Anti-flushing expansion type damping rubber and preparation method thereof

Abstract

The invention provides an anti-flushing expansion type vibration damping rubber and a preparation method thereof. The anti-flushing expansion type vibration damping rubber is prepared from the following raw materials: epoxy resin, PVC (Polyvinyl Chloride) resin, butadiene styrene rubber, a diluent, an adhesion promoter, a curing agent, a foaming agent, fiber cotton and filler. According to the vibration reduction rubber product provided by the invention, on the basis of a previous vibration reduction rubber product, the sinking resistance of the vibration reduction rubber is improved from 3-5 times to 10 times or more, the washing resistance is improved from 130 RPM to 150 RPM, and the expansion rate is improved to 100% or more, so that the problems that the vibration reduction rubber is washed away in a coating workshop and a vehicle body is polluted are solved, and the requirements of the vehicle body attractiveness and the vibration reduction performance are improved.

Description

Technical Field

[0001] This invention belongs to the field of vibration damping adhesive technology, specifically relating to an anti-washing and swelling type vibration damping adhesive and its preparation method. Background Technology

[0002] With the increasing demand for lightweight vehicles, the steel panels of the car body are being thinned or lightweight aluminum panels are being used, leading to a decrease in the strength of the outer sheet metal. Damping adhesives are applied between the panels and reinforcing ribs in the four doors, two hoods, and roof area to buffer vibrations and reduce noise. To better adapt to changes in panel spacing under different working conditions, damping adhesives are typically designed to expand. Currently, sealants and damping adhesives are prone to being washed away during the washing process of painting and repainting, failing to adequately meet the performance and appearance requirements of OEMs. Therefore, it is necessary to improve the wash resistance of sealants and damping adhesives. Summary of the Invention

[0003] In view of this, the present invention provides an anti-washing expansion type vibration damping adhesive and its preparation method, which improves the dent resistance, anti-washing performance and expansion rate of the vibration damping adhesive.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: On the one hand, the present invention provides an anti-washing expansion type vibration damping adhesive, the raw materials of which include: epoxy resin, PVC resin, styrene-butadiene rubber, diluent, adhesion promoter, curing agent, foaming agent, fiber cotton and filler.

[0005] Preferably, the styrene-butadiene rubber comprises styrene-butadiene rubber with a styrene content of 22.5-4.5% by mass; and / or, The fiber cotton includes ceramic fiber cotton containing 44-55 wt% alumina and 44%-55 wt% silica. In some embodiments, preferably, it is slag-free ceramic fiber cotton containing 46-47 wt% alumina and 51-52 wt% silica.

[0006] Preferably, the epoxy resin has a mass fraction of 7-9%, the PVC resin has a mass fraction of 10-20%, the styrene-butadiene rubber has a mass fraction of 8-12%, the diluent has a mass fraction of 24-36%, the adhesion promoter has a mass fraction of 1-2%, the curing agent has a mass fraction of 1-2%, the foaming agent has a mass fraction of 0.6-1%, the fiber cotton has a mass fraction of 1-4%, and the filler has a mass fraction of 25-48%.

[0007] Preferably, the epoxy resin comprises at least one of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether; and / or, The PVC resin includes polyvinyl chloride homopolymer paste resin.

[0008] Preferably, the diluent includes at least one of diisononyl phthalate and diisodecyl phthalate.

[0009] Preferably, the adhesion promoter includes at least one of silane coupling agents, rosin resin, phenolic resin, terpene resin, and silane coupling agents.

[0010] Preferably, the curing agent comprises a mixture of dicyandiamide, 4,4'-methylenebis(phenyl dimethylurea), and di-(tert-butylperoxyisopropyl)benzene.

[0011] Preferably, the foaming agent includes at least one of azodicarbonamide, 4,4'-oxobisbenzenesulfonyl hydrazine, and microsphere foaming agent.

[0012] Preferably, the filler comprises at least one of calcium carbonate, mica powder, kaolin, wollastonite powder, bentonite, and calcium oxide.

[0013] On the other hand, the present invention provides a method for preparing the aforementioned anti-washing and swelling damping adhesive, comprising the following steps: S1. Mix styrene-butadiene rubber and diluent to obtain a mixture; S2. The mixture is mixed with epoxy resin, PVC resin, adhesion promoter, curing agent, foaming agent, fiber cotton and filler to obtain an intermediate mixture; S3. Vacuum stir the intermediate mixture to remove bubbles and obtain an anti-washing expansion type vibration damping adhesive.

[0014] Compared with the prior art, the beneficial effects of the present invention are as follows: (1) By adding fiber cotton, the present invention improves the volume expansion rate and dent resistance of the product, thus achieving the technical requirements of anti-washing and expansion vibration reduction.

[0015] (2) The vibration damping adhesive product provided by the present invention improves the dent resistance of the vibration damping adhesive from 3-5 times to more than 10 times, the wash resistance from being washed away at 130 RPM to not being washed away at 150 RPM, and the expansion rate to more than 100%, thereby solving the problem of the vibration damping adhesive being washed away in the painting workshop and contaminating the car body, and improving the requirements of car body aesthetics and vibration damping performance. Attached Figure Description

[0016] Figure 1 The anti-dent tooling diagram provided for the performance testing of this invention; Figure 2 Custom tooling drawings provided for performance testing of this invention; Figure 3 Stainless steel sheet diagram provided for performance testing of this invention; Figure 4 The pagoda spring diagram provided for performance testing of this invention; Figure 5 A diagram of the IKA magnetic stirrer provided for performance testing of this invention; Figure 6 The sample preparation diagram provided for performance testing of this invention. Detailed Implementation

[0017] The present invention will now be described in further detail with reference to specific embodiments, so that those skilled in the art can more clearly understand the present invention.

[0018] The specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit the scope of protection of the present invention.

[0019] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0020] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0021] Key experimental material sources and physicochemical parameters: Epoxy resin: BE-188EL was purchased from Changchun Chemical, and YDF-170 was purchased from Guodu Chemical. PVC resin: Polyvinyl chloride homopolymer paste resin PSM-31 was purchased from Shenyang Chemical. Styrene-butadiene rubber: Styrene-butadiene rubber SBR1009 was purchased from Nanjing Guochen Chemical. Diluents: Diisononyl phthalate (DINP) was purchased from Liancheng Chemical, and diisodecyl phthalate (DPHP) was purchased from Shanghai Kunrui Chemical. Adhesion promoters: silane coupling agent A-189 was purchased from Momentive, rosin resin was purchased from Shaxian Licheng Chemical, and phenolic resin was purchased from Hangmo New Materials.

[0022] Curing agents: Dicyandiamide was purchased from OMICURE, organic urea 4,4'-methylenebis(phenyl dimethylurea) was purchased from CVC, and di-(tert-butylperoxyisopropyl)benzene was purchased from ARKEMA.

[0023] Blowing agents: OBSH blowing agent: 4,4'-oxobisbenzenesulfonyl hydrazine purchased from Lanxess; AC blowing agent: azodicarbonamide purchased from Jiangsu Suopu; microsphere blowing agent purchased from AkzoNobel. Fiber cotton: Residue-free ceramic fiber cotton T-1000 / T-1260 / T-1400 was purchased from Zhejiang Jiahua; Fillers: Nano calcium carbonate SP200 was purchased from Shanxi Lanhua, calcium carbonate CC905 was purchased from Guangxi Kelong, and calcium oxide was purchased from Zibo Hainuo.

[0024] All other reagents were commercially available.

[0025] This invention provides an anti-washing and swelling type vibration damping adhesive, the raw materials of which include: epoxy resin, PVC resin, styrene-butadiene rubber, diluent, adhesion promoter, curing agent, foaming agent, fiber cotton and filler.

[0026] Further, the styrene-butadiene rubber comprises styrene-butadiene rubber with a styrene content of 22.5-4.5% by mass; and / or, The fiber cotton includes ceramic fiber cotton containing 44-55 wt% alumina and 44%-55 wt% silica. In some embodiments, preferably, it is slag-free ceramic fiber cotton containing 46-47 wt% alumina and 51-52 wt% silica.

[0027] Further, the epoxy resin has a mass fraction of 7-9%, the PVC resin has a mass fraction of 10-20%, the styrene-butadiene rubber has a mass fraction of 8-12%, the diluent has a mass fraction of 24-36%, the adhesion promoter has a mass fraction of 1-2%, the curing agent has a mass fraction of 1-2%, the foaming agent has a mass fraction of 0.6-1%, the fiber cotton has a mass fraction of 1-4%, and the filler has a mass fraction of 25-48%. In some embodiments, preferably, the epoxy resin has a mass fraction of 7.5-8.5%, the PVC resin has a mass fraction of 12-18%, the styrene-butadiene rubber has a mass fraction of 9-11%, the diluent has a mass fraction of 27-33%, the adhesion promoter has a mass fraction of 1-2%, the curing agent has a mass fraction of 1-1.8%, the foaming agent has a mass fraction of 0.6-1%, the fiber cotton has a mass fraction of 2-3%, and the filler has a mass fraction of 30-41%.

[0028] Further, the epoxy resin includes at least one of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether; and / or, The PVC resin includes polyvinyl chloride homopolymer paste resin.

[0029] Furthermore, the diluent includes at least one of diisononyl phthalate and diisodecyl phthalate.

[0030] Furthermore, the adhesion promoter includes at least one of silane coupling agents, rosin resin, phenolic resin, terpene resin, and silane coupling agents.

[0031] Furthermore, the curing agent comprises a mixture of dicyandiamide, 4,4'-methylenebis(phenyl dimethylurea), and di-(tert-butylperoxyisopropyl)benzene.

[0032] Furthermore, the foaming agent includes at least one of azodicarbonamide, 4,4'-oxobisbenzenesulfonylhydrazine, and microsphere foaming agent.

[0033] Furthermore, the filler includes at least one of calcium carbonate, mica powder, kaolin, wollastonite powder, bentonite, and calcium oxide.

[0034] On the other hand, the present invention provides a method for preparing the aforementioned anti-washing and swelling damping adhesive, comprising the following steps: S1. Mix styrene-butadiene rubber and diluent to obtain a mixture; S2. The mixture is mixed with epoxy resin, PVC resin, adhesion promoter, curing agent, foaming agent, fiber cotton and filler to obtain an intermediate mixture; S3. Vacuum stir the intermediate mixture to remove bubbles and obtain an anti-washing expansion type vibration damping adhesive.

[0035] In the above technical solution, the specific steps are as follows: Styrene-butadiene rubber and diluent are kneaded at 60℃-70℃ until completely dissolved to obtain a mixture; the obtained mixture, epoxy resin, PVC resin, adhesion promoter, curing agent, foaming agent, fiber cotton, and filler are added separately to a dynamic mixer, and stirred at 20℃-40℃ with a rotation / revolution speed of 100-200 rpm / 10-20 rpm for 60 minutes until uniformly dispersed to obtain an intermediate mixture; the intermediate mixture is then subjected to vacuum stirring and degassing, wherein the vacuum degree is above -0.090 MPa, and the rotation / revolution speed is 100-200 rpm / 10-20 rpm for 30-40 minutes, and then filled to obtain an anti-wash-expansion type vibration damping adhesive.

[0036] Example 1 This embodiment provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 1 below: Table 1 Composition of the damping adhesive provided in Example 1

[0037] The preparation method of the vibration damping adhesive in this embodiment includes the following steps: S1. Weigh each raw material according to the component ratios provided in Table 1.

[0038] S2: Knead the weighed styrene-butadiene rubber and diluent at 60°C until completely dissolved to obtain a mixture; S3: Add the mixture obtained in step S2 and the epoxy resin, PVC resin, adhesion promoter, curing agent, foaming agent, fiber cotton and filler weighed in step S1 into a dynamic mixer, and stir at a low speed of 150 rpm / 15 rpm for 60 minutes at 30°C until the mixture is evenly dispersed to obtain an intermediate mixture. S4: The intermediate mixture obtained in step S3 is subjected to vacuum stirring and degassing, wherein the vacuum degree is above -0.090MPa, the rotation / revolution is 150rpm / 15rpm, the stirring is carried out for 35min, and the mixture is then filled to obtain the anti-washing expansion type vibration damping adhesive.

[0039] Example 2 This embodiment provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 2 below: Table 2 Composition of the damping adhesive provided in Example 2

[0040] The preparation method of the vibration damping adhesive in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0041] Example 3 This embodiment provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 3 below: Table 3 Composition of the damping adhesive provided in Example 3

[0042] The preparation method of the vibration damping adhesive in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0043] Example 4 This embodiment provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 4 below: Table 4 Composition of the damping adhesive provided in Example 4

[0044] The preparation method of the vibration damping adhesive in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0045] Example 5 This embodiment provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 5 below: Table 5 Composition of the damping adhesive provided in Example 5

[0046] The preparation method of the vibration damping adhesive in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0047] Example 6 This embodiment provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 6 below: Table 6 Composition of the damping adhesive provided in Example 6

[0048] The preparation method of the vibration damping adhesive in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0049] Example 7 This embodiment provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 7 below: Table 7 Composition of the damping adhesive provided in Example 7

[0050] The preparation method of the vibration damping adhesive in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0051] Example 8 This embodiment provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 8 below: Table 8 Composition of the damping adhesive provided in Example 8

[0052] The preparation method of the vibration damping adhesive in this embodiment is basically the same as that in Example 1, and will not be repeated here.

[0053] Comparative Example 1 This comparative example provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 9 below: Table 9 Composition of the damping adhesive provided in Comparative Example 1

[0054] The preparation method of the damping adhesive in this comparative example is basically the same as that in Example 1, and will not be repeated here.

[0055] Comparative Example 2 This comparative example provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 10 below: Table 10 Composition of the damping adhesive provided in Comparative Example 2

[0056] The preparation method of the damping adhesive in this comparative example is basically the same as that in Example 1, and will not be repeated here.

[0057] Comparative Example 3 This comparative example provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 11 below: Table 11 Composition of the damping adhesive provided in Comparative Example 3

[0058] The preparation method of the damping adhesive in this comparative example is basically the same as that in Example 1, and will not be repeated here.

[0059] Comparative Example 4 This comparative example provides a vibration damping adhesive, which is prepared from the raw materials shown in Table 12 below: Table 12 Composition of the damping adhesive provided in Comparative Example 4

[0060] The preparation method of the damping adhesive in this comparative example is basically the same as that in Example 1, and will not be repeated here.

[0061] Performance Tests and Results The vibration damping adhesives obtained in the above embodiments and comparative examples were subjected to performance tests, and the test methods are as follows: 1. Dent resistance: 1.1 Anti-dent tooling (e.g.) Figure 1 (as shown) a) Steel plates (2 pieces): 150*25*3.8mm stainless steel plates (6mm holes at both ends, about 6mm from the edge), with a smooth surface; b) Pagoda springs (2 pieces): wire diameter 0.5mm * small outer diameter 6mm * large outer diameter 13mm * height 15mm; c) Bolts (2): M6, with matching nuts.

[0062] 1.2 Other assistive devices: 10mm gap thickness control pad (aluminum); 2mm thick PTFE pad; vernier caliper (150mm); glue gun (300mL).

[0063] 1.3 Test Procedure 1.3.1 Use a special auxiliary tool to make a 5mm diameter * 100mm long adhesive strip in the center of the stainless steel plate (ensure there are no cavities or air bubbles) to fix the stainless steel plate. Prepare two sets of samples as parallel samples. 1.3.2 Use 10mm standard shims and vernier calipers to control the gap between stainless steel plates to be 10±0.5mm; 1.3.3 Press both ends of the stainless steel plate to 2mm (using 2mm pads for control), repeat pressing 10 times, and observe whether there are visible cracks or holes of ≥1mm on the spindle-shaped rubber strip. The result is used as the direct judgment result of dent resistance OK or NG. 1.3.4 If no cracks or holes of ≥1mm visible to the naked eye appear, continue pressing the stainless steel plate and record the number of times from the start of pressing until a crack or hole of ≥1mm visible to the naked eye appears. This number is n. 1.3.5 Repeat the test once for parallel samples and take the average value.

[0064] 1.3.4 If no cracks or holes of ≥1mm visible to the naked eye appear, continue pressing the stainless steel plate and record the number of times from the start of pressing until a crack or hole of ≥1mm visible to the naked eye appears. This number is n. 1.3.5 Repeat the test once for parallel samples and take the average value.

[0065] 2. Rinse resistance 2.1 Rotary rinsing fixture: a) Custom-made workwear, The outer frame dimensions are 200mm (length) x 25mm (width) x 2mm (thickness); the inner frame dimensions are 100mm (length) x 25mm (width) x 2mm (thickness); the long rod (with fan blades) is approximately 400mm long and 10mm in diameter. Figure 2 As shown; b) Stainless steel sheet: 100*25*1.6mm stainless steel sheet (6mm holes at both ends, approximately 6mm from the edge), requiring a flat surface, such as... Figure 3 As shown; c) Pagoda Spring: Wire diameter 0.5mm * Small outer diameter 6mm * Large outer diameter 13mm * Height 15mm, such as... Figure 4 As shown; 2.2 Test Equipment: IKA magnetic stirrer: speed range 50-2000rpm, accuracy 1±rpm; Figure 5 As shown: 2.3 Other accessories: 10mm gap control pad; bolts: M6, with matching nuts; pads: 3mm thickness; vernier caliper (150mm); glue gun (300mL); vernier caliper (150mm); stopwatch; constant temperature water bath (23±2℃).

[0066] 2.4 Sample preparation (e.g.) Figure 6 (As shown) 2.4.1 Use a special auxiliary tool to make two adhesive strips with a diameter of 6mm and a length of about 100mm in the center of the stainless steel sheet. Fix the stainless steel sheet to the left and right crossbeams of the rotating fixture. Prepare two sets of samples as parallel samples. 2.4.2 Use 10mm standard shims and vernier calipers to control the gap between the stainless steel sheet and the crossbeam to be 10±0.5mm; 2.4.3 Press both ends of the stainless steel sheet to 3mm (using 3mm pads for control), and repeat pressing 3 times; 2.4.4 Observe whether the adhesive strip forms a uniform spindle shape and check for pores or defects (if pores or defects are present, a new sample needs to be prepared). 2.4.5 Record the appearance of the adhesive strip and take photos for archiving.

[0067] 2.5 Flushing Test 2.5.1 Fix the tooling after sample preparation onto the magnetic stirrer, ensuring that the water in the tank can submerge the adhesive layer; 2.5.2 Start the rinsing program and rinse at progressively increasing speeds of 120 rpm for 5 minutes, 130 rpm for 5 minutes, 140 rpm for 5 minutes, and 150 rpm for 5 minutes until a noticeable difference is observed. 2.5.3 After rinsing, remove the sample, take photos to record the state of the adhesive strips on both sides, and record whether the holes on both sides have been punched open.

[0068] 3. Volume expansion rate 3.1 Determine the mass m1 of a (100×25) mm aluminum plate in air and the mass m2 in water; 3.2 Coat a semi-circular sample with a length of 80 mm and a diameter of 10 mm onto a dry aluminum plate, and weigh the aluminum plate and the sample in air (m3) and in water (m4) using a balance. 3.3 Place the sample in an oven at 170℃ for 20 minutes, remove it and cool it, then measure the mass m5 of the aluminum plate and the sample in air and the mass m6 of the sample in water. 3.4 Calculate the volumetric expansion rate using the following formula. Perform parallel tests on three samples per group and take the average value:

[0069] Table 13 Performance Test Results Statistics

[0070] Based on the performance test results table, it can be seen that, compared with Comparative Examples 1 to 4, the anti-washing expansion type vibration damping adhesives of Examples 1 to 8, by selecting specific types of resins, rubbers, foaming agents, fiber cotton and fillers, and using specific proportions and preparation methods, improve the volume expansion rate and dent resistance of the products, meet the technical requirements of anti-washing and expansion vibration damping, maintain the appearance of the vehicle body, and at the same time meet the process requirements of expansion vibration damping and automated construction.

[0071] Unless otherwise specified, all raw materials used in this invention are existing substances that can be purchased directly from the market.

[0072] The above are merely preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A washout resistant intumescent damping gel, characterized in that The raw materials include: epoxy resin, PVC resin, styrene-butadiene rubber, diluent, adhesion promoter, curing agent, foaming agent, fiber cotton and filler.

2. The wash-out resistant expansion-type damping gel according to claim 1, wherein The styrene-butadiene rubber includes styrene-butadiene rubber with a styrene mass content of 22.5-4.5%; and / or, The fiber cotton includes ceramic fiber cotton containing 44-55 wt% of alumina and 44%-55 wt% of silicon oxide.

3. The wash-out resistant expansion-type damping gel according to claim 1, wherein The mass fraction of the epoxy resin is 7-9%, the mass fraction of the PVC resin is 10-20%, the mass fraction of the styrene-butadiene rubber is 8-12%, the mass fraction of the diluent is 24-36%, the mass fraction of the adhesion promoter is 1-2%, the mass fraction of the curing agent is 1-2%; the mass fraction of the foaming agent is 0.6-1%, the mass fraction of the fiber cotton is 1-4%, and the mass fraction of the filler is 25-48%.

4. The washout resistant expansion damping gel of claim 1, wherein, The epoxy resin includes at least one of bisphenol A diglycidyl ether and bisphenol F diglycidyl ether; and / or, The PVC resin includes polyvinyl chloride homopolymer paste resin.

5. The wash-out resistant expansion-type damping gel according to claim 1, wherein The diluent includes at least one of diisononyl phthalate and diisodecyl phthalate.

6. The wash-out resistant expansion-type damping gel according to claim 1, wherein The adhesion promoter includes at least one of silane coupling agent, rosin resin, phenolic resin, terpene resin, and silane coupling agent.

7. The wash-out resistant expansion-type damping gel of claim 1, wherein, The curing agent includes a mixture of dicyandiamide, 4,4'-methylenebis(phenyl dimethylurea), and di-(tert-butyl peroxyisopropyl) benzene.

8. The wash-out resistant expansion-type damping gel according to claim 1, wherein The foaming agent includes at least one of azodicarbonamide, 4,4'-oxybisbenzenesulfonyl hydrazide, and microsphere foaming agent.

9. The wash-out resistant expansion-type damping gel of claim 1, wherein, The filler includes at least one of calcium carbonate, mica powder, kaolin, wollastonite powder, bentonite, and calcium oxide.

10. The method of claim 1-9, wherein the method is characterized by, The method includes the following steps: S1, mixing styrene-butadiene rubber and diluent to obtain a mixed solution; S2, mixing the mixed solution with epoxy resin, PVC resin, adhesion promoter, curing agent, foaming agent, fiber cotton and filler to obtain an intermediate mixture; S3, vacuum stirring and defoaming the intermediate mixture to obtain an anti-washing expansion type damping glue.

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