Outdoor anti-aging grafting type nail-free glue as well as preparation method and application thereof
By grafting SBS with methyl methacrylate and methacrylic acid and adding hydrogenated petroleum resin, the problem of SBS nail-free adhesive aging outdoors has been solved, achieving a high-strength bonding effect, suitable for bonding outdoor boards, wood strips and iron frames.
Patent Information
- Application Number
- CN202511365206.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-23
- Publication Date
- 2025-12-12
AI Technical Summary
Existing SBS nail-free adhesive is prone to aging when used outdoors, resulting in reduced strength of the bonded areas and making it unable to effectively bond outdoor panels, advertising iron frames, and wooden frames for a long time.
SBS (styrene-butadiene thermoplastic elastomer) was grafted with methyl methacrylate and methacrylic acid to introduce acrylate segments and polar groups with good weather resistance. Large sterically hindered groups were introduced near the double bonds through the grafting reaction, and hydrogenated saturated double bonds of transparent hydrogenated petroleum resin were added to improve heat, oxygen and UV resistance.
It significantly improves the aging resistance and bonding strength of SBS nail-free adhesive, and can maintain its bonding performance for a long time in outdoor environments.
Smart Images
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of high polymer sealing materials, and provides an outdoor anti-aging grafting type nail-free glue, a preparation method and application thereof, in particular to an outdoor special high-strength anti-aging grafting type nail-free glue of styrene-butadiene thermoplastic elastomer and a preparation method thereof. BACKGROUND
[0002] The nail-free glue generally refers to an adhesive for bonding building materials, commonly known as liquid nails, and is generally packaged with plastic round tubes or aluminum film paper tubes. The early nail-free glue is a chloroprene rubber type, but contains harmful solvents such as toluene, and has slow drying speed, poor initial adhesion, and cannot be widely promoted. Subsequently, solvent type polyvinyl acetate nail-free glue was developed, but the molecular weight of polyvinyl acetate nail-free glue is small, the molecular group has poor water resistance, and the anti-aging performance is limited. SBS (styrene-butadiene thermoplastic elastomer) nail-free glue appeared in 2013, which has the advantages of fast curing, low odor and low organic solvent content, and has good application prospect. The main material of ordinary SBS nail-free glue is composed of styrene-butadiene thermoplastic elastomer and carbon nine petroleum resin. The styrene-butadiene thermoplastic elastomer contains carbon-carbon double bonds, and the carbon nine petroleum resin is an aromatic hydrocarbon structure containing double bonds. They have the common characteristic of poor anti-aging performance. If used for bonding materials such as outdoor boards, advertising iron racks, wooden racks, etc., aging will occur in a short time, resulting in a decrease in the bonding strength of the bonding part, and even damage. SUMMARY
[0003] In view of the problems of ordinary nail-free glue, such as poor bonding force for outdoor boards, advertising iron racks, wooden racks, advertising characters and other materials, and easy aging and falling off, an outdoor anti-aging grafting type nail-free glue and a preparation method thereof are provided.
[0004] In the first aspect, an outdoor anti-aging grafting type nail-free glue is provided, which comprises, by weight, 10-15 parts of linear styrene-butadiene thermoplastic elastomer, 3-6 parts of methyl methacrylate, 0.5-1 part of methacrylic acid, 15-25 parts of butanone, 8-12 parts of ethyl acetate, 0.3-1 part of benzoyl peroxide toluene solution, 1-2 parts of antioxidant, 16-30 parts of hydrogenated petroleum resin, 10-15 parts of isohexane, 25-40 parts of nano calcium carbonate, and 10-15 parts of heavy calcium carbonate.
[0005] In some embodiments, the antioxidant is at least one of BHT, DLTP, tetra[ methyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester, and tri[2,4-di-tert-butylphenyl] phosphite. The antioxidant can absorb and eliminate free radicals generated in the thermal oxidation process of high polymers and other organic compounds, thereby preventing the progress of free radical chain reactions and ensuring the stability of the polymer structure and properties.
[0006] In some embodiments, the concentration of the benzoyl peroxide in toluene is 15-25 wt%, preferably 15 wt%, 20 wt%, 25 wt%, and any range formed by any two of the above values.
[0007] In some embodiments, the linear butadiene-styrene thermoplastic elastomer is 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, and any range formed by any two of the above values.
[0008] In some embodiments, the methyl methacrylate is 3 parts, 4 parts, 5 parts, 6 parts, and any range formed by any two of the above values.
[0009] In some embodiments, the methyl methacrylate is 3 parts, 4 parts, 5 parts, 6 parts, and any range formed by any two of the above values.
[0010] In some embodiments, the butanone is 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, and any range formed by any two of the above values.
[0011] In some embodiments, the butanone is 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, and any range formed by any two of the above values.
[0012] In some embodiments, the benzoyl peroxide in toluene is 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1 part, and any range formed by any two of the above values.
[0013] In some embodiments, the antioxidant is 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 2 parts, and any range formed by any two of the above values.
[0014] In some embodiments, the hydrogenated petroleum resin is 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 28 parts, 30 parts, and any range formed by any two of the above values.
[0015] In some embodiments, the isohexane is 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, and any range formed by any two of the above values.
[0016] The diluent cyclohexane, the solvent butanone and the ethyl acetate are environmentally friendly, have relatively low toxicity and low cost, and are conducive to realizing industrialized scale production and processing.
[0017] In some embodiments, the nano calcium carbonate accounts for any one of the ranges formed by any two values in the range of 25 parts, 28 parts, 30 parts, 33 parts, 35 parts, 38 parts, 40 parts and above.
[0018] In some embodiments, the heavy calcium carbonate accounts for any one of the ranges formed by any two values in the range of 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts and above.
[0019] The nano calcium carbonate and the heavy calcium carbonate are conducive to improving the solid content requirement and the overall strength requirement of the glue.
[0020] In some embodiments, the outdoor anti-aging grafting type non-studded glue comprises, by weight fraction, 14 parts of linear butadiene styrene thermoplastic elastomer, 5 parts of methyl methacrylate, 1 part of methacrylic acid, 21 parts of butanone, 12 parts of ethyl acetate, 0.8 parts of benzoyl peroxide toluene solution, 1.5 parts of antioxidant BHT, 22 parts of hydrogenated petroleum resin, 13 parts of isohexane, 35 parts of nano calcium carbonate and 10 parts of heavy calcium carbonate.
[0021] In a second aspect, a preparation method of an outdoor anti-aging grafting type non-studded glue is provided, comprising the following steps:
[0022] S1 linear butadiene styrene thermoplastic elastomer is dissolved in butanone and ethyl acetate to obtain solution A;
[0023] S2 solution A is heated to a reaction temperature, and solution B and solution C are simultaneously added dropwise by using a double-drop process, wherein solution B is a mixed solution of methyl methacrylate and methacrylic acid; solution C is a benzoyl peroxide toluene solution; after the dropwise addition is completed, the reaction is completed, the temperature is lowered, and solution D is obtained;
[0024] S3 antioxidant, hydrogenated petroleum resin and isohexane are added to solution D, and stirring is performed to obtain a glue solution;
[0025] S4 under stirring, nano calcium carbonate and heavy calcium carbonate are added to the glue solution, and a non-studded glue is obtained by reaction.
[0026] In some embodiments, the solution A is prepared by stirring at a temperature of 15-35 °C for 1.5-2 hours at a stirring speed of 60-80 rpm. Preferably, the temperature is 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, and any one of the ranges defined by any two of the above values. Preferably, the stirring speed is 60 rpm, 65 rpm, 70 rpm, 75 rpm, 80 rpm, and any one of the ranges defined by any two of the above values. Preferably, the stirring time is 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 2 hours, and any one of the ranges defined by any two of the above values.
[0027] In some embodiments, the reaction temperature in S2 is 75-85 °C. Preferably, the temperature is 75 °C, 78 °C, 80 °C, 82 °C, 85 °C, and any one of the ranges defined by any two of the above values.
[0028] In some embodiments, the dropping speed of the solution B and the solution C is independently 1-10 drops / 10 s. Preferably, the dropping speed is 1 drop / 10 s, 2 drops / 10 s, 3 drops / 10 s, 4 drops / 10 s, 5 drops / 10 s, 6 drops / 10 s, 7 drops / 10 s, 8 drops / 10 s, 9 drops / 10 s, 10 drops / 10 s, and any one of the ranges defined by any two of the above values.
[0029] In some embodiments, the dropping time of the solution B and the solution C is 2-3 h, preferably 2 h, 2.5 h, 3 h, and any one of the ranges defined by any two of the above values.
[0030] In some embodiments, the reaction time in S2 is 2-3 h, preferably 2 h, 2.5 h, 3 h, and any one of the ranges defined by any two of the above values.
[0031] In some embodiments, the temperature in S2 is lowered to 40-45 °C. Preferably, the temperature is 40 °C, 41 °C, 42 °C, 43 °C, 44 °C, 45 °C, and any one of the ranges defined by any two of the above values.
[0032] In some embodiments, the stirring speed in S3 is 60-80 rpm, and the temperature is lowered to 15-35 °C to enter S4. Preferably, the temperature is 15 °C, 20 °C, 25 °C, 30 °C, 35 °C, and any one of the ranges defined by any two of the above values. Preferably, the stirring speed is 60 rpm, 65 rpm, 70 rpm, 75 rpm, 80 rpm, and any one of the ranges defined by any two of the above values.
[0033] In some embodiments, in S4, the stirring speed is 800-1200 rpm, and the stirring time is 40-60 minutes.
[0034] In a third aspect, the application provides an application of the outdoor anti-aging grafting type nail-free adhesive in bonding of outdoor plates, advertising iron racks, wooden racks and other materials.
[0035] Compared with the prior art, one of the technical solutions has the following advantages or beneficial effects:
[0036] The grafting polymerization process of SBS (styrene butadiene thermoplastic elastomer), methyl methacrylate and methyl methacrylate is adopted to introduce the acrylate segment and the polar group with better weather resistance into the molecular chain, shield the weak bond, improve the stability, realize the introduction of the large steric group for physical shielding near the double bond through the grafting reaction, add the transparent hydrogenated petroleum resin, saturate the double bond through hydrogenation, significantly improve the heat resistance and ultraviolet resistance, maintain long-term adhesion, and improve the anti-aging property of the SBS nail-free adhesive.
[0037] The outdoor anti-aging grafting type nail-free adhesive provided by the application can improve the hardness and rigidity of the SBS molecular chain, i.e., the molecular chain strength of the SBS nail-free adhesive, and the methyl methacrylate contains the polar group carboxyl, which can improve the adhesion of the molecular chain to the base material and the bonding strength of the nail-free adhesive after being grafted into the SBS molecular chain segment.
[0038] Term explanation
[0039] Certain embodiments of the application are now described in detail by reference to the accompanying figures and the following description. The application is intended to encompass all alternatives, modifications and equivalents thereof which are included within the scope of the application as defined by the claims. One skilled in the art will recognize that many methods and materials equivalent to those described herein can be used in the practice of the application. The present application is not limited to the methods and materials described herein. In the event of a conflict between the incorporated documents, patents and similar materials and the present application, including but not limited to defined terms, term application, described techniques, and the like, the present application controls.
[0040] It is to be further understood that, for brevity, certain aspects of the application are described in terms of separate embodiments; however, descriptions of features in separate embodiments are interchangeable and apply to multiple embodiments. Conversely, various features of the application are described in terms of a single embodiment or a several embodiments. However, descriptions of features in a single embodiment are also applicable to other embodiments except where clearly inconsistent with the context.
[0041] Unless defined otherwise, 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 application belongs. All patents and publications referred to in this application are incorporated in their entirety by reference into this application.
[0042] In the description of the specification, the description using the terms "one embodiment", "some embodiments", "an example", "a specific example", or "some examples" and the like means that the particular feature, structure, material, or characteristic following the term is included in at least one embodiment or example of the application. The repeatedly used above-mentioned terms do not necessarily refer to the same embodiment or example. Also, the particular features, structures, materials, or characteristics can be combined in any suitable manner in one or more embodiments or examples. Further, the various embodiments or examples described in the specification can be combined and combined with each other in appropriate manners without mutual contradiction.
[0043] In the following disclosure, all numbers disclosed herein are approximations that can vary depending on the desired properties sought to be obtained by those of ordinary skill in the art. The numerical parameters are approximations that can vary by 1%, 2%, 5%, 7%, 8%, 10%, 15%, or 20% and other values. Whenever a numerical range is disclosed, any ending point of a range can be explicitly combined with any starting point of another range, in the same way as explicitly combining any minimum with any maximum. It is intended to cover and disclose all possible combinations between any minimum and any maximum. It is intended to cover and disclose all possible combinations of numerical values of the dimensional, component, and other properties disclosed herein. DETAILED DESCRIPTION
[0044] In order to make the objectives, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the embodiments. The specific embodiments described herein are only used to explain the present application and do not constitute any limitation on the present application. In addition, in the following description, the description of the known structures and technologies is omitted to avoid unnecessary confusion of the concept of the present disclosure. Such structures and technologies are also described in many publications.
[0045] The reagents used in the present application can be purchased from the market or can be prepared by the methods described in the present application.
[0046] Embodiment
[0047] A manufacturing method of a high-strength outdoor special-purpose aging-resistant SBS grafted type non-studded glue, the specific steps are as follows:
[0048] Preparation formula: (parts by weight)
[0049] Linear SBS 1401 10-15 parts, methyl methacrylate 3-6 parts, methacrylic acid 0.5-1 part, butanone 15-25 parts, ethyl acetate 8-12 parts, benzoyl peroxide (20% toluene solution) 0.3-1 part, antioxidant BHT 1-2 parts, hydrogenated petroleum resin 16-30 parts, isohexane 10-15 parts, nano calcium carbonate 25-40 parts, heavy calcium carbonate 10-15 parts
[0050] Manufacturing process:
[0051] S1: In a reaction kettle with stirring speed of 60-80 revolutions per minute, add solvent butanone, ethyl acetate, linear SBS 1401, stir and dissolve at temperature of 15-35℃ for 1.5-2 hours to obtain solution A.
[0052] S2: Solution A is heated to 78-85℃, while solution B is added at a speed of 1-10 drops per 10 seconds and solution C is added at a speed of 1-10 drops per 10 seconds, wherein solution B is a mixed solution of methyl methacrylate and methacrylic acid; solution C is a toluene solution of benzoyl peroxide. The dropping time is 2-3h, and after the dropping is completed, the reaction continues for 2-2.5h until the viscosity of the glue solution increases obviously (the climbing rod effect appears). The temperature is lowered to 40-45℃. Solution D is obtained.
[0053] S3: Immediately add antioxidant BHT, hydrogenated petroleum resin and diluent isohexane to solution D, and stir at a speed of 60-80 revolutions per minute. The reaction process temperature is lowered to 15-35℃ to release the glue solution.
[0054] S4: The glue solution is transferred to a closed high-speed stirred tank. Nano calcium carbonate and heavy calcium carbonate are added. Stirring is carried out for 40-60 minutes under high-speed stirring (stirring speed 800-1200 rpm). A white paste-like outdoor aging-resistant grafting type nail-free glue is prepared. Pressurized extrusion is carried out for barrel loading.
[0055] The specific components and weight parts are as shown in Table 1 (in weight parts):
[0056]
[0057]
[0058] Comparative Example 1
[0059] The composition components and preparation process are consistent with Example 1, and the difference from Example 1 is that methyl methacrylate is omitted.
[0060] Comparative Example 2
[0061] The composition components and preparation process are consistent with Example 1, and the difference from Example 1 is that methacrylic acid is omitted.
[0062] Comparative Example 3
[0063] The composition components and preparation process are consistent with Example 1, and the difference from Example 1 is that the hydrogenated petroleum resin is omitted.
[0064] Comparative Example 4
[0065] The composition components and preparation process are consistent with Example 1, and the difference from Example 1 is that solution B and solution C are directly added to the reaction system without double dropwise addition.
[0066] Performance Test:
[0067] 100*30*5mm wood is selected, and the performance test of the bonded assembly is carried out according to the method of standard AS2329-1999. The nail-free glues prepared in Examples 1-3 and Comparative Examples 1-4 are subjected to corresponding performance tests, and the specific test results are as shown in Table 2:
[0068]
[0069] The shear strength detected in the table refers to the bonding performance between wood and wood assemblies, the initial shear strength refers to the shear strength performance after curing for 30 minutes, and the maximum shear strength refers to the shear strength performance after curing for 24 hours.
[0070] The nail-free glue prepared by the application is subjected to temperature resistance test, and the maximum temperature resistance range is-25 DEG C to 90 DEG C, and the nail-free glue has good bonding performance in the range, which shows that the nail-free glue has good service life. After 72 hours of bonding at 90 DEG C, no falling phenomenon occurs, and it can be seen that the nail-free glue prepared by the application has strong aging resistance in outdoor environment.
[0071] As can be seen from the performance test data of the comparative examples 1-4 and the examples 1-3 of the application, the SBS (styrene butadiene thermoplastic elastomer), methyl methacrylate and methyl methacrylate graft polymerization are used in the application, and the transparent hydrogenated petroleum resin is added to hydrogenate the double bond, so that the prepared nail-free glue has super strong bonding and strength, and the double drop processing technology is used, so that the prepared nail-free glue is uniform and is not prone to flow and the like, and has excellent durability.
[0072] The method of the application has been described by preferred examples, and the related personnel can obviously make changes or appropriate changes and combinations to the method and application described herein within the content, spirit and scope of the application to realize and apply the technical solution of the application. The skilled in the art can refer to the content herein to appropriately improve the process parameters. It should be particularly pointed out that all similar replacements and changes are obvious to the skilled in the art, and they are regarded as included in the application.
Claims
1. An outdoor use aging resistant grafted nail-free adhesive, characterized by, The linear styrene-butadiene thermoplastic elastomer 10-15 parts by weight, methyl methacrylate 3-6 parts, methacrylic acid 0.5-1 part, butanone 15-25 parts, ethyl acetate 8-12 parts, toluene solution of benzoyl peroxide 0.3-1 part, antioxidant 1-2 parts, hydrogenated petroleum resin 16-30 parts, isohexane 10-15 parts, nano calcium carbonate 25-40 parts, heavy calcium carbonate 10-15 parts.
2. The graft-type nail-repellent adhesive according to claim 1, wherein The antioxidant is at least one of BHT, DLTP, tetra [methyl-beta-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and tri [2,4-di-tert-butylphenyl] phosphite.
3. The graft-type nail-repellent adhesive according to claim 1, wherein The concentration of the toluene solution of benzoyl peroxide is 15-25wt%.
4. The graft-type nail-repelling adhesive according to claim 1, wherein The linear styrene-butadiene thermoplastic elastomer 14 parts by weight, methyl methacrylate 5 parts, methacrylic acid 1 part, butanone 21 parts, ethyl acetate 12 parts, toluene solution of benzoyl peroxide 0.8 parts, antioxidant BHT 1.5 parts, hydrogenated petroleum resin 22 parts, isohexane 13 parts, nano calcium carbonate 35 parts, heavy calcium carbonate 10 parts.
5. A method for preparing the outdoor aging-resistant grafted nail-free adhesive as described in claim 1, characterized in that, The method comprises the following steps: S1 linear styrene-butadiene thermoplastic elastomer is dissolved in butanone and ethyl acetate to obtain solution A; S2 solution A is heated to reaction temperature, and solution B and solution C are added simultaneously by double-drop process, wherein solution B is a mixed solution of methyl methacrylate and methacrylic acid; solution C is a toluene solution of benzoyl peroxide; After the dropwise addition is completed, the reaction is complete, and the temperature is lowered to obtain solution D; S3 antioxidant, hydrogenated petroleum resin and isohexane are added to solution D, and stirring is performed to obtain a glue solution; S4 under stirring, nano calcium carbonate and heavy calcium carbonate are added to the glue solution, and reaction is performed to obtain a nail-free glue.
6. The preparation method according to claim 5, characterized in that, The solution A is prepared by stirring at a temperature of 15-35℃ for 1.5-2 hours, and the rotating speed is 60-80 revolutions per minute.
7. The preparation method according to claim 5, characterized in that, The reaction temperature in S2 is 75-85℃; The dropwise addition speed of solution B and solution C is independently 1-10 drops per 10 seconds; The dropwise addition time of solution B and solution C is 2-3 hours; the reaction time in S2 is 2-3 hours; and the temperature is lowered to 40-45℃ in S2.
8. The preparation method according to claim 5, characterized in that, The stirring speed in S3 is 60-80 revolutions per minute, and the temperature is lowered to 15-35℃ during the reaction process, and then S4 is entered.
9. The preparation method according to claim 5, characterized in that, In S4, the stirring speed is 800-1200 revolutions per minute, and the stirring time is 40-60 minutes.
10. The use of the outdoor aging-resistant grafted nail-free glue of claim 1 in the preparation of an adhesive for outdoor boards, advertising iron racks and wooden rack materials.