Preparation method and application of olefin unsaturated polymer
By catalyzing the synthesis of olefin-based unsaturated polymers using organic or inorganic bases, the problems of low yield and transition metal residue in the prior art are solved, and efficient and environmentally friendly polymer synthesis is achieved, and good anti-ultraviolet aging properties are good.
Patent Information
- Application Number
- CN202510430725.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-08
- Publication Date
- 2025-06-13
AI Technical Summary
The prior art has problems such as low yield, residual contamination of transition metals and limited substrate range when catalyzing diazon compounds to synthesize olefin-based unsaturated polymers.
Organic or inorganic bases are used as catalysts to construct an olefin-based unsaturated polymer through homopolymerization. The reaction conditions are mild and the process is simple, which avoids the use of transition metals.
It has achieved high yield, high molecular weight and clear structure of olefinic unsaturated polymers, compatible with a variety of diazonium monomers, and has good resistance to UV aging.
Smart Images
Figure CN120137151A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the fields of polymer synthesis technology and polymer-based ultraviolet absorbers, and relates to a preparation method and application of an olefinic unsaturated polymer compound. Specifically, it relates to a method for homopolymerizing diazo monomers catalyzed by organic and inorganic bases to construct an olefinic unsaturated polymer. The olefinic unsaturated polymer has potential application value in improving the ultraviolet aging of materials when used as an ultraviolet absorber. Background Art
[0002] Polymer materials play an extremely important role in the progress and development of human society. In recent years, unsaturated polymers containing olefins have played an important role in modern chemistry due to their unique chemical properties and diverse reactivity, being able to undergo various transformations. Unsaturated polymers exhibit unique advantages in the field of material protection as ultraviolet absorbers. The conjugated double bonds or aromatic ring systems rich in their molecular structures endow them with excellent ultraviolet light absorption ability, and at the same time have the stability and processability of polymer materials. First is efficient ultraviolet absorption and broad-spectrum protection. The conjugated double bonds (such as the benzene ring in polystyrene and the continuous double bonds in polyacetylene) or aromatic structures in unsaturated polymers can effectively absorb ultraviolet light (UVA: 315 - 400 nm, UVB: 280 - 315 nm) through π-π* electronic transitions, especially showing a significant shielding effect on short-wave high-energy ultraviolet light. Second is long-term stability and anti-migration. Traditional small-molecule ultraviolet absorbers are prone to failure due to volatilization, migration, or photodegradation, while unsaturated polymers anchor functional groups in the molecular chain through chemical bonds, significantly reducing the risk of migration and loss. And there are advantages such as wide application and process adaptability. Unsaturated polymers can be combined with matrix materials through various processing forms (such as solution coating, melt blending, in-situ polymerization), etc.
[0003] Diazo compounds, as an important class of organic compounds, can synthesize olefinic compounds and play a key role in modern synthetic chemistry (Synthesis of thioesters using an electrochemical three-component reaction involving elemental sulfur). Since Grundmann first discovered the carbene dimerization reaction in 1938 ( Regarding the decomposition of diazo ketones, various methods have been developed to enhance this specific transformation as a valuable alternative route for synthesizing functionalized alkenes. Among various carbene precursors, toluene-p-sulphonylhydrazones (Tos-hydrazones) were first reported to yield alkene compounds via a transient diazo intermediate under the action of strong bases (The Decomposition of Toluene-p-Sulphonylhydrazones by Alkali). In addition to the indirect hydrazone route, methods for directly forming carbene intermediates from diazo compounds to construct alkenes have been extensively reported, and these methods can directly prepare alkene compounds from diazo compounds. Currently, two main strategies are employed for preparing alkenes from diazo compounds: transition metal catalysis and photocatalysis. Diazo compounds exhibit excellent reactivity and selectivity under transition metal catalysis or photocatalysis conditions. For example, under the action of transition metal catalysts such as ruthenium and rhodium, diazo compounds can achieve efficient intramolecular or intermolecular olefination reactions to produce products with specific stereoconfigurations (Single-Component Polycondensation of Bis(alkoxycarbonyldiazomethyl)aromatic Compounds To Afford Poly(arylenevinylene)s with an Alkoxycarbonyl Group on Each Vinylene Carbon Atom). However, the products prepared using transition metals as catalysts have problems such as low product yields and the tendency of transition metals to remain inside the polymer, thereby contaminating the products. In addition, the development of photocatalytic technology enables efficient transformation of diazo compounds under metal-free conditions, further expanding their application scope (Blue light-promoted cross-coupling of aryldiazoacetates and diazocarbonyl compounds). However, photocatalysis has poor substrate generality because only diazo compounds with specific structures are sensitive to visible light and undergo diazo coupling reactions. Based on the above problems, developing more convenient and efficient catalytic synthesis of diazo compounds to prepare novel alkene-based unsaturated polymers is full of challenges and prospects. Summary of the Invention
[0004] To address the existing deficiencies and drawbacks of the above technologies, the present invention provides a method for constructing an olefinic unsaturated polymer compound through a homopolymerization reaction using an organic base or an inorganic base as a catalyst and a diazo compound as a monomer. This method features mild reaction conditions, a simple process, and high polymerization efficiency. The resulting polymer has the advantages of a high molecular weight, a high yield, and a well-defined structure. At the same time, the polymer obtained by this method has unique potential applications in the field of anti-ultraviolet aging. The olefinic unsaturated polymer of the present invention, as an ultraviolet absorber, has good compatibility with the matrix and does not affect the performance of the matrix. After 60 days of ultraviolet light irradiation, the performance change of the material is slight.
[0005] The technical solution of the present invention:
[0006] A method for preparing an olefinic unsaturated polymer, the steps are as follows:
[0007] Accurately weigh 1 molar equivalent of diazo compound monomer A and 1 - 7 molar equivalents of base, dissolve them in a solvent to obtain a reaction solution, and control the concentration of diazo compound monomer A in the reaction solution to be 0.05 - 0.4 M; continuously stir the reaction solution in an air environment at 10 - 80 °C for 8 - 48 h, stop the reaction and restore to room temperature; dissolve the crude product with N,N-dimethylformamide (DMF), centrifuge, and filter with an organic filter membrane to filter out the residual base, sediment the crude product in a precipitant, and centrifuge to collect the precipitate; redissolve the precipitate with N,N-dimethylformamide (DMF), and sediment it again in the precipitant, repeat the above process three times; wash the precipitate twice with the precipitant, then dialyze the crude product in deionized water for 24 - 48 h (MWCO = 1 kDa), and obtain a red solid after freeze-drying, which is the olefinic unsaturated polymer.
[0008] The reaction general formula is as follows:
[0009]
[0010] The degree of polymerization n of the olefinic unsaturated polymer is greater than 5, the weight-average molecular weight range of the olefinic unsaturated polymer is 6200 - 16000 g / mol, and the molecular weight distribution range is 1.03 - 1.75.
[0011] The base is sodium sulfide (Na 2 2S), potassium hydroxide (KOH), potassium carbonate (K 2 2CO 3 3), potassium tert-butoxide (t-BuOK), 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU);
[0012] The solvent is one or more of dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), N,N-dimethylformamide (DMF) mixed in any proportion;
[0013] The settling agent is ethyl acetate and / or methanol;
[0014] The structure of the diazo monomer A is as follows:
[0015] The corresponding structure is as follows:
[0016]
[0017] The olefinic unsaturated polymer obtained by the above preparation method is used in the field of anti-ultraviolet aging, and the steps are as follows:
[0018] First, dissolve the matrix material with a solvent, and then add the prepared olefinic unsaturated polymer to the solution containing the matrix material respectively. Stir at room temperature for 12 - 24 h, filter out the insoluble substances, collect the filtrate in a glass bottle and seal it. Then place the glass bottle in an ultrasonic cleaner for ultrasonic treatment for 1 - 6 h for defoaming treatment. Then evenly coat the treated film solution in a clean and horizontal glass petri dish. Then place the glass dish in an oven to heat and volatilize the solvent to obtain a transparent and uniform polymer composite film.
[0019] The matrix material is PBAT.
[0020] The solvent is one or more of N,N-dimethylformamide (DMF), chloroform (CHCl 3 ), N-methylpyrrolidone (NMP) mixed in any proportion.
[0021] Advantages of the present invention:
[0022] (1) The present invention provides a method for constructing an olefinic unsaturated polymer compound by using an organic base or an inorganic base as a catalyst and a diazo compound as a monomer for a homopolymerization reaction;
[0023] (2) Compared with the photocatalytic method, the present invention has a wider substrate range, can be compatible with a variety of diazo monomers, and the yield of the obtained polyunsaturated polymer is as high as 81%, having the advantages of a relatively high molecular weight and a well-defined structure (the weight-average molecular weight range is 6200 - 16000 g / mol);
[0024] (3) The synthesis method proposed by the present invention has easily available raw materials, mild reaction conditions, simple operation steps, high reaction efficiency, and avoids the problems of low yield and catalyst residue pollution of products caused by the use of transition metals, and is an environmentally friendly polymerization method;
[0025] (4) The polymer obtained by the present invention can be used as an ultraviolet absorber and has unique application value in protecting the matrix material and improving its ultraviolet aging performance. Brief Description of the Drawings
[0026] Figure 1 This is the NMR spectrum of the olefinic unsaturated polymer prepared in Example 1 of the present invention.
[0027] Figure 2 This is the NMR spectrum of the olefinic unsaturated polymer prepared in Example 2 of the present invention.
[0028] Figure 3 This is the NMR spectrum of the olefinic unsaturated polymer prepared in Example 3 of the present invention.
[0029] Figure 4 This is the NMR spectrum of the olefinic unsaturated polymer prepared in Example 4 of the present invention.
[0030] Figure 5 This is the NMR spectrum of the olefinic unsaturated polymer prepared in Example 5 of the present invention.
[0031] Figure 6 This is the NMR spectrum of the olefinic unsaturated polymer prepared in Example 6 of the present invention.
[0032] Figure 7 This is the NMR spectrum of the olefinic unsaturated polymer prepared in Example 7 of the present invention.
[0033] Figure 8 This is the NMR spectrum of the olefinic unsaturated polymer prepared in Example 8 of the present invention.
[0034] Figure 9 This is the NMR spectrum of the olefinic unsaturated polymer prepared in Example 9 of the present invention.
[0035] Figure 10 This is the NMR spectrum of the olefinic unsaturated polymer prepared in Example 10 of the present invention.
[0036] Figure 11 This is the NMR spectrum of the olefinic unsaturated polymer before and after ultraviolet light irradiation of the film in Example 12 of the present invention. Detailed Description of the Invention
[0037] The following further describes the specific embodiments of the present invention in conjunction with the drawings and technical solutions.
[0038] Example 1
[0039] In an air environment, the diazo monomer A1 (35.4 mg, 0.1 mmol) and potassium hydroxide (5.6 mg, 0.1 mmol) were dissolved in a solvent (1 mL) of N,N-dimethylformamide (DMF). The reaction was carried out at 40 °C for 8 h, and then the reaction was stopped and the mixture was returned to room temperature. The crude product was dissolved in N,N-dimethylformamide (DMF), centrifuged, and the supernatant was filtered through an organic filter membrane to remove the residual potassium hydroxide. The crude product was precipitated in ethyl acetate, and the precipitate was collected by centrifugation; the precipitate was redissolved in N,N-dimethylformamide (DMF) and then precipitated in ethyl acetate again. The above process was repeated three times. After washing the precipitate twice with ethyl acetate, the crude product was dialyzed in deionized water for 48 h (MWCO = 1 kDa), and the powdery product P1 was obtained by freeze-drying. The yield was 81%. The molecular weight was 16000 g / mol, and the polydispersity (PDI) was 1.25.
[0040] Example 2
[0041] In an air environment, the diazo monomer A2 (30.6 mg, 0.1 mmol) and sodium sulfide (54.6 mg, 0.7 mmol) were dissolved in a solvent (2 mL) of dimethyl sulfoxide (DMSO). The reaction was carried out at 10 °C for 48 h, and then the reaction was stopped and the mixture was returned to room temperature. The crude product was dissolved in N,N-dimethylformamide (DMF), centrifuged, and the supernatant was filtered through an organic filter membrane to remove the residual sodium sulfide. The crude product was precipitated in ethyl acetate, and the precipitate was collected by centrifugation; the precipitate was redissolved in N,N-dimethylformamide (DMF) and then precipitated in ethyl acetate again. The above process was repeated three times. After washing the precipitate twice with ethyl acetate, the crude product was dialyzed in deionized water for 48 h (MWCO = 1 kDa), and the powdery product P2 was obtained by freeze-drying. The yield was 73%. The molecular weight was 9100 g / mol, and the polydispersity (PDI) was 1.07.
[0042] Example 3
[0043] In an air environment, the diazo monomer A3 (31.8 mg, 0.1 mmol) and sodium sulfide (7.8 mg, 0.1 mmol) were dissolved in a solvent (2 mL) of tetrahydrofuran (THF). The reaction was carried out at 80 °C for 24 h, and then the reaction was stopped and the mixture was returned to room temperature. The crude product was dissolved in N,N-dimethylformamide (DMF), centrifuged, and the supernatant was filtered through an organic filter membrane to remove the residual sodium sulfide. The crude product was precipitated in ethyl acetate, and the precipitate was collected by centrifugation; the precipitate was redissolved in N,N-dimethylformamide (DMF) and then precipitated in ethyl acetate again. The above process was repeated three times. After washing the precipitate twice with ethyl acetate, the crude product was dialyzed in deionized water for 48 h (MWCO = 1 kDa), and the powdery product P3 was obtained by freeze-drying. The yield was 78%. The molecular weight was 13000 g / mol, and the polydispersity (PDI) was 1.13.
[0044] Example 4
[0045] In an air environment, the diazo monomer A4 (21.4 mg, 0.1 mmol) and potassium carbonate (13.8 mg, 0.1 mmol) were dissolved in a solvent (1 mL) of dimethyl sulfoxide (DMSO). The reaction was carried out at 40 °C for 24 h, and then the reaction was stopped and the mixture was allowed to return to room temperature. The crude product was dissolved in N,N-dimethylformamide (DMF), centrifuged, and the supernatant was filtered through an organic filter membrane to remove the residual potassium carbonate. The crude product was precipitated in ethyl acetate, and the precipitate was collected by centrifugation; the precipitate was redissolved in N,N-dimethylformamide (DMF) and then precipitated again in ethyl acetate. The above process was repeated three times. After washing the precipitate twice with ethyl acetate, the crude product was dialyzed in deionized water for 48 h (MWCO = 1 kDa), and the powdery product P4 was obtained by freeze-drying. The yield was 65%. The molecular weight was 8300 g / mol, and the polydispersity (PDI) was 1.11.
[0046] Example 5
[0047] In an air environment, the diazo monomer A5 (30.4 mg, 0.1 mmol) and sodium sulfide (31.2 mg, 0.4 mmol) were dissolved in a solvent (1 mL) of a mixed solvent of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) (v / v = 4:1). The reaction was carried out at 60 °C for 36 h, and then the reaction was stopped and the mixture was allowed to return to room temperature. The crude product was dissolved in N,N-dimethylformamide (DMF), centrifuged, and the supernatant was filtered through an organic filter membrane to remove the residual sodium sulfide. The crude product was precipitated in a mixture of ethyl acetate and methanol (v / v = 4:1), and the precipitate was collected by centrifugation; the precipitate was redissolved in N,N-dimethylformamide (DMF) and then precipitated again in ethyl acetate. The above process was repeated three times. After washing the precipitate twice with a mixture of ethyl acetate and methanol (v / v = 4:1), the crude product was dialyzed in deionized water for 24 h (MWCO = 1 kDa), and the powdery product P5 was obtained by freeze-drying. The yield was 63%. The molecular weight was 11800 g / mol, and the polydispersity (PDI) was 1.43.
[0048] Example 6
[0049] In an air environment, diazo monomer A6 (29.0 mg, 0.1 mmol) and potassium tert-butoxide (11.2 mg, 0.1 mmol) were dissolved in a solvent (0.25 mL) of dimethyl sulfoxide (DMSO). The reaction was carried out at 40 °C for 24 h, and then the reaction was stopped and the mixture was allowed to return to room temperature. The crude product was dissolved in N,N-dimethylformamide (DMF), centrifuged, and the supernatant was filtered through an organic filter membrane. The crude product was precipitated in ethyl acetate, and the precipitate was collected by centrifugation; the precipitate was redissolved in N,N-dimethylformamide (DMF) and then precipitated again in ethyl acetate. The above process was repeated three times. After washing the precipitate with ethyl acetate twice, the crude product was dialyzed in deionized water for 48 h (MWCO = 1 kDa), and the powdered product P6 was obtained by freeze-drying. The yield was 56%. The molecular weight was 7800 g / mol, and the polydispersity (PDI) was 1.07.
[0050] Example 7
[0051] In an air environment, diazo monomer A7 (31.8 mg, 0.1 mmol) and 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) (15.2 mg, 0.1 mmol) were dissolved in a solvent (0.5 mL) of a mixed solvent of dimethyl sulfoxide (DMSO) and N,N-dimethylformamide (DMF) (v / v = 5:1). The reaction was carried out at 50 °C for 24 h, and then the reaction was stopped and the mixture was allowed to return to room temperature. The crude product was dissolved in N,N-dimethylformamide (DMF), centrifuged, and the supernatant was filtered through an organic filter membrane. The crude product was precipitated in methanol, and the precipitate was collected by centrifugation; the precipitate was redissolved in N,N-dimethylformamide (DMF) and then precipitated again in methanol. The above process was repeated three times. After washing the precipitate with ethyl acetate twice, the crude product was dialyzed in deionized water for 24 h (MWCO = 1 kDa), and the powdered product P7 was obtained by freeze-drying. The yield was 67%. The molecular weight was 10200 g / mol, and the polydispersity (PDI) was 1.21.
[0052] Example 8
[0053] In an air environment, diazo monomer A8 (21.4 mg, 0.1 mmol) and sodium sulfide (7.8 mg, 0.1 mmol) were dissolved in a solvent (2 mL) of dimethyl sulfoxide (DMSO). The reaction was carried out at 40 °C for 24 h, and then the reaction was stopped and the mixture was allowed to return to room temperature. The crude product was dissolved in N,N-dimethylformamide (DMF), centrifuged, and the supernatant was filtered through an organic filter membrane to remove the residual sodium sulfide. The crude product was precipitated in ethyl acetate, and the precipitate was collected by centrifugation; the precipitate was redissolved in N,N-dimethylformamide (DMF) and then precipitated again in ethyl acetate. The above process was repeated three times. After washing the precipitate with ethyl acetate twice, the crude product was dialyzed in deionized water for 48 h (MWCO = 1 kDa), and the powdery product P8 was obtained by freeze-drying. The yield was 58%. The molecular weight was 6200 g / mol, and the polydispersity (PDI) was 1.03.
[0054] Example 9
[0055] In an air environment, diazo monomer A9 (24.6 mg, 0.1 mmol) and sodium sulfide (7.8 mg, 0.1 mmol) were dissolved in a solvent (1 mL) of dimethyl sulfoxide (DMSO). The reaction was carried out at 40 °C for 48 h, and then the reaction was stopped and the mixture was allowed to return to room temperature. The crude product was dissolved in N,N-dimethylformamide (DMF), centrifuged, and the supernatant was filtered through an organic filter membrane to remove the residual sodium sulfide. The crude product was precipitated in ethyl acetate, and the precipitate was collected by centrifugation; the precipitate was redissolved in N,N-dimethylformamide (DMF) and then precipitated again in ethyl acetate. The above process was repeated three times. After washing the precipitate with ethyl acetate twice, the crude product was dialyzed in deionized water for 48 h (MWCO = 1 kDa), and the powdery product P9 was obtained by freeze-drying. The yield was 70%. The molecular weight was 10800 g / mol, and the polydispersity (PDI) was 1.15.
[0056] Example 10
[0057] In an air environment, diazo monomer A10 (27.4 mg, 0.1 mmol) and sodium sulfide (7.8 mg, 0.1 mmol) were dissolved in a solvent (1 mL) of dimethyl sulfoxide (DMSO). The reaction was carried out at 40 °C for 48 h, and then the reaction was stopped and the mixture was allowed to return to room temperature. The crude product was dissolved in N,N-dimethylformamide (DMF), centrifuged, and the supernatant was filtered through an organic filter membrane to remove the residual sodium sulfide. The crude product was precipitated in ethyl acetate, and the precipitate was collected by centrifugation; the precipitate was redissolved in N,N-dimethylformamide (DMF) and then precipitated again in ethyl acetate. The above process was repeated three times. After washing the precipitate with ethyl acetate twice, the crude product was dialyzed in deionized water for 48 h (MWCO = 1 kDa), and the powdery product P10 was obtained by freeze-drying. The yield was 63%. The molecular weight was 8900 g / mol, and the polydispersity (PDI) was 1.75.
[0058] The results of Examples 1-10 show that compared with the traditional transition metal catalysis method, the yields of the P1-P3 series polymers synthesized by this method are significantly improved (the yields of P1-P3 are 73%-81%); the remaining P4-P10 polymers can still maintain relatively high yields (56%-70%).
[0059] Example 11
[0060] Weigh 1.5 g of poly(butylene adipate-co-terephthalate) (PBAT) and add it to a clean and dry 30 mL glass bottle. Add 15 mL of a mixed solvent of N-methylpyrrolidone (NMP) and chloroform (CHCl 3 )(v / v = 3:2) as the solvent. Stir at room temperature for 12 h until the solution becomes transparent to obtain the PBAT film solution. Next, use a non-woven fabric filter to filter the film solution to filter out a small amount of undissolved parts in the film solution. After collecting the filtrate in the glass bottle and sealing it, then place the glass bottle in an ultrasonic cleaner and ultrasonically treat it for 1 h for defoaming. Then evenly coat the treated film solution in a clean and horizontal glass petri dish. Then place the glass dish in an oven to heat and volatilize the solvent to obtain a transparent and uniform PBAT polymer film.
[0061] Example 12
[0062] Weigh 1.5 g of poly(butylene adipate-co-terephthalate) (PBAT) and add it to a clean and dry 30 mL glass bottle. Add 15 mL of a mixed solvent of N-methylpyrrolidone (NMP) and N,N-dimethylformamide (DMF) (v / v = 3:1) as the solvent. Stir at room temperature for 24 h until dissolved. The next day, add 15.0 mg of P3 polymer to the NMP solvent in which PBAT has been dissolved, and continue to stir until P3 is dissolved and the solution becomes transparent. Obtain the PBAT / P3-1 film solution. Next, use a non-woven fabric filter to filter the film solution to filter out a small amount of undissolved parts in the film solution. After collecting the filtrate in the glass bottle and sealing it, then place the glass bottle in an ultrasonic cleaner and ultrasonically treat it for 6 h for defoaming. Then evenly coat the treated film solution in a clean and horizontal glass petri dish. Then place the glass dish in an oven to heat and volatilize the solvent to obtain a transparent and uniform PBAT / P3-1 polymer composite film. After irradiating the PBAT and PBAT / P3-1 polymer films with ultraviolet light for 60 days, use nuclear magnetic resonance hydrogen spectroscopy ( 1 1H NMR) to test their degradation degree.
[0063] Table 1 shows the degradation ratios of the films before and after ultraviolet light irradiation in Examples 11 and 12 of the present invention.
[0064]
[0065] Note:
[0066] Among them: The samples of Items 1 and 2 are PBAT films without ultraviolet absorbers prepared in Example 11; the sample of Item 3 is a PBAT composite film containing only P3 compound as an ultraviolet absorber prepared in Example 12.
Claims
1. A method for preparing an olefinic unsaturated polymer, characterized in that: Here are the steps: Accurately weigh 1 molar equivalent of a diazo compound monomer A and 1-7 molar equivalents of a base, dissolve them in a solvent to obtain a reaction solution, wherein the concentration of the diazo compound monomer A in the reaction solution is controlled to be 0.05-0.4M; the reaction solution is continuously stirred at 10-80°C for 8-48 hours in an air environment, the reaction is stopped and restored to room temperature; the crude product is dissolved with N,N-dimethylformamide, centrifuged, and filtered with an organic filter membrane to filter out residual alkali, the crude product is precipitated in a precipitant, and the precipitate is collected by centrifugation; the precipitate is redissolved with N,N-dimethylformamide, and precipitated in the precipitant again, and the above process is repeated three times; After washing the precipitate twice with a sedimentation agent, the crude product was dialyzed in deionized water for 24-48 hours and freeze-dried to obtain a red solid, which was an olefin unsaturated polymer; The general reaction formula is as follows:
2. The preparation method according to claim 1, characterized in that: The structure of the diazo compound monomer A is:
3. The preparation method according to claim 1, characterized in that: The polymerization degree n of the olefinic unsaturated polymer is greater than 5, the weight average molecular weight of the olefinic unsaturated polymer is in the range of 6200-16000 g / mol, and the molecular weight distribution range is 1.03-1.
75.
4. The preparation method according to claim 1, characterized in that: The base is sodium sulfide, potassium hydroxide, potassium carbonate, potassium tert-butoxide, and 1,8-diazabicyclo[5,4,0]undec-7-ene.
5. The preparation method according to claim 1, characterized in that: The solvent is one of dimethyl sulfoxide, tetrahydrofuran and N,N-dimethylformamide or a mixture of two or more of them in any proportion.
6. The preparation method according to claim 1, characterized in that: The sedimentation agent is ethyl acetate and / or methanol.
7. The preparation method according to claim 1, characterized in that: The MWCO of the dialysis was 1 kDa.
8. Application of the olefinic unsaturated polymer obtained by the preparation method according to claims 1 to 8 in anti-ultraviolet aging, characterized in that: The steps are as follows: first dissolve the matrix material with a solvent, and then add the olefin unsaturated polymer to the solution containing the matrix material; stir at room temperature for 12-24 hours, filter to remove insoluble matter, collect the filtrate in a glass bottle and seal it, then put the glass bottle in an ultrasonic cleaner for ultrasonic treatment for 1-6 hours to perform defoaming treatment; then evenly apply the treated film liquid on a clean, horizontal glass culture dish; then place the glass dish in an oven and heat it to volatilize the solvent to obtain a transparent and uniform polymer composite film.
9. The use according to claim 8, characterized in that: The matrix material is PBAT.
10. The use according to claim 8, characterized in that: The solvent is: one or two or more of N,N-dimethylformamide, chloroform, and N-methylpyrrolidone mixed in any proportion.