according to claim 5, characterized in that: The plasticizer is aromatic oil and dimethyl phthalate in a weight ratio of 9:(3-5).

7. The graphene self-adhesive according to claim 1, characterized in that: The filler is selected from one of calcium carbonate, titanium dioxide, zinc oxide, zinc sulfide, lithopone, barium sulfate and silicon dioxide.

8. A cold adhesive tape, characterized in that: The cold adhesive tape comprises, from top to bottom, a PVDF fluoroalloy film layer, a graphene self-adhesive layer according to any one of claims 1 to 7, and a PET peelable film layer.

9. The cold adhesive tape according to claim 8, characterized in that: The PVDF fluorine alloy membrane is composed of an A layer with a thickness of 0.028-0.032 mm and a B layer with a thickness of 0.068-0.072 mm. In parts by weight, the A layer is composed of the following components: 65-74 parts of thermoplastic fluoropolymer and 26-35 parts of acrylic polymer; the B layer is composed of the following components: 12-28 parts of thermoplastic fluoropolymer, 4-28 parts of acrylic polymer, 32-49 parts of polyethylene and ethylene-methyl acrylate blend, and 10-28 parts of mineral pigment.

10. The method for preparing the cold adhesive tape according to any one of claims 8 to 9, characterized in that: The specific steps include: The resin and the plasticizer are stirred and mixed at 180-220° C., and after swelling and stirring evenly, the aluminate coupling agent, the graphene, the filler, and the auxiliary agent are added, stirred evenly, and the temperature is lowered to 165-170° C. to obtain the graphene self-adhesive for standby use; The materials of the two layers A and B in the PVDF fluorine alloy membrane are mixed separately, and then the two layers are co-extruded to obtain the PVDF fluorine alloy membrane; The graphene self-adhesive layer and the PVDF fluorine alloy film layer with a thickness of 0.28-0.32 mm are sequentially coated on the surface of the PET peelable film layer by coating and thermal compounding.

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