Compostable C9 petroleum resin with main chain containing photosensitive group as well as preparation method and application of compostable C9 petroleum resin

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to compostable C9 petroleum resin with a main chain containing photosensitive groups as well as a preparation method and application of the compostable C9 petroleum resin. Raw materials comprise a C9 fraction, a photosensitive functional monomer, a polymerization reaction catalyst and a molecular regulator. The preparation method comprises the following steps: mixing the pretreated C9 fraction, the photosensitive functional monomer and the molecular regulator, and preheating to obtain a mixture; adding a polymerization reaction catalyst into the mixture, and carrying out cationic polymerization reaction; after the polymerization reaction catalyst is dropwise added, carrying out constant-temperature reaction; and terminating the reaction, washing and purifying to obtain the product. The product can be applied to preparation of adhesives, coatings or rubber products. The invention provides a method for introducing a photosensitive group into a C9 petroleum resin main chain through molecular design to realize compostability of the C9 petroleum resin main chain. The product has the characteristic of rapid degradation in a compost environment (especially under an illumination condition) while maintaining good use performance. The preparation process is simple and easy for industrial production.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a compostable C9 petroleum resin with photosensitive groups in its main chain, its preparation method, and its application. Background Technology

[0002] C9 petroleum resin is a thermoplastic resin obtained through cationic polymerization using C9 fraction, a byproduct of petroleum cracking, as the main raw material. Due to its excellent tackifying properties, water resistance, acid and alkali resistance, and low price, it is widely used in adhesives, coatings, rubber processing, inks, and other fields.

[0003] However, the main chain of traditional C9 petroleum resin molecules is composed of stable carbon-carbon bonds, resulting in a dense structure that is extremely difficult for microorganisms to degrade in the natural environment. After their service life, products made from these resins are typically disposed of through landfill or incineration, which not only wastes resources but also leads to long-term "white pollution" and microplastic problems, placing enormous pressure on the environment.

[0004] With increasingly stringent global environmental regulations and growing consumer awareness of environmental protection, the development of environmentally degradable petroleum resins has become an urgent industry need. Currently, while methods exist for physically blending biodegradable materials, these methods suffer from poor compatibility, incomplete degradation, and negative impacts on the performance of the main material. Therefore, designing an inherently biodegradable C9 petroleum resin at the molecular structure level is a technical challenge that urgently needs to be addressed by those skilled in the art. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the purpose of this invention is to provide a compostable C9 petroleum resin with photosensitive groups in its main chain, its preparation method, and its applications.

[0006] To achieve the above and other related objectives, the present invention provides the following technical solutions: In a first aspect, a compostable C9 petroleum resin containing photosensitive groups in its main chain is provided, characterized in that it is prepared by cationic polymerization from raw materials comprising the following parts by weight: 70-90 parts C9 fraction, 5-25 parts photosensitive functional monomer, 0.5-5 parts polymerization catalyst, 0.1-2 parts molecular regulator.

[0007] In one embodiment, the photosensitive functional monomer is a compound containing a styrene group and a photosensitive group, wherein the photosensitive group is a ketone group.

[0008] In one embodiment, the photosensitive functional monomer is selected from one or a combination of two of styrylphenyl ketone, styrylmethylphenyl ketone, or styrylcyclopentanone.

[0009] It should be noted that the photosensitive functional monomer is a compound containing a carbon-carbon double bond and a photosensitive group in its molecular structure, and its general formula can be represented as St-Photo-X, where St is a styrene group or a substituted styrene group, Photo is a photosensitive group, preferably a ketone structure, and X is another substituent (phenyl, substituted phenyl, or alkyl, etc.). Preferably, the photosensitive functional monomer is a styrene-phenyl ketone. These monomers can effectively participate in the cationic copolymerization of C9 fractions through the styrene group structure, and also introduce the photosensitive ketone group into the polymer backbone or side chain.

[0010] In one embodiment, the polymerization catalyst comprises aluminum trichloride or boron trifluoride diethyl ether complex.

[0011] In one embodiment, the molecular weight modifier includes divinylbenzene or α-methylstyrene.

[0012] Secondly, a method for preparing a compostable C9 petroleum resin with a main chain containing photosensitive groups is provided, comprising the following steps: The pretreated C9 fraction, photosensitive functional monomer, and molecular regulator are mixed and preheated to obtain a mixture. Under stirring and inert gas protection, a polymerization catalyst is added to the mixture to carry out a cationic polymerization reaction; After the polymerization catalyst is added dropwise, the reaction is kept at a constant temperature to allow the polymerization reaction to proceed fully. The reaction was terminated by adding a terminator, and after washing and purification, compostable C9 petroleum resin with photosensitive groups in the main chain was obtained.

[0013] It should be noted that the polymerization catalyst is a Friedel-Crafts catalyst, preferably an aluminum trichloride or boron trifluoride diethyl ether complex.

[0014] In one embodiment, the pretreated C9 fraction is obtained by vacuum distillation of the C9 fraction, collecting the fraction at 145°C-195°C; The C9 fraction, photosensitive functional monomer, and molecular regulator are mixed and preheated to 30-60℃ to obtain a mixture.

[0015] In one embodiment, under stirring and inert gas protection, a polymerization catalyst is added to the mixture, and a cationic polymerization reaction is carried out at 50-90°C for 2-6 hours; after the polymerization catalyst is added dropwise, the reaction is kept at 60°C-100°C for 2-6 hours to allow the polymerization reaction to proceed fully.

[0016] Furthermore, the reaction is terminated by adding hot water or an alcohol-based terminator (such as a 5% NaOH solution) to the reaction vessel to stop the polymerization reaction. The mixture is then allowed to stand and separate into layers; the acidic aqueous layer is then removed.

[0017] In one embodiment, the terminating agent includes an alkaline aqueous solution or an alcohol solvent.

[0018] Further purification involves washing the resin layer with water until neutral, then removing unreacted monomers and oligomers by vacuum distillation or steam stripping to obtain a light yellow to brownish-red solid compostable C9 petroleum resin.

[0019] Thirdly, an adhesive, coating, or rubber product is provided, comprising the aforementioned compostable C9 petroleum resin with a main chain containing photosensitive groups.

[0020] The beneficial effects of this invention are: This invention provides a method for achieving compostability by introducing photosensitive groups into the main chain of C9 petroleum resin through molecular design. The resulting resin maintains good performance while exhibiting rapid degradation under composting conditions (especially under light). The preparation process is simple and easily scalable for industrial production.

[0021] The preparation process of this invention is divided into: raw material pretreatment (C9 fraction pretreatment), partial raw material premixing, catalytic polymerization, isothermal reaction, termination and post-treatment, and purification.

[0022] More specifically, Molecular-level degradability: Photosensitive groups are attached to the main chain of C9 petroleum resin through copolymerization, rather than simple physical mixing. These photosensitive groups act as "pre-set breakage points," absorbing light energy under natural light or specific illumination in composting facilities to undergo Norrish type I or II reactions, initiating molecular chain breakage and degrading the high-molecular-weight resin into low-molecular-weight fragments. These fragments have a larger specific surface area, making them more easily biodegraded by microorganisms in the environment, thus achieving the beneficial property of "compostability."

[0023] Good performance is maintained: The selected photosensitive functional monomer (such as styrene-phenyl ketone) has a styrene structure that has extremely high polymerization compatibility with components such as indene and styrene in the C9 fraction, and can form a copolymer with a uniform structure. This ensures that the final product is comparable to traditional C9 petroleum resin in key indicators such as softening point, adhesion performance and compatibility, without affecting its practical application.

[0024] High process feasibility: The preparation method described in this invention does not require changes to the traditional C9 petroleum resin production equipment and core process (cationic polymerization). It only requires the addition of photosensitive functional monomers during the feeding stage, which is easy to carry out technical transformation and industrial scale-up on existing production lines, and the increase in cost is controllable. Detailed Implementation

[0025] The present invention will now be further described in conjunction with specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments.

[0026] In this invention, unless otherwise specified, all parts are by weight, and the equipment and raw materials used are commercially available or commonly used in the art. Unless otherwise specified, the methods in the following embodiments are conventional methods in the art.

[0027] It should be noted that: The typical composition of the effective C9 fraction is shown in Table 1: Table 1

[0028] C9: C9 fraction from refining and chemical enterprises under Sinopec.

[0029] Yangba C9: C9 fraction from Yangzi Petrochemical.

[0030] Due to differences in raw materials and processes, the two have different compositions.

[0031] The embodiments and comparative examples of this invention use the refined C9 from Table 1 for experiments.

[0032] In addition, the C9 fraction of the present invention needs to be pretreated in advance: the C9 fraction is distilled under reduced pressure, and the fraction at 145℃-195℃ is collected to remove the polymerization inhibitor and water.

[0033] Example 1 By weight, 90 parts of C9 fraction, 8 parts of styrene-phenyl ketone, and 0.5 parts of α-methylstyrene were added to a reactor, and the mixture was heated to 50°C and stirred until homogeneous. Under nitrogen protection and stirring, 1.5 parts of aluminum trichloride catalyst were slowly added dropwise, controlling the reaction temperature at 60-70°C. After the addition was complete, the reaction was maintained at 70°C for 4 hours.

[0034] The reactants were transferred to a termination vessel, and a 5% NaOH aqueous solution was added to terminate the reaction. The mixture was allowed to stand and separate into layers, and the aqueous layer was discarded. The resin layer was washed with hot water until neutral, and then subjected to vacuum distillation at 250℃ and -0.095MPa to remove volatiles, yielding the product.

[0035] Example 2 Unlike Example 1, in this example, 93 parts by weight of the C9 fraction, 5 parts by weight of styrene-phenyl ketone, and 0.5 parts by weight of α-methylstyrene were added to the reactor, heated to 50°C, and stirred until homogeneous. Under nitrogen protection and stirring, 1.5 parts by weight of aluminum trichloride catalyst were slowly added, controlling the reaction temperature at 60-70°C. After the addition was complete, the reaction was maintained at 70°C for 4 hours.

[0036] The rest is the same as in Example 1.

[0037] Example 3 Unlike Example 1, in this example, 91 parts by weight of the C9 fraction, 8 parts by weight of styrene-phenyl ketone, and 0.5 parts by weight of α-methylstyrene were added to the reactor, heated to 50°C, and stirred until homogeneous. Under nitrogen protection and stirring, 1.0 part by weight of boron trifluoride diethyl ether catalyst was slowly added dropwise, controlling the reaction temperature at 60-70°C. After the addition was complete, the reaction was maintained at 70°C for 4 hours.

[0038] The rest is the same as in Example 1.

[0039] Example 4 Unlike Example 1, in this example, 88 parts by weight of C9 fraction, 10 parts by weight of styrene-phenyl ketone, and 0.5 parts by weight of α-methylstyrene were added to the reactor, heated to 50°C, and stirred until homogeneous. Under nitrogen protection and stirring, 2.0 parts by weight of boron trifluoride diethyl ether catalyst were slowly added dropwise, controlling the reaction temperature at 60-70°C. After the addition was complete, the reaction was maintained at 70°C for 4.5 hours.

[0040] The rest is the same as in Example 1.

[0041] Comparative Example 1 By weight, 98 parts of C9 fraction and 0.5 parts of α-methylstyrene were added to the reactor, heated to 50°C, and stirred until homogeneous. Under nitrogen protection and stirring, 1.5 parts of aluminum trichloride catalyst were slowly added, controlling the reaction temperature at 60-70°C. After the addition was complete, the reaction was maintained at 70°C for 4.5 hours.

[0042] The reactants were transferred to a termination vessel, and a 5% NaOH aqueous solution was added to terminate the reaction. The mixture was allowed to stand and separate into layers, and the aqueous layer was discarded. The resin layer was washed with hot water until neutral, and then subjected to vacuum distillation at 250℃ and -0.095MPa to remove volatiles, yielding the product.

[0043] Comparative Example 2 Unlike Comparative Example 1, in this comparative example, 98.5 parts of C9 fraction and 0.5 parts of α-methylstyrene were added to a reactor, heated to 50°C, and stirred until homogeneous. Under nitrogen protection and stirring, 1.5 parts of boron trifluoride diethyl ether catalyst were slowly added, controlling the reaction temperature at 60-70°C. After the addition was complete, the reaction was maintained at 70°C for 4.0 hours.

[0044] The rest is the same as Comparative Example 1.

[0045] The products from Examples 1-4 and Comparative Examples 1-2 were used as samples for performance testing: 1. Softening point: The softening point tester was used according to the method specified in GB / T 2294-1997.

[0046] 2. Molecular weight: The sample was dissolved in tetrahydrofuran to prepare a resin solution with a concentration of 0.1 wt%. The test was performed on a GPC instrument equipped with a differential refractive index detector, using tetrahydrofuran as the mobile phase, at a column temperature of 25 °C and a flow rate of 10.0 mL / min.

[0047] The results are shown in Table 2.

[0048] Table 2. Basic performance tests of products from different groups

[0049] 3. Peel strength test: 30g of the resin product from Examples 1-4 and Comparative Examples 1-2, 50g of commercially available styrene-butadiene copolymer (SBS) with a number average molecular weight of 90,000, 20g of naphthenic oil, 2g of 2,6-di-tert-butyl-4-methylphenol, and 2g of phenyl phthalate were mixed and stirred at 180°C for 3 hours to obtain a uniform and viscous hot melt adhesive. The hot melt adhesive was then coated onto a PET film to test its 180° peel strength. The method for determining the 180° peel strength of the hot melt adhesive was carried out according to GB / T 4851-1998.

[0050] Table 3. Adhesion performance test of products in different groups

[0051] 4. Degradation performance (laboratory accelerated light irradiation test): The samples were irradiated in an accelerated UV aging chamber for 100 hours. Then, the softening point and molecular weight of the samples from Examples 1-4 and Comparative Examples 1-2 were tested according to the aforementioned method (softening point and molecular weight).

[0052] Table 4. Degradation performance tests of products from different groups

[0053] As can be seen from the data in Table 2-4, the prepared C9 petroleum resin with photosensitive groups has similar appearance and thickening properties to that of C9 petroleum resin without photosensitive groups. At the same time, the resin containing photosensitive groups can decompose more quickly under ultraviolet light stimulation, thereby achieving the harmless treatment of waste petroleum resin.

[0054] Furthermore, the compostable C9 petroleum resin prepared by this invention can be used to prepare adhesives, coatings, or rubber products.

[0055] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A compostable C9 petroleum resin with a main chain containing photosensitive groups, characterized in that, It is prepared by cationic polymerization from raw materials comprising the following parts by weight: 70-90 parts C9 fraction, 5-25 parts photosensitive functional monomer, 0.5-5 parts polymerization catalyst, 0.1-2 parts molecular regulator.

2. The compostable C9 petroleum resin with a main chain containing photosensitive groups according to claim 1, characterized in that, The photosensitive functional monomer is a compound containing a styrene group and a photosensitive group, the photosensitive group being a ketone group.

3. The compostable C9 petroleum resin with a main chain containing photosensitive groups according to claim 2, characterized in that, The photosensitive functional monomer is selected from one or a combination of two of styrylphenyl ketone, styrylmethylphenyl ketone, or styrylcyclopentanone.

4. The compostable C9 petroleum resin with a main chain containing photosensitive groups according to claim 1, characterized in that, The catalysts for the polymerization reaction include aluminum trichloride or boron trifluoride diethyl ether complexes.

5. The compostable C9 petroleum resin with a main chain containing photosensitive groups according to claim 1, characterized in that, Molecular weight modifiers include divinylbenzene or α-methylstyrene.

6. A method for preparing a compostable C9 petroleum resin with a main chain containing photosensitive groups according to any one of claims 1-5, characterized in that, Includes the following steps: The pretreated C9 fraction, photosensitive functional monomer, and molecular regulator are mixed and preheated to obtain a mixture. Under stirring and inert gas protection, a polymerization catalyst is added to the mixture to carry out a cationic polymerization reaction; After the polymerization catalyst is added dropwise, the reaction is kept at a constant temperature to allow the polymerization reaction to proceed fully. The reaction was terminated by adding a terminator, and after washing and purification, compostable C9 petroleum resin with photosensitive groups in the main chain was obtained.

7. The method for preparing a compostable C9 petroleum resin with a main chain containing photosensitive groups according to claim 6, characterized in that, The pretreated C9 fraction is obtained by vacuum distillation of the C9 fraction, collecting the fraction at 145℃-195℃; The C9 fraction, photosensitive functional monomer, and molecular regulator are mixed and preheated to 30-60℃ to obtain a mixture.

8. The method for preparing a compostable C9 petroleum resin with a main chain containing photosensitive groups according to claim 6, characterized in that, Under stirring and inert gas protection, a polymerization catalyst is added to the mixture, and a cationic polymerization reaction is carried out at 50-90℃ for 2-6 hours. After the polymerization catalyst is completely added, the reaction is kept at 60℃-100℃ for 2-6 hours to ensure that the polymerization reaction is fully carried out.

9. The method for preparing a compostable C9 petroleum resin with a main chain containing photosensitive groups according to claim 6, characterized in that, Terminating agents include alkaline aqueous solutions or alcoholic solvents.

10. An adhesive, coating, or rubber product, characterized in that, The compostable C9 petroleum resin comprising a main chain containing photosensitive groups as described in any one of claims 1-5.

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