A phenyl multifunctional epoxy-modified rosin-based polymer, preparation method and application thereof

Abstract

The invention discloses a phenyl multifunctional epoxy-modified rosin-based polymer, a preparation method thereof and an application thereof, a preparation method of a phenyl multifunctional epoxy-modified rosin-based polymer, prepared by reacting an epoxy soybean oil rosin ester with a phenyl multifunctional epoxy compound, wherein the phenyl multifunctional epoxy compound is at least one of N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane, triglycidyl-p-aminophenol or 9,9-bis[(2,3-epoxypropoxy)phenyl]fluorene. The present invention uses biomass rosin as raw material to synthesize brand-new substances, belongs to green environment-friendly resource chemicals, does not have the problems of biological toxicity and environmental pollution, and raw materials are easily available, and a synthesis process is simple, environmentally friendly, and meets the concept of sustainable development; good plasticizing properties for polyvinyl chloride, not only improves the flexibility, processability and tensile strength of polyvinyl chloride, but also improves the stability of the material, and can effectively suppress the thermal damage caused by high temperature during migration problems and PVC processing and use.

Description

Technical Field

[0001] The invention relates to a phenyl multifunctional epoxy-modified rosin-based polymer, a preparation method and application thereof, and belongs to the technical field of natural resource modification and utilization. Background Art

[0002] Polyvinyl chloride (PVC) is a thermoplastic polymer formed by the polymerization of vinyl chloride monomers. It has the advantages of relatively low cost and simple processing. Plasticizers are needed during the processing of polyvinyl chloride to improve the flexibility and processability of PVC. Among them, phthalates are the most used plasticizers. Such plasticizers are toxic in themselves and have the risk of migration during use. They not only pollute the environment, but also pose certain health risks. Hydrogen chloride (HCl) that is easily produced during the processing or use of PVC can be easily removed from the structure of PVC, thereby further catalyzing its degradation. Therefore, the development of environmentally friendly and non-toxic plasticizers that are harmless to organisms has become a new industry trend.

[0003] Rosin is a renewable forest resource, natural and non-toxic, low-priced, and contains a ternary phenanthrene skeleton, two double bonds and a carboxyl group in its resin acid structure, which can be used for modification and has been widely used in the electronics, coatings, inks and other industries. The present invention uses rosin as a raw material to synthesize a novel phenyl multifunctional epoxy-modified rosin-based polymer, which not only promotes the deep processing and utilization of natural resource rosin, but also has certain application value for the development of environmentally friendly plasticizers. Summary of the invention

[0004] The invention provides a phenyl multifunctional epoxy-modified rosin-based polymer, a preparation method and an application thereof, which are green, environmentally friendly, high in yield, have good plasticizing properties for polyvinyl chloride, and can effectively inhibit heat damage caused by high temperature during PVC processing and use.

[0005] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0006] A method for preparing a phenyl multifunctional epoxy-modified rosin-based polymer is prepared by reacting epoxy soybean oil rosin ester with a phenyl multifunctional epoxy compound, wherein the phenyl multifunctional epoxy compound is at least one of N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane, triglycidyl p-aminophenol or 9,9-bis[(2,3-epoxypropoxy)phenyl]fluorene.

[0007] The above method uses bio-based materials as raw materials, does not require any solvent, and has high raw material activity, and can achieve about 100% conversion. This application regards a conversion greater than 99.99% as 100% conversion.

[0008] In order to further improve the discovery efficiency and product yield, the reaction temperature is 105-130°C and the reaction time is 1.5-3h.

[0009] In order to improve the performance of the product, the molar ratio of the epoxy soybean rosin ester to the phenyl multifunctional epoxy compound is 1: (1-2.5).

[0010] More preferably, the phenyl multifunctional epoxy compound is N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane.

[0011] The preparation method of the epoxy soybean oil rosin ester of the present application is: rosin, epoxy soybean oil and a catalyst are mixed and reacted to obtain the ester, wherein the catalyst is at least one of tetrabutylammonium hydrogen sulfate, triethoxybenzyl ammonium chloride or dodecyl ammonium trichloride; the reaction temperature is 105-130° C., and the reaction time is 1-3 hours; the molar ratio of the epoxy group of the epoxy soybean oil to the carboxyl functional group of the rosin is 1:(6-6.5).

[0012] A phenyl multifunctional epoxy-modified rosin-based polymer is prepared by the above preparation method, and its structural formula is: in,

[0013] R is the residue of epoxidized soybean oil.

[0014] The above-mentioned phenyl multifunctional epoxy-modified rosin-based polymer can be used as a polyvinyl chloride plasticizer. The applicant has found through research that the above-mentioned novel modified rosin-based polymer plasticizer introduces more ester groups and benzene rings. Through the interaction between the ester groups of the plasticizer and the polar parts of the polyvinyl chloride molecules, and the shielding effect of the benzene ring groups on the degradation of the polyvinyl chloride molecular chains due to their large volume, the thermal damage caused by high temperature during the processing and use of PVC can be effectively inhibited.

[0015] The mass dosage of the above-mentioned phenyl multifunctional epoxy-modified rosin-based polymer is 10-25% of the mass of polyvinyl chloride.

[0016] In order to further improve the plasticizing effect, the phenyl multifunctional epoxy-modified rosin-based polymer is mixed with dihexyl succinate for use as a polyvinyl chloride plasticizer. Preferably, the mass ratio of the phenyl multifunctional epoxy-modified rosin-based polymer to dihexyl succinate is (9-12):1.

[0017] The technologies not mentioned in the present invention are all referred to the prior art.

[0018] The phenyl multifunctional epoxy-modified rosin-based polymer of the present invention is a brand-new substance synthesized with biomass rosin as a raw material, belongs to green and environment-friendly resource chemicals, has no problems such as biological toxicity and environmental pollution, is easy to obtain raw materials, has a simple synthesis process, is environment-friendly, and conforms to the concept of sustainable development; has good plasticizing performance on polyvinyl chloride, not only improves the flexibility, processability and tensile strength of polyvinyl chloride, but also improves the stability and water resistance of the material, can effectively inhibit migration problems and thermal damage caused by high temperature during PVC processing and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the infrared spectrum of the phenyl multifunctional epoxy-modified rosin-based polymer obtained in Example 1;

[0020] Figure 2 This is the H NMR spectrum of the phenyl multifunctional epoxy-modified rosin-based polymer obtained in Example 1;

[0021] Figure 3 This is the C NMR spectrum of the phenyl multifunctional epoxy-modified rosin-based polymer obtained in Example 1. DETAILED DESCRIPTION

[0022] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0023] In each case, unless otherwise specified, the reaction was carried out at room temperature (15-25°C).

[0024] Example 1

[0025] A phenyl multifunctional epoxy-modified rosin-based polymer, the preparation method of which comprises the following steps:

[0026] 22.68g of rosin (first grade, softening point 71°C, Henan Yuheng Chemical Co., Ltd.) and 20.00g of epoxidized soybean oil (Qingzhou Hongwei Additive Co., Ltd., viscosity 325mpa.S) were blended, and 0.05g of triethoxybenzyl ammonium chloride was added to catalyze the reaction. After stirring and heating to 115°C under a nitrogen atmosphere, the mixture was reacted for 2h to obtain epoxidized soybean oil rosin ester. Then, 12.68g of N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane was added while maintaining the reaction temperature, and the reaction was continued for 2h to obtain a phenyl multifunctional epoxy-modified rosin-based polymer with a conversion rate of 100%.

[0027] Figure 1 The infrared spectrum of Example 1, wherein a is rosin, b is product 1, and c is phenyl multifunctional epoxy-modified rosin-based polymer. In a, 1696 cm -1 The carboxyl peak is near the center. In b, the carboxyl peak disappears.-1 The ester peak appears at 3460 cm -1 The hydroxyl peak appears at 3519 cm, indicating that the rosin and epoxidized soybean oil have reacted. The hydroxyl peak in c shifts to 3519 cm -1 , and at 1241cm -1 The peak of ether bond appears on the surface, indicating that the epoxy group on N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane reacts with the hydroxyl group in product 1 to generate ether bond and new hydroxyl group. In addition, the peak at 1516cm -1 and 1462cm -1 The peak of benzene ring appeared at 3078cm -1 The appearance of the CN bond peak also indicates that N,N,N,N-tetracyclyl-4,4-diaminodiphenylmethane has reacted with product 1.

[0028] Figure 2 This is the H NMR spectrum of Example 1, 5.73ppm is the H atomic peak of the double bond carbon atom of rosin, 2.29ppm is the H atomic peak on the methylene next to the epoxy soybean oil ester group, 7.0ppm is the H atomic peak on the benzene ring structure of N,N,N,N-tetracyclyl-4,4-diaminodiphenylmethane. The results show that the target product was successfully synthesized.

[0029] Figure 3 The NMR C spectrum of Example 1 shows that 122.45ppm and 135.49ppm are characteristic peaks of double bonds in the rosin structure, 173.23ppm is a characteristic peak of the epoxy soybean oil ester group, and 109.31ppm and 145.23ppm are C atom peaks on the benzene ring structure of N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane. The results show that the target product was successfully synthesized. The structure of the target product is:

[0030] Wherein, R is the reaction residue of epoxidized soybean oil.

[0031] Example 2

[0032] A phenyl multifunctional epoxy-modified rosin-based polymer, the preparation method of which comprises the following steps:

[0033] 18.90 g of rosin and 16.20 g of epoxy soybean oil were blended, and 0.044 g of triethoxybenzyl ammonium chloride was added to catalyze the reaction. The mixture was stirred and heated to 118° C. under a nitrogen atmosphere, and the mixture was reacted for 1.5 h to obtain epoxy soybean oil rosin ester. The reaction temperature was then adjusted to 122° C., 9.50 g of N,N,N,N-tetracyclyl-4,4-diaminodiphenylmethane was added, and the mixture was reacted for 2 h to obtain a phenyl multifunctional epoxy-modified rosin-based polymer with a conversion rate of 100%.

[0034] Example 3

[0035] A phenyl multifunctional epoxy-modified rosin-based polymer, the preparation method of which comprises the following steps:

[0036] 17.65 g of rosin and 19.20 g of epoxy soybean oil were blended, and 0.055 g of triethoxybenzyl ammonium chloride was added to catalyze the reaction. The mixture was stirred and heated to 128° C. under a nitrogen atmosphere, and the mixture was reacted for 1.5 h to obtain epoxy soybean oil rosin ester. The reaction temperature was then adjusted to 110° C., 10.00 g of N,N,N,N-tetracyclyl-4,4-diaminodiphenylmethane was added, and the mixture was reacted for 2 h to obtain a phenyl multifunctional epoxy-modified rosin-based polymer with a conversion rate of 100%.

[0037] Example 4

[0038] A phenyl multifunctional epoxy-modified rosin-based polymer, the preparation method of which comprises the following steps:

[0039] 19.40 g of rosin and 16.85 g of epoxy soybean oil were blended, and 0.046 g of triethoxybenzyl ammonium chloride was added to catalyze the reaction. The mixture was stirred and heated to 120° C. under a nitrogen atmosphere, and the mixture was reacted for 2 h to obtain epoxy soybean oil rosin ester. The reaction temperature was then adjusted to 125° C., 9.88 g of N,N,N,N-tetracyclyl-4,4-diaminodiphenylmethane was added, and the mixture was reacted for 2.5 h to obtain a phenyl multifunctional epoxy-modified rosin-based polymer with a conversion rate of 100%.

[0040] Example 5

[0041] A phenyl multifunctional epoxy-modified rosin-based polymer, the preparation method of which comprises the following steps:

[0042] 19.40 g of rosin and 16.85 g of epoxy soybean oil were blended, and 0.046 g of triethoxybenzyl ammonium chloride was added to catalyze the reaction. The mixture was stirred and heated to 120° C. under a nitrogen atmosphere, and the mixture was reacted for 2 h to obtain epoxy soybean oil rosin ester. The reaction temperature was then adjusted to 115° C., 9.88 g of N,N,N,N-tetracyclyl-4,4-diaminodiphenylmethane was added, and the mixture was reacted for 2.5 h to obtain a phenyl multifunctional epoxy-modified rosin-based polymer with a conversion rate of 100%.

[0043] Application Example 1

[0044] Weigh 4.0 g of polyvinyl chloride powder (Aladdin Reagent Co., Ltd., specification: K-value 72-71), 0.9 g of the phenyl multifunctional epoxy-modified rosin-based polymer obtained in Example 1 and 0.1 g of dihexyl succinate, add them into 65 ml of tetrahydrofuran, stir at 40°C for 0.5 h, pour the solution into a watch glass and dry it at 40°C for 24 h to obtain a modified polyvinyl chloride film.

[0045] Application Example 2

[0046] Weigh 4.0 g of polyvinyl chloride powder (Aladdin Reagent Co., Ltd., specification: K-value 72-71), 0.6 g of the phenyl multifunctional epoxy-modified rosin-based polymer obtained in Example 1 and 0.4 g of dihexyl succinate, add them into 65 ml of tetrahydrofuran, stir at 40°C for 0.5 h, pour the solution into a watch glass and dry it at 40°C for 24 h to obtain a modified polyvinyl chloride film.

[0047] Application Example 3

[0048] 4.0 g of polyvinyl chloride powder (Aladdin Reagent Co., Ltd., specification: K-value 72-71) and 1.0 g of the phenyl multifunctional epoxy-modified rosin-based polymer obtained in Example 1 were weighed, added to 65 ml of tetrahydrofuran, stirred at 50° C. for 0.5 h, poured the solution into a watch glass and dried at 45° C. for 24 h to obtain a modified polyvinyl chloride film.

[0049] Comparative Example 1

[0050] Weigh 3.0 g of polyvinyl chloride powder and dissolve it in 50 ml of tetrahydrofuran at 45°C with stirring for 0.5 h. Pour the solution into a watch glass and dry it at 45°C for 24 h to obtain a modified polyvinyl chloride film.

[0051] Comparative Example 2

[0052] Weigh 3.0 g of polyvinyl chloride powder and 1.8 g of dioctyl phthalate in 50 ml of tetrahydrofuran, stir at 45°C for 0.5 h, pour the solution into a watch glass and dry at 45°C for 24 h to obtain a modified polyvinyl chloride film.

[0053] Comparative Example 3

[0054] Weigh 3.0 g of polyvinyl chloride powder, 0.9 g of dioctyl phthalate and 0.1 g of dihexyl succinate in 50 ml of tetrahydrofuran, stir at 45°C for 0.5 h, pour the solution into a watch glass and dry at 45°C for 24 h to obtain a modified polyvinyl chloride film.

[0055] According to GB / T 3830-2008, the performance of the modified polyvinyl chloride film was tested. The results are shown in Table 1.

[0056] Table 1 Mechanical properties results

[0057] sample Tensile strength(Mpa) Elongation at break (%) Temperature at which weight loss reaches 5% (℃) Application Example 1 31.85 380.91 305 Application Example 2 30.96 371.31 293 Application Example 3 30.68 370.26 290 Comparative Example 1 28.32 2.61 182 Comparative Example 2 16.53 205.64 225 Comparative Example 3 20.11 153.52 190

[0058] As can be seen from Table 1, the phenyl multifunctional epoxy-modified rosin-based polymer prepared in the present application has improved tensile strength and elongation at break at the same time, while improving stability, avoiding migration, and effectively inhibiting thermal damage caused by high temperature during PVC processing and use; the modified polyvinyl chloride film prepared in Application Example 1 was immersed in water for one week, and the surface did not change, the water absorption rate was less than 0.001%, and it had excellent water resistance.

Claims

1. A phenyl multifunctional epoxy-modified rosin-based polymer, characterized in that: It is prepared by the following method: 22.68 g of rosin and 20.00 g of epoxy soybean oil are blended, 0.05 g of triethoxybenzyl ammonium chloride is added to catalyze the reaction, and the mixture is heated to 115 °C under stirring under a nitrogen atmosphere and reacted for 2 hours to obtain epoxy soybean oil rosin ester. Then, while maintaining the reaction temperature, 12.68 g of N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane is added and the reaction is continued for 2 hours to obtain a phenyl multifunctional epoxy-modified rosin-based polymer.

2. A phenyl multifunctional epoxy-modified rosin-based polymer, characterized in that: It is prepared by the following method: 18.90g of rosin and 16.20g of epoxy soybean oil are blended, 0.044g of triethoxybenzyl ammonium chloride is added to catalyze the reaction, and the mixture is heated to 118°C under a nitrogen atmosphere with stirring, and the mixture is reacted for 1.5h to obtain epoxy soybean oil rosin ester. The reaction temperature is then adjusted to 122°C, 9.50g of N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane is added, and the mixture is reacted for 2h to obtain a phenyl multifunctional epoxy-modified rosin-based polymer.

3. A phenyl multifunctional epoxy-modified rosin-based polymer, characterized in that: It is prepared by the following method: 17.65g of rosin and 19.20g of epoxy soybean oil are blended, 0.055g of triethoxybenzyl ammonium chloride is added to catalyze the reaction, and the mixture is stirred and heated to 128°C under a nitrogen atmosphere, and the mixture is reacted for 1.5h to obtain epoxy soybean oil rosin ester. The reaction temperature is then adjusted to 110°C, 10.00g of N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane is added, and the mixture is reacted for 2h to obtain a phenyl multifunctional epoxy-modified rosin-based polymer.

4. A phenyl multifunctional epoxy-modified rosin-based polymer, characterized in that: It is prepared by the following method: 19.40g of rosin and 16.85g of epoxy soybean oil are blended, 0.046g of triethoxybenzyl ammonium chloride is added to catalyze the reaction, and the mixture is heated to 120°C under stirring under a nitrogen atmosphere and reacted for 2h to obtain epoxy soybean oil rosin ester. The reaction temperature is then adjusted to 125°C, 9.88g of N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane is added, and the reaction is reacted for 2.5h to obtain a phenyl multifunctional epoxy-modified rosin-based polymer.

5. A phenyl multifunctional epoxy-modified rosin-based polymer, characterized in that: It is prepared by the following method: 19.40g of rosin and 16.85g of epoxy soybean oil are blended, 0.046g of triethoxybenzyl ammonium chloride is added to catalyze the reaction, and the mixture is heated to 120°C under stirring under a nitrogen atmosphere and reacted for 2h to obtain epoxy soybean oil rosin ester. The reaction temperature is then adjusted to 115°C, 9.88g of N,N,N,N-tetraepoxypropyl-4,4-diaminodiphenylmethane is added, and the reaction is carried out for 2.5h to obtain a phenyl multifunctional epoxy-modified rosin-based polymer.

6. An application of the phenyl multifunctional epoxy-modified rosin-based polymer according to any one of claims 1 to 5, characterized in that: The phenyl multifunctional epoxy-modified rosin-based polymer is used as a polyvinyl chloride plasticizer.

7. The use according to claim 6, characterized in that: The mass dosage of the phenyl multifunctional epoxy-modified rosin-based polymer is 10-25% of the mass of the polyvinyl chloride.

8. The use according to claim 6 or 7, characterized in that: The phenyl multifunctional epoxy-modified rosin-based polymer is mixed with dihexyl succinate and used as a polyvinyl chloride plasticizer.

9. The use according to claim 8, characterized in that: The mass ratio of the phenyl multifunctional epoxy-modified rosin-based polymer to dihexyl succinate is (9-12):1.

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