Preparation method of ester modified SBC C5 petroleum resin
By introducing carboxylic acid ester modifiers into petroleum resins, their polarity is enhanced, and their adhesion to polar materials is improved, which solves the problem of insufficient adhesion of existing petroleum resins and achieves wider application.
Patent Information
- Application Number
- CN202411816114.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-12-11
- Publication Date
- 2025-03-04
AI Technical Summary
The existing petroleum resins have shortcomings in adhesion and are difficult to meet the needs of high adhesion.
Ester-modified SBC Carbon Five petroleum resin was prepared by stirring the styrene block copolymers SBC and C5 petroleum resin with the solvent in the reactor, and adding a carboxylic acid ester modifier under the control of temperature and time for grafting reaction.
The polarity of modified SBC Carbon Five Petroleum resin has been enhanced, greatly enhancing its adhesion to polar materials, meeting a wider application demand.
Smart Images
Figure CN119552307A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of adhesives, and particularly relates to a method for preparing an ester-modified SBC C5 petroleum resin. Background Art
[0002] The application of adhesives in many fields is constantly expanding, and its development prospects are very broad, especially in the manufacturing field, where adhesives are increasingly widely used. Adhesives have become an important material used for bonding, fixing and sealing various parts. With the continuous upgrading of the manufacturing industry and the continuous improvement of technological level, the demand for adhesives will also continue to increase.
[0003] The pressure-sensitive adhesive commonly used on the market has high requirements for the adhesion of the adhesive. It needs to be able to form a relatively strong bond under a small force, and usually will not affect the surface of the adherend after use, and no adhesive traces will remain. Therefore, it is necessary to develop a new adhesive composition to cope with high-adhesion scenarios. Summary of the invention
[0004] The technical problem to be solved by the present invention is to provide a method for preparing an ester-modified SBC C5 petroleum resin, which has better adhesion than the existing petroleum resin.
[0005] The present invention provides a method for preparing an ester-modified SBC C5 petroleum resin, comprising the following steps:
[0006] (1) adding styrene block copolymer SBC, C5 petroleum resin and solvent into a reaction kettle and stirring evenly;
[0007] (2) Adding a carboxylic acid ester modifier to the above reactor for grafting, controlling the reaction temperature to 170-220° C., the reaction time to 1-4 hours, and then recovering the solvent by stripping to obtain an ester-modified SBC C5 petroleum resin.
[0008] Preferably, the styrene block copolymer SBC in step (1) includes one or more of styrene-isoprene-styrene block copolymer SIS, styrene-butadiene-styrene block copolymer SBS, and hydrogenated styrene-butadiene-styrene block copolymer SEBS.
[0009] Preferably, the solvent in step (1) comprises one or more of benzene, toluene, xylene and hydrogenated white oil.
[0010] Preferably, the mass ratio of SBC to C5 petroleum resin and solvent in step (1) is (10-70):(10-70):240.
[0011] Preferably, the carboxylate modifier in step (2) includes one or more of dimethyl methylene malonate, diethyl methylene malonate, dipropyl methylene malonate, and dibutyl methylene malonate.
[0012] Preferably, the amount of the carboxylate modifier added in step (2) is 1.5-2.5% of the total mass of SBC and C5 petroleum resin.
[0013] Preferably, the reaction temperature in step (2) is 170-220° C., and the reaction time is 1-4 hours.
[0014] Furthermore, an initiator is added during the grafting process in step (2).
[0015] Preferably, the initiator is dicumyl peroxide; the added amount of the initiator is 1-2% of the total mass of SBC and C5 petroleum resin.
[0016] Furthermore, the ester-modified SBC C5 petroleum resin obtained in step (2) is used to prepare an adhesive.
[0017] Preferably, the adhesive comprises the following components in parts by mass:
[0018]
[0019] In the molecular structure of the carboxylate modifier of the present invention, the carboxyl group (COOH) is the main polar group. The electronegativity difference between the oxygen atom and the hydrogen atom in the carboxyl group is large, so that the oxygen atom carries a partial negative charge, while the hydrogen atom carries a partial positive charge, forming a dipole moment and showing polarity. This polarity makes the carboxyl group have good solubility in water or other polar solvents. SBC is a non-polar material, and as an adhesive, its adhesion to many polar materials is poor, and it is difficult to meet the adhesion requirements of some polar materials. Therefore, the present invention introduces polar groups on the main chain of C5 petroleum resin and SBC, enhances the polarity of C5 petroleum resin and SBC, and greatly increases the adhesion of the modified SBC carbon five petroleum resin to polar materials, so that it can be more widely used.
[0020] Beneficial Effects
[0021] The present invention introduces polar groups into the main chains of SBC and C5 petroleum resin, thereby enhancing the polarity of C5 petroleum resin and SBC, greatly increasing the adhesion of the modified SBC C5 petroleum resin to polar materials, and enabling it to be more widely used to meet the needs of more different scenarios. BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Figure 1 This is the infrared spectrum of SBC C5 petroleum resin before ester grafting.
[0023] Figure 2 This is the infrared spectrum of ester grafted SBC C5 petroleum resin.
[0024] Figure 3 This is the infrared spectrum comparison of SBC C5 petroleum resin before and after ester grafting.
[0025] Figure 4 The effect of different proportions of C5 petroleum resin on the adhesive's lasting effect.
[0026] Figure 5 The effect of different proportions of C5 petroleum resin on the peel strength of adhesive.
[0027] Figure 6 The effect of the percentage of modified SIS resin added on the bonding strength of the adhesive.
[0028] Figure 7 The effect of different grafting percentages of carboxylate modifiers on the peel strength of adhesives. DETAILED DESCRIPTION
[0029] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.
[0030] The raw materials used in the embodiments and comparative examples are as follows:
[0031] Styrene block copolymer SBC: styrene-isoprene-styrene block copolymer SIS, commercially available.
[0032] The source of C5 resin is C5 petroleum resin sold in the market.
[0033] Softener: Dioctyl phthalate.
[0034] Antioxidant: 2,4-dimethylphenol (DMQ).
[0035] Comparative Example
[0036] 30 parts of SIS, 50 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol were heated and completely dissolved, coated with a coating machine, and the mechanical properties were tested.
[0037] Example 1
[0038] Weigh 30g SIS and 50g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 2% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A1. 8 parts of resin A1, 27 parts of SIS, 45 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol are heated and completely dissolved, coated with a coating machine, and the mechanical properties are tested.
[0039] Example 2
[0040] Weigh 30g SIS and 50g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 2% of the material weight of dibutyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A2. 8 parts of resin A2, 27 parts of SIS, 45 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol are heated and completely dissolved, coated with a coating machine, and the mechanical properties are tested.
[0041] Example 3
[0042] Weigh 10g SIS and 70g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 2% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A3. 8 parts of resin A3, 29 parts of SIS, 43 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol are heated and completely dissolved, coated with a coating machine, and the mechanical properties are tested.
[0043] Example 4
[0044] Weigh 50g SIS and 30g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 2% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A4. 8 parts of resin A4, 25 parts of SIS, 47 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol are heated and completely dissolved, coated with a coating machine, and the mechanical properties are tested.
[0045] Example 5
[0046] Weigh 70g SIS and 10g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 2% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A5. 8 parts of resin A5, 23 parts of SIS, 49 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol are heated and completely dissolved, coated with a coating machine, and the mechanical properties are tested.
[0047] Example 6
[0048] Weigh 30g SIS and 50g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 2% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A6. 4 parts of resin A6, 28.5 parts of SIS, 47.5 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol are heated and completely dissolved, coated with a coating machine, and the mechanical properties are tested.
[0049] Example 7
[0050] Weigh 30g SIS and 50g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 2% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A7. Heat 12 parts of resin A7, 25.5 parts of SIS, 42.5 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol to completely dissolve, apply with a coating machine, and test the mechanical properties.
[0051] Example 8
[0052] Weigh 30g SIS and 50g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 2% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A8. Heat 16 parts of resin A8, 24 parts of SIS, 40 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol to completely dissolve, apply with a coating machine, and test the mechanical properties.
[0053] Example 9
[0054] Weigh 30g SIS and 50g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 1.5% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A9. 8 parts of resin A9, 27 parts of SIS, 45 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol are heated and completely dissolved, coated with a coating machine, and the mechanical properties are tested.
[0055] Example 10
[0056] Weigh 30g SIS and 50g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 1.7% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A10. 8 parts of resin A10, 27 parts of SIS, 45 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol are heated and completely dissolved, coated with a coating machine, and the mechanical properties are tested.
[0057] Embodiment 11
[0058] Weigh 30g SIS and 50g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 2.3% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A11. 8 parts of resin A11, 27 parts of SIS, 45 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol are heated and completely dissolved, coated with a coating machine, and the mechanical properties are tested.
[0059] Example 12
[0060] Weigh 30g SIS and 50g C5 petroleum resin respectively, dissolve them in 240g xylene, and add them to the reactor and stir evenly; add 2.5% of the material weight of dimethyl methylene malonate and 1% of the material weight of diisopropylbenzene peroxide to the above reactor for grafting, control the polymerization reaction temperature to 195℃, and the reaction time to 2h. After the reaction is completed, the reaction product is stripped to recover the solvent oil to obtain the modified SIS C5 petroleum resin A12. 8 parts of resin A12, 27 parts of SIS, 45 parts of C5 petroleum resin, 19.5 parts of dioctyl phthalate, and 0.5 parts of 2,4-dimethylphenol are heated and completely dissolved, coated with a coating machine, and the mechanical properties are tested.
[0061] Table 1
[0062]
[0063]
[0064] It can be seen from the test results in Table 1 that the adhesive performance of Example 1 is much better than that of the comparative example, so the addition of ester-grafted SIS and ester-grafted C5 petroleum resin can achieve better adhesiveness.
[0065] It can be seen from the test results in Table 1 that the grafting effect of dimethyl methylene malonate is better than that of dibutyl methylene malonate.
[0066] Table 2
[0067]
[0068] Proportion of C5 petroleum resin used for modification 180° peel strength / N / cm 12.5% (Example 3) 5 37.5% (Example 4) 8 62.5% (Example 1) 10 87.8% (Example 5) 8.5
[0069] According to the test results in Table 2 and Figure 4 and Figure 5 It can be seen that the bonding effect is best when the C5 petroleum resin used for modification accounts for 62.5%, that is, the best effect is achieved when the ratio of modified SIS to C5 petroleum resin is 3:5.
[0070] Table 3
[0071] The percentage of modified SIS resin added Bonding strength / N / mm 0% (Comparative ratio) 3.5 5% (Example 6) 5.5 10% (Example 1) 6.8 15% (Example 7) 7.3 20% (Example 8) 7.5
[0072] From Table 3 and Figure 6 The test results show that, while meeting economic benefits, adding 10% modified SIS resin is the best ratio.
[0073] Table 4
[0074] Grafting ratio 180° peel strength / N / cm 1.50% (Example 9) 5 1.70% (Example 10) 7.4 2% (Example 1) 10 2.30% (Example 11) 8.9 2.50% (Example 12) 7.5
[0075] From Table 4 and Figure 7 It can be seen from the test results that the best effect is achieved when the grafting ratio of the carboxylate modifier is 2% of the total material.
[0076] Although the embodiments of the present invention are described in detail above, it is obvious to those skilled in the art that various modifications and variations can be made to these embodiments. However, it should be understood that such modifications and variations are within the scope and spirit of the present invention as described in the claims. Moreover, the present invention described herein may have other embodiments and may be implemented or realized in a variety of ways.
Claims
1. A method for preparing an ester-modified SBC C5 petroleum resin, comprising the following steps: (1) adding styrene block copolymer SBC, C5 petroleum resin and solvent into a reaction kettle and stirring evenly; (2) Adding a carboxylic acid ester modifier to the above reactor for grafting, controlling the reaction temperature to 170-220° C., the reaction time to 1-4 hours, and then recovering the solvent by stripping to obtain an ester-modified SBC C5 petroleum resin.
2. The preparation method according to claim 1, characterized in that: The styrene block copolymer SBC in the step (1) includes one or more of styrene-isoprene-styrene block copolymer SIS, styrene-butadiene-styrene block copolymer SBS, and hydrogenated styrene-butadiene-styrene block copolymer SEBS.
3. The preparation method according to claim 1, characterized in that: The solvent in step (1) includes one or more of benzene, toluene, xylene and hydrogenated white oil.
4. The preparation method according to claim 1, characterized in that: The mass ratio of SBC to C5 petroleum resin and solvent in the step (1) is (10-70):(10-70):
240.
5. The preparation method according to claim 1, characterized in that: The carboxylate modifier in step (2) includes one or more of dimethyl methylene malonate, diethyl methylene malonate, dipropyl methylene malonate, and dibutyl methylene malonate.
6. The preparation method according to claim 1, characterized in that: The amount of the carboxylate modifier added in step (2) is 1.5-2.5% of the total mass of SBC and C5 petroleum resin.
7. The preparation method according to claim 1, characterized in that: An initiator is also added during the grafting process in step (2).
8. The preparation method according to claim 7, characterized in that: The initiator is dicumyl peroxide; the added amount of the initiator is 1-2% of the total mass of SBC and C5 petroleum resin.
9. The preparation method according to claim 1, characterized in that: The ester-modified SBC C5 petroleum resin obtained in step (2) is used to prepare an adhesive.