Bio-based thumb glue for automobile and preparation method of bio-based thumb glue

Abstract

The invention discloses bio-based thumb glue for an automobile and a preparation method of the bio-based thumb glue. The thumb glue is prepared from the following raw materials in parts by weight: 60-70 parts of a high-melting-point bio-based premix, 10-20 parts of reinforced resin, 2-5 parts of a curing agent, 5-10 parts of reinforcing filler and 20-30 parts of a rheology modifier. The method comprises the following steps: 1) putting a high-melting-point bio-based premix into a reaction kettle, heating to 50 DEG C, sequentially adding reinforced resin, a curing agent and reinforcing filler, and stirring at 75 DEG C for 30 minutes at the speed of 200 revolutions per minute to obtain a mixture; (2) when the consistency of the sampled and tested mixture is 6.0-7.5, transferring the material in the reaction kettle into a kneading machine; and step 3) adding the rheology modifier into the kneading machine, mixing for 20 minutes at 40 DEG C at the speed of 20 revolutions per minute, sampling and testing the material, and discharging when the needle penetration is in the range of 100-250, thereby obtaining the bio-based thumb glue. According to the thumb glue and the method, the dependence on traditional o-benzene and p-benzene plasticizer raw materials can be reduced on the premise that the performance is not reduced.

Description

Technical Field

[0001] The invention relates to the technical field of automobile polymer materials, in particular to a bio-based thumb glue for automobiles and a preparation method thereof. Background Art

[0002] Thumb glue is a lump-shaped adhesive material designed for filling and repairing process holes, large gaps and local defects in automobile bodies. It can be cured after electrophoresis, intermediate coating and baking of topcoat, and play the role of repair, waterproof and dustproof. The construction of thumb glue is different from conventional adhesives. It does not use injection pumps and injection guns. Instead, it is kneaded by fingers to shape the thumb glue into the required size and shape, and then pressed and fixed at the bonding site. It has the characteristics of strong plasticity and easy operation.

[0003] In recent years, low-carbon and environmental protection have become the research direction in the field of automotive polymer materials technology. Reducing dependence on non-renewable materials by using environmentally friendly and renewable bio-based raw materials in the formula has become the future development trend of the industry. Currently, most similar products on the market use ortho-phthalate and para-phthalate plasticizers, and there is no relevant technology for bio-based thumb glue products.

[0004] In view of this, the present invention is proposed. Summary of the invention

[0005] The purpose of the present invention is to provide a bio-based thumb glue for automobiles and a preparation method thereof. By using renewable bio-based raw materials, the dependence on traditional ortho-phthalate and para-phthalate plasticizer raw materials can be reduced while ensuring that the performance is not reduced, thereby solving the above-mentioned technical problems existing in the prior art.

[0006] The objective of the present invention is achieved through the following technical solutions:

[0007] A bio-based thumb glue for automobiles is prepared from the following raw materials in parts by weight:

[0008] 60-70 parts of high melting point bio-based premix, 10-20 parts of reinforcing resin, 2-5 parts of curing agent, 5-10 parts of reinforcing filler and 20-30 parts of rheology regulator.

[0009] A method for preparing the bio-based thumb glue for automobiles of the present invention comprises:

[0010] According to the formula of the bio-based thumb glue for automobiles of the present invention, various raw materials are taken;

[0011] Step 1) putting a high melting point bio-based premix into a reactor, heating it to 50° C. to melt the high melting point bio-based premix, then adding a reinforcing resin, a curing agent and a reinforcing filler in sequence, stirring at a stirring speed of 200 revolutions per minute at 75° C. for 30 minutes to allow the reinforcing resin and the curing agent to react preliminarily, to obtain a mixture;

[0012] Step 2) when sampling and testing the consistency of the mixture obtained in step 1, when the test consistency is in the range of 6.0 to 7.5, the material in the reaction kettle is transferred to the kneader;

[0013] Step 3) Add a rheology modifier to the material in the kneader and set the kneading blade speed to 20 revolutions per minute, mix at 40° C. for 20 minutes, take samples to test the needle penetration of the material, and discharge the material when the needle penetration at 40° C. is within the range of 100 to 250, thereby obtaining the bio-based thumb glue.

[0014] Compared with the prior art, the bio-based thumb glue for automobiles and the preparation method thereof provided by the present invention have the following beneficial effects:

[0015] By using renewable bio-based raw materials, the dependence on traditional phthalates and para-phenylene plasticizer raw materials can be reduced while ensuring that performance is not reduced. The thumb glue significantly reduces the traditional formula's dependence on non-renewable raw materials such as phthalates and para-phenylene plasticizers; it can improve the operational convenience during construction. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0017] Figure 1 This is a performance test diagram of the bio-based thumb glue for automobiles provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0018] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in combination with the specific content of the present invention; it is obvious that the described embodiments are only part of the embodiments of the present invention, not all of the embodiments, which does not constitute a limitation of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the protection scope of the present invention.

[0019] First, the terms that may be used in this article are explained as follows:

[0020] The term “and / or” means that either or both of them can be realized at the same time. For example, X and / or Y means both “X” or “Y” and “X and Y”.

[0021] The terms "include", "comprises", "contains", "has" or other descriptions with similar semantics should be interpreted as non-exclusive inclusion. For example, including certain technical feature elements (such as raw materials, components, ingredients, carriers, dosage forms, materials, dimensions, parts, components, mechanisms, devices, steps, procedures, methods, reaction conditions, processing conditions, parameters, algorithms, signals, data, products or products, etc.) should be interpreted as including not only certain technical feature elements explicitly listed, but also other technical feature elements known in the art that are not explicitly listed.

[0022] The term "consisting of..." means excluding any technical feature elements not explicitly listed. If this term is used in a claim, it will make the claim closed, so that it does not contain technical feature elements other than the technical feature elements explicitly listed, except for the conventional impurities related to them. If this term only appears in a clause of a claim, it only limits the elements explicitly listed in the clause, and the elements recorded in other clauses are not excluded from the overall claim.

[0023] The term "parts by mass" refers to the mass ratio relationship between multiple components. For example, if it is described that component X is x parts by mass and component Y is y parts by mass, then the mass ratio of component X to component Y is x:y. 1 part by mass can represent any mass, for example, 1 part by mass can be represented as 1 kg or 3.1415926 kg. The sum of the parts by mass of all components is not necessarily 100 parts, but can be greater than 100 parts, less than 100 parts or equal to 100 parts. Unless otherwise specified, the parts, proportions and percentages described herein are all measured by mass.

[0024] When concentration, temperature, pressure, size or other parameters are expressed in the form of a numerical range, the numerical range should be understood to specifically disclose all ranges formed by the pairing of any upper limit, lower limit, and preferred value in the numerical range, regardless of whether the range is explicitly stated; for example, if a numerical range of "2 to 8" is stated, the numerical range should be interpreted as including ranges such as "2 to 7", "2 to 6", "5 to 7", "3 to 4 and 6 to 7", "3 to 5 and 7", "2 and 5 to 7", etc. Unless otherwise specified, the numerical ranges stated herein include both their end values ​​and all integers and fractions within the numerical range.

[0025] The scheme provided by the present invention is described in detail below. The contents not described in detail in the embodiments of the present invention belong to the prior art known to professionals in the field. If the specific conditions are not specified in the embodiments of the present invention, they are carried out according to the conventional conditions in the field or the conditions recommended by the manufacturer. If the manufacturers are not specified in the reagents or instruments used in the embodiments of the present invention, they are all conventional products that can be purchased commercially.

[0026] The embodiment of the present invention provides a bio-based thumb glue for automobiles, which is prepared from the following raw materials in parts by weight:

[0027] 60-70 parts of high melting point bio-based premix, 10-20 parts of reinforcing resin, 2-5 parts of curing agent, 5-10 parts of reinforcing filler and 20-30 parts of rheology regulator.

[0028] Preferably, in the above-mentioned thumb glue, the high melting point bio-based premix is ​​a mixture of high melting point modified bio-based plant ester and PVC resin in a mass ratio of 1:2 to 2.5.

[0029] Preferably, in the above thumb glue, the high melting point modified bio-based plant ester is prepared in the following manner, including:

[0030] Step 11) adding palm oil or coconut oil into a reaction kettle, adding polyethylene glycol diacrylate to the palm oil or coconut oil in a mass ratio of 5-7:0.7-1, and raising the temperature of the entire system to 90° C.;

[0031] Step 12) adding tetrabutylammonium propionate as a catalyst under the conditions of the above step, adjusting the pH value to a range of 8.5 to 9.5, and continuing the reaction at a speed of 400 revolutions per minute for 2 hours;

[0032] Step 13) Cooling the plant ester obtained after the reaction to 23° C. to obtain the high melting point modified bio-based plant ester.

[0033] Using tetrabutylammonium propionate catalyst, renewable bio-based raw materials such as palm oil or coconut oil are reacted with polyethylene glycol diacrylate to generate high-melting-point modified bio-based plant esters, which are then applied to the formula system of thumb glue to produce bio-based thumb glue products that meet the industry's environmental protection trends.

[0034] Preferably, in the above thumb glue, the high melting point bio-based premix is ​​prepared in the following manner, including:

[0035] Step 21) placing the high melting point modified bio-based plant ester into a reactor, adjusting the temperature to 50° C. and stirring at a speed of 300 revolutions per minute until the modified bio-based plant ester in the reactor is completely melted;

[0036] Step 22) adding PVC resin to the reactor in a mass ratio of 1:2 to 2.5 of the high melting point modified bio-based plant ester to the PVC resin, and continuing stirring, setting the speed to 200 revolutions per minute, and continuing stirring for 30 to 50 minutes to fully mix the PVC resin and the high melting point modified bio-based plant ester;

[0037] Step 23) During the mixing process, when the viscosity of the material in the reactor is observed to be in the range of 75,000 to 85,000 CPS, the heating is stopped and the material is allowed to cool and solidify, thereby obtaining a solid high melting point bio-based premix.

[0038] Preferably, in the above thumb glue, the reinforcing resin is isocyanate-modified bisphenol A diglycidyl ether.

[0039] Preferably, in the above thumb glue, the curing agent is N,N-dimethylbenzenesulfonamide.

[0040] Preferably, in the above thumb glue, the reinforcing filler is nano-silicon dioxide;

[0041] The rheology regulator is nano calcium carbonate.

[0042] The bio-based thumb glue for automobiles according to the embodiment of the present invention,

[0043] The embodiment of the present invention also provides a method for preparing the above-mentioned bio-based thumb glue for automobiles, comprising:

[0044] Take various raw materials according to the above formula of bio-based thumb glue for automobiles;

[0045] Step 1) putting a high melting point bio-based premix into a reactor, heating it to 50° C. to melt the high melting point bio-based premix, then adding a reinforcing resin, a curing agent and a reinforcing filler in sequence, stirring at a stirring speed of 200 revolutions per minute at 75° C. for 30 minutes to allow the reinforcing resin and the curing agent to react preliminarily, to obtain a mixture;

[0046] Step 2) when sampling and testing the consistency of the mixture obtained in step 1, when the test consistency is in the range of 6.0 to 7.5, the material in the reaction kettle is transferred to the kneader;

[0047] Step 3) Add a rheology modifier to the material in the kneader and set the kneading blade speed to 20 revolutions per minute, mix at 40°C for 20 minutes, take samples to test the needle penetration of the material, and discharge the material when the needle penetration at 40°C is within the range of 100 to 250 (0.1 mm), thereby obtaining the bio-based thumb glue.

[0048] Preferably, in step 2 of the above method, the mixture obtained in step 1 is tested using an emulsified asphalt slurry seal consistency tester;

[0049] In step 3, an asphalt penetration tester is used to take samples to test the penetration of the material.

[0050] Preferably, the high melting point bio-based premix in step 1 of the above method is prepared in the following manner, including:

[0051] Step 21) placing the high melting point modified bio-based plant ester into a reactor, adjusting the temperature to 50° C. and stirring at a speed of 300 revolutions per minute until the modified bio-based plant ester in the reactor is completely melted;

[0052] Step 22) adding PVC resin to the reactor in a mass ratio of 1:2 to 2.5 of the high melting point modified bio-based plant ester to the PVC resin, and continuing stirring, setting the speed to 200 revolutions per minute, and continuing stirring for 30 to 50 minutes to fully mix the PVC resin and the high melting point modified bio-based plant ester;

[0053] Step 23) During the mixing process, when the viscosity of the material in the reactor is observed to be in the range of 75000 to 85000 CPS, the heating is stopped, and the material is allowed to cool and solidify, thereby obtaining a solid high melting point bio-based premix;

[0054] The high melting point modified bio-based plant ester is prepared in the following manner, including:

[0055] Step 11) adding palm oil or coconut oil into a reaction kettle, adding polyethylene glycol diacrylate to the palm oil or coconut oil in a mass ratio of 5-7:0.7-1, and raising the temperature of the entire system to 90° C.;

[0056] Step 12) adding tetrabutylammonium propionate as a catalyst under the conditions of the above step, adjusting the pH value to a range of 8.5 to 9.5, and continuing the reaction at a speed of 400 revolutions per minute for 2 hours;

[0057] Step 13) Cooling the plant ester obtained after the reaction to 23° C. to obtain the high melting point modified bio-based plant ester.

[0058] The automotive bio-based thumb glue and preparation method of the embodiment of the present invention can reduce the dependence on traditional phthalate and paraben plasticizer raw materials while ensuring that the performance does not decrease by using renewable bio-based raw materials. The thumb glue significantly reduces the dependence of traditional formulas on non-renewable raw materials such as phthalate and paraben plasticizers; it can improve the convenience of operation during construction. During the kneading process of the construction personnel, the human body temperature is close to the melting point of the thumb glue, which will soften and reduce the hardness, making it easier to operate; when the thumb glue is pressed to the target part, as the temperature drops to the same level as the steel plate, the thumb glue will gradually solidify and harden. This feature ensures that even if there is severe bumps during subsequent transportation, the thumb glue will not fall off from the holes and gaps in the construction site, thereby improving the transportation resistance of the workpiece where the product is located on the assembly line.

[0059] In order to more clearly demonstrate the technical solution and technical effects provided by the present invention, the solution provided by the embodiment of the present invention is described in detail with specific embodiments below.

[0060] Example 1

[0061] This embodiment provides a bio-based thumb glue for automobiles, and the preparation method thereof comprises:

[0062] Step 11) Preparation of high melting point modified bio-based plant ester for high melting point bio-based premix: Add palm oil to the reactor, add polyethylene glycol diacrylate at a mass ratio of 5:1. Raise the temperature of the entire system to 90°C; under this condition, add tetrabutylammonium propionate as a catalyst, adjust the pH value to 8.5-9.5, and continue the reaction at a speed of 400 revolutions per minute for 2 hours. Discharge the reacted plant ester and cool it at room temperature of 23°C to obtain the desired high melting point modified bio-based plant ester.

[0063] Step 12) Prepare a high melting point bio-based premix: Place the modified high melting point bio-based plant ester prepared above into a reactor. Then adjust the temperature control device to 50°C and start the agitator with the speed set to 300 rpm. Wait until the high melting point modified bio-based plant ester in the reactor is completely melted. Add raw materials to the reactor in a mass ratio of 1:2 of high melting point modified bio-based plant ester to PVC resin, and continue stirring; set the speed to 200 rpm to ensure that the PVC resin and the high melting point modified bio-based plant ester are fully mixed for 40 minutes. Stop heating when the viscosity of the material in the reactor is in the range of 75,000 to 85,000 CPS. Subsequently, allow the material to cool and solidify to obtain a solid high melting point bio-based premix.

[0064] Step 13) Prepare bio-based thumb glue (each raw material is by weight): put 60 parts of high melting point bio-based premix into the reactor and heat it to 50°C to melt the premix. Then add 15 parts of reinforcing resin isocyanate-modified bisphenol A diglycidyl ether, 2 parts of curing agent N,N-dimethylbenzenesulfonamide, and 7 parts of reinforcing filler nano-silica in sequence. Set the stirring speed to 200 rpm and stir at 75°C for 30 minutes to allow the reinforcing resin and curing agent to react preliminarily. Use an emulsified asphalt slurry seal consistency tester to test the mixture. When the sample test consistency is in the range of 6.0 to 7.5, transfer the material in the reactor to the kneader. 20 parts of rheology modifier nano calcium carbonate were added and the kneading blade speed was set to 20 revolutions per minute, mixed at 40°C for 20 minutes, and sampled and tested using an asphalt penetration tester. When the penetration at 40°C was within the range of 100 to 250 (0.1 mm), the material was discharged to obtain the bio-based thumb glue described above.

[0065] Example 2

[0066] This embodiment provides a bio-based thumb glue for automobiles, and the preparation method thereof comprises:

[0067] Step 11) Prepare a high melting point modified bio-based plant ester for a high melting point bio-based premix: Add coconut oil to a reactor and add polyethylene glycol diacrylate at a mass ratio of 7:1. Raise the temperature of the entire system to 90°C. Under this condition, add tetrabutylammonium propionate as a catalyst, adjust the pH value to 8.5 to 9.5, and allow the reaction to continue for 2 hours at 400 rpm. Cool the resulting plant ester at 23°C to obtain the desired high melting point modified bio-based plant ester.

[0068] Step 12) Prepare a high melting point bio-based premix: Place the modified high melting point bio-based plant ester prepared above into a reactor. Then adjust the temperature control device to 50°C and start the stirrer with the speed set to 300 rpm. Wait until the high melting point modified bio-based plant ester in the reactor is completely melted. Add raw materials to the reactor at a mass ratio of 1:2.5 of high melting point modified bio-based plant ester to PVC resin, and continue stirring. Set the speed to 200 rpm to ensure that the PVC resin and the high melting point modified bio-based plant ester are fully mixed for 50 minutes. Stop heating when the viscosity of the material in the reactor is in the range of 75,000 to 85,000 CPS. Subsequently, allow the material to cool and solidify to obtain a solid high melting point bio-based premix.

[0069] Step 13) Prepare bio-based thumb glue (each raw material is by weight): put 70 parts of high melting point bio-based premix into the reactor and heat it to 50°C to melt the premix. Then add 18 parts of reinforcing resin isocyanate-modified bisphenol A diglycidyl ether, 2.5 parts of curing agent N,N-dimethylbenzenesulfonamide, and 5 parts of reinforcing filler nanosilica in sequence. Set the stirring speed to 200 revolutions per minute and stir at 75°C for 30 minutes to allow the reinforcing resin and curing agent to react preliminarily. Use an emulsified asphalt slurry seal consistency tester to test the mixture. When the sample test consistency is in the range of 6.0 to 7.5, transfer the material in the reactor to the kneader. 30 parts of rheology modifier nano calcium carbonate were added and the kneading blade speed was set to 20 revolutions per minute. The mixture was mixed at 40°C for 20 minutes. The asphalt penetration tester was used to take samples for testing. When the penetration at 40°C was within the range of 100 to 250 (0.1 mm), the material was discharged to obtain the bio-based thumb glue described above.

[0070] (II) Preparation method of comparative thumb glue

[0071] Comparative Example 1

[0072] Step 1) Add diisononyl phthalate and PVC resin to a reactor in a mass ratio of 1:2 and continue stirring. Set the speed to 200 revolutions per minute to ensure that the PVC resin and the plasticizer are fully mixed for 45 minutes. Stop stirring when the viscosity of the material in the reactor is within the range of 75000 to 85000 CPS. Obtain a premix.

[0073] Step 2) 70 parts of the premix are put into the reactor, and then 20 parts of the reinforcing resin isocyanate-modified bisphenol A diglycidyl ether, 2.5 parts of the curing agent N,N-dimethylbenzenesulfonamide, and 5 parts of the reinforcing filler nano-silica are added in sequence. The stirring speed is set to 200 rpm, and the reinforcing resin and the curing agent are stirred at 75°C for 30 minutes to allow the reinforcing resin and the curing agent to react preliminarily. The mixture is tested using an emulsified asphalt slurry seal consistency tester, and the material in the reactor is transferred to a kneader when the sample test consistency is in the range of 7.0 to 7.5. 20 parts of rheology modifier nano-calcium carbonate are added and the kneading blade speed is set to 20 rpm, mixed at 40°C for 20 minutes, and sampled and tested using an asphalt penetration tester. When the 40°C penetration is in the range of 100 to 250 (0.1 mm), the material is discharged to obtain thumb glue.

[0074] Comparative Example 2

[0075] Step 1) Add dioctyl terephthalate and PVC resin to a reactor in a mass ratio of 1:2.5 and continue stirring. Set the speed to 200 revolutions per minute to ensure that the PVC resin and the plasticizer are fully mixed for 45 minutes. Stop stirring when the viscosity of the material in the reactor is within the range of 75000 to 85000 CPS. Obtain a premix.

[0076] Step 2) 60 parts of the premix are put into the reactor, and then 15 parts of the reinforcing resin isocyanate-modified bisphenol A diglycidyl ether, 2 parts of the curing agent N,N-dimethylbenzenesulfonamide, and 10 parts of the reinforcing filler nano-silica are added in sequence. The stirring speed is set to 200 rpm, and the reinforcing resin and the curing agent are stirred at 75°C for 30 minutes to allow the reinforcing resin and the curing agent to react preliminarily. The mixture is tested using an emulsified asphalt slurry seal consistency tester, and the material in the reactor is transferred to a kneader when the sample test consistency is in the range of 6.0 to 6.5. 30 parts of rheology modifier nano-calcium carbonate are added and the kneading blade speed is set to 20 rpm, mixed at 40°C for 20 minutes, and sampled and tested using an asphalt penetration tester. When the 40°C penetration is in the range of 100 to 250 (0.1 mm), the material is discharged to obtain thumb glue.

[0077] (III) Performance comparison

[0078] Step 1) Shear strength performance comparison:

[0079] Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were cured at 140° C. for 40 minutes, and the shear strength performance was compared and tested as shown in Table 1 below.

[0080] Table 1 is the test shear strength performance data

[0081] Customer Request Example 1 Example 2 Comparative Example 1 Comparative Example 2 Shear strength, MPa ≥1.0 2.57 2.64 2.28 2.15

[0082] From the results in Table 1, it can be concluded that after using bio-based raw materials in Examples 1 and 2, the shear strength performance of the thumb glue is higher than that of Comparative Examples 1 and 2 using o-phthalate and paraphthalate plasticizers, which can ensure that the post-curing performance of the thumb glue after using bio-based environmentally friendly materials can still be maintained at a good level.

[0083] Step 2) Operational performance comparison

[0084] The operating performances of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 were compared, and the results are shown in Table 2 below.

[0085] Table 2 shows the operating performance data

[0086]

[0087] After the data in Table 2 are plotted into a curve graph, Figure 1 As shown. Figure 1 , From the results in Table 2, it can be seen that the penetration of Examples 1 and 2 is low in the range of 16-30°C, and rises slowly with the increase of temperature. When the temperature is in the range of 30-40°C, the penetration increases significantly, which is reflected in the operability that it is not easy to deform in a low temperature environment and can withstand factory assembly line transportation. It is softer and easier to knead at a temperature close to body temperature. The hardness of Comparative Example 1 is similar to that of the embodiment and is easy to knead when the temperature is in the range of 30-40°C, but it is significantly softer in the range of 16-30°C. It is easy to deform after being pasted on parts or steel plates at temperatures within this range, and its resistance to factory assembly line transportation is lower than that of Examples 1 and 2. The penetration of Comparative Example 2 is similar to that of the embodiment in the range of 16-30°C, but the penetration is significantly greater than that of Examples 1 and 2 in the range of 30-40°C, so it has the disadvantage of being difficult to operate.

[0088] Combined with Table 1, Table 2, Figure 1 Taking the results of the test into consideration, the thumb glue of Example 1 and Example 2 can improve the convenience of operation during construction. During the kneading process of the construction personnel, the thumb glue will soften and reduce the hardness in the range of 30 to 40°C, making it easier to operate. After the thumb glue is pressed to the target part, as the temperature drops to 16 to 30°C, the same level as the steel plate, the thumb glue will gradually solidify and harden. This ensures that the thumb glue will not fall off from the holes and gaps at the construction site during subsequent transportation, and can improve the transportation resistance of the workpiece on the assembly line.

[0089] In summary, the automotive bio-based thumb glue of the present invention and its preparation method, the preparation process includes reacting renewable plant esters such as palm oil or coconut oil with polyethylene glycol diacrylate under the action of tetrabutylammonium propionate catalyst to generate high melting point modified bio-based plant esters, and then mixing with PVC resin to form a bio-based premix with a high melting point. Then, through a series of processes such as premix processing, enhanced resin pre-curing, rheological adjustment and needle penetration adjustment, it is ensured that the material can be softened at human body temperature during construction and hardened after cooling, thereby improving the thumb glue's resistance to factory assembly line transportation performance while having excellent operating performance. At the same time, the bio-based thumb glue has good mechanical properties after baking and curing, which significantly reduces the dependence of traditional formulas on non-renewable raw materials such as ortho-phthalate and para-phthalate plasticizers, and conforms to the industry's environmental protection trend.

[0090] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by any technician familiar with the technical field within the technical scope disclosed in the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims. The information disclosed in the background technology section of this article is only intended to deepen the understanding of the overall background technology of the present invention, and should not be regarded as an admission or in any form that the information constitutes prior art known to those skilled in the art.

Claims

1. A bio-based thumb glue for automobiles, characterized in that: It is prepared from the following raw materials in parts by weight: 60-70 parts of high melting point bio-based premix, 10-20 parts of reinforcing resin, 2-5 parts of curing agent, 5-10 parts of reinforcing filler and 20-30 parts of rheology regulator.

2. The bio-based thumb glue for automobile according to claim 1, characterized in that: The high melting point bio-based premix is ​​a mixture of high melting point modified bio-based plant ester and PVC resin in a mass ratio of 1:2 to 2.

5.

3. The bio-based thumb glue for automobile according to claim 2, characterized in that: The high melting point modified bio-based plant ester is prepared in the following manner, comprising: Step 11) adding palm oil or coconut oil into a reaction kettle, adding polyethylene glycol diacrylate to the palm oil or coconut oil in a mass ratio of 5-7:0.7-1, and raising the temperature of the entire system to 90° C.; Step 12) adding tetrabutylammonium propionate as a catalyst under the conditions of the above step, adjusting the pH value to a range of 8.5 to 9.5, and continuing the reaction at a speed of 400 revolutions per minute for 2 hours; Step 13) Cooling the plant ester obtained after the reaction to 23° C. to obtain the high melting point modified bio-based plant ester.

4. The bio-based thumb glue for automobile according to claim 2 or 3, characterized in that: The high melting point bio-based premix is ​​prepared in the following manner, comprising: Step 21) placing the high melting point modified bio-based plant ester into a reactor, adjusting the temperature to 50° C. and stirring at a speed of 300 revolutions per minute until the modified bio-based plant ester in the reactor is completely melted; Step 22) adding PVC resin to the reactor in a mass ratio of 1:2 to 2.5 of the high melting point modified bio-based plant ester to the PVC resin, and continuing stirring, setting the speed to 200 revolutions per minute, and continuing stirring for 30 to 50 minutes to fully mix the PVC resin and the high melting point modified bio-based plant ester; Step 23) During the mixing process, when the viscosity of the material in the reactor is observed to be in the range of 75,000 to 85,000 CPS, the heating is stopped and the material is allowed to cool and solidify, thereby obtaining a solid high melting point bio-based premix.

5. The bio-based thumb glue for automobile according to any one of claims 1 to 3, characterized in that: The reinforcing resin is isocyanate-modified bisphenol A diglycidyl ether.

6. The bio-based thumb glue for automobile according to any one of claims 1 to 3, characterized in that: The curing agent is N,N-dimethylbenzenesulfonamide.

7. The bio-based thumb glue for automobile according to any one of claims 1 to 3, characterized in that: The reinforcing filler is nano silicon dioxide; The rheology regulator is nano calcium carbonate.

8. A method for preparing the bio-based thumb glue for automobiles according to any one of claims 1 to 7, characterized in that: include: The raw materials are taken according to the formula of the bio-based thumb glue for automobiles according to any one of claims 1 to 7; Step 1) putting a high melting point bio-based premix into a reactor, heating it to 50° C. to melt the high melting point bio-based premix, then adding a reinforcing resin, a curing agent and a reinforcing filler in sequence, stirring at a stirring speed of 200 revolutions per minute at 75° C. for 30 minutes to allow the reinforcing resin and the curing agent to react preliminarily, to obtain a mixture; Step 2) when sampling and testing the consistency of the mixture obtained in step 1, when the test consistency is in the range of 6.0 to 7.5, the material in the reaction kettle is transferred to the kneader; Step 3) Add a rheology modifier to the material in the kneader and set the kneading blade speed to 20 revolutions per minute, mix at 40° C. for 20 minutes, take samples to test the needle penetration of the material, and discharge the material when the needle penetration at 40° C. is within the range of 100 to 250, thereby obtaining the bio-based thumb glue.

9. The method for preparing the bio-based thumb glue for automobile according to claim 8, characterized in that: In the step 2, the mixture obtained in step 1 is tested using an emulsified asphalt slurry seal consistency tester; In step 3, an asphalt penetration tester is used to take samples to test the penetration of the material.

10. The method for preparing the bio-based thumb glue for automobile according to claim 8, characterized in that: The high melting point bio-based premix in step 1 is prepared in the following manner, including: Step 21) placing the high melting point modified bio-based plant ester into a reactor, adjusting the temperature to 50° C. and stirring at a speed of 300 revolutions per minute until the modified bio-based plant ester in the reactor is completely melted; Step 22) adding PVC resin to the reactor in a mass ratio of 1:2 to 2.5 of the high melting point modified bio-based plant ester to the PVC resin, and continuing stirring, setting the speed to 200 revolutions per minute, and continuing stirring for 30 to 50 minutes to fully mix the PVC resin and the high melting point modified bio-based plant ester; Step 23) During the mixing process, when the viscosity of the material in the reactor is observed to be in the range of 75000 to 85000 CPS, the heating is stopped, and the material is allowed to cool and solidify, thereby obtaining a solid high melting point bio-based premix; The high melting point modified bio-based plant ester is prepared in the following manner, including: Step 11) adding palm oil or coconut oil into a reaction kettle, adding polyethylene glycol diacrylate to the palm oil or coconut oil in a mass ratio of 5-7:0.7-1, and raising the temperature of the entire system to 90° C.; Step 12) adding tetrabutylammonium propionate as a catalyst under the conditions of the above step, adjusting the pH value to a range of 8.5 to 9.5, and continuing the reaction at a speed of 400 revolutions per minute for 2 hours; Step 13) Cooling the plant ester obtained after the reaction to 23° C. to obtain the high melting point modified bio-based plant ester.

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