CN116970124B - Antioxidant functionalized cycloolefin polar copolymer and preparation method and application thereof - Google Patents

Antioxidant functionalized cycloolefin polar copolymer and preparation method and application thereof Download PDF

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CN116970124B
CN116970124B CN202310941553.6A CN202310941553A CN116970124B CN 116970124 B CN116970124 B CN 116970124B CN 202310941553 A CN202310941553 A CN 202310941553A CN 116970124 B CN116970124 B CN 116970124B
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cycloolefin
antioxidant
pyrimidine
copolymer
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钟柳
谢东
李发勇
王珂
孙晓燕
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Institute of Biological and Medical Engineering of Guangdong Academy of Sciences
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Abstract

The invention discloses an antioxidant functionalized cycloolefin polar copolymer and a preparation method and application thereof. An antioxidant functionalized cyclic olefin polar copolymer having the structure shown in the following formula (I), wherein: n is more than or equal to 32 and less than or equal to 240, FG is hindered phenol or hindered amine polar functional groups with different chain lengths, the weight average molecular weight M w of the cycloolefin polar copolymer is 4000-30000 g/mol, the molecular weight distribution coefficient PDI is 1.5-2.2, and the polar monomer insertion rate is 0.5% -1.7%. The cycloolefin polar copolymer provided by the invention has thermal oxygen and photooxygen stability, good compatibility and dispersibility with nonpolar COC cycloolefin resin, excellent migration resistance and capability of perfectly meeting the antioxidant requirement of medical high-end COC materials.

Description

Antioxidant functionalized cycloolefin polar copolymer and preparation method and application thereof
Technical Field
The invention relates to the technical field of polymer anti-aging, in particular to an antioxidant functionalized cycloolefin polar copolymer, a preparation method and application thereof.
Background
Cycloolefin copolymers (COC) were first developed and produced by the Japanese rayleigh company in the 90 s of the 20 th century and are mainly used for optical parts and high-end pharmaceutical packaging materials. Because of its high transparency, low birefringence, low water absorption, high rigidity, heat resistance, good water vapor tightness and compliance with FDA standard, it has been widely used in medical, pharmaceutical and cosmetic fields such as prefilled syringes, plastic penicillin bottles, infusion bags, contrast media, etc. in developed countries such as Europe and America.
When the COC material is used as a medical product, radiation sterilization is generally adopted to ensure biological safety, however, researches show that gamma rays or electron beams used in the radiation process can break polymer molecular chains to generate free radicals and chromophores, and phenomena such as radiation degradation, oxidation and color change can be inevitably generated.
The addition of the micromolecular antioxidant in the COC has a certain inhibition effect on radiation oxidation, but the currently commercialized antioxidant has poor compatibility with a cycloolefin polymer matrix and poor migration resistance, and the content of the antioxidant after irradiation is obviously reduced; and no additives are required for packaging materials for blood products, vaccines and biological agents. The small molecular antioxidant compounds provided by the prior art cannot meet the requirements of migration resistance and no addition in medical nonpolar cycloolefin copolymer COC. Therefore, the preparation of the macromolecular antioxidant which has good compatibility and dispersibility with COC and does not influence the optical performance of the macromolecular antioxidant is an effective strategy for realizing migration resistance of the additive.
Because of the inherent strong electrophilicity of the early transition metal, the early transition metal is easily poisoned by polar functional groups in catalyzing the copolymerization of olefins and polar monomers, and has great limitation. Thus, the direct copolymerization of olefins with polar monomers by means of pre-transition metal catalysts is very challenging. Literature (polym. Degrad. Stabil.2017, 144:167-175) reports the use of metallocene catalysts to catalyze the copolymerization of ethylene with polar norbornene derivatives, but requires the prior use of aluminum oxide compounds (e.g., triisobutylaluminum) to pre-protect the polar functionality, and then deprotection reaction after the reaction is completed, resulting in low polar functionality content. The metal center of the transition metal catalyst has weaker oxygen affinity, so that the transition metal catalyst has greater advantages in the process of catalyzing the copolymerization of the polar monomer, and can directly catalyze the copolymerization of the polar monomer and the olefin by a one-step method, thereby becoming the first choice in the synthesis of the functionalized cycloolefin polar copolymer.
Disclosure of Invention
The invention provides an antioxidant functionalized cycloolefin polar copolymer, a preparation method and application thereof, and the cycloolefin polar copolymer provided by the invention has thermal oxygen and photooxygen stability, good compatibility and dispersibility with nonpolar COC cycloolefin resin, excellent migration resistance and capability of perfectly meeting the antioxidant requirement of medical COC materials.
The first object of the present invention is to provide an antioxidant functionalized cyclic olefin polar copolymer having a structure represented by formula (I):
Wherein: n is more than or equal to 32 and less than or equal to 240, FG is hindered phenol or hindered amine polar functional groups with different chain lengths, the weight average molecular weight M w of the cycloolefin polar copolymer is 4000-30000 g/mol, the molecular weight distribution coefficient PDI is 1.5-2.2, and the polar monomer insertion rate is 0.5% -1.7%.
More preferably, the cycloolefin polar copolymer has a weight average molecular weight M w of 4100 to 27000g/mol, a molecular weight distribution coefficient PDI of 1.51 to 2.13, and a polar monomer insertion rate of 0.53 to 1.57%.
Preferably, the formula (I) has one of the following structures of formula (II):
The second object of the present invention is to provide a process for preparing the antioxidant functionalized cyclic olefin polar copolymer, comprising the steps of: copolymerizing Norbornene (NBE) and a polar vinyl monomer under the action of a post-transition metal nickel catalyst to obtain a cycloolefin polar copolymer shown in a formula (I), wherein the polar vinyl monomer is selected from hindered phenol or hindered amine substituted polar vinyl monomer, the metal nickel catalyst comprises a main catalyst of a pyrimidine imine nickel complex and a cocatalyst of alkyl aluminum, and the pyrimidine imine nickel complex has a structure shown in a formula (III):
Wherein R 1 is benzhydryl or isopropyl, and R 2 is methyl or hydrogen.
Preferably, the nickel pyrimidyl complex is nickel pyrimidyl complex Ni-1, R 1 is benzhydryl, and R 2 is methyl; or pyrimidine imine nickel complex Ni-2, R 1 is isopropyl, R 2 is hydrogen.
Further preferably, the pyrimidine imine nickel complex Ni-1/Ni-2 is prepared by the following steps:
(1) Preparation of pyrimidine imine ligand L1/L2: sequentially adding toluene, acetyl pyrimidine, 2, 6-benzhydryl aniline or 2, 6-diisopropylaniline into a reaction container under the condition of nitrogen and room temperature, adding catalytic amount of p-toluenesulfonic acid to obtain a reaction solution, wherein the molar concentration of the 2, 6-benzhydryl aniline or 2, 6-diisopropylaniline in the reaction solution is 0.8-0.9 mol/L, the molar ratio of the acetyl pyrimidine to the 2, 6-benzhydryl aniline or 2, 6-diisopropylaniline is 1:1, heating and refluxing the reaction solution at 100-120 ℃ for 20-28 hours, removing the solvent by rotary evaporation of the reacted mixture, and recrystallizing the solid by ethanol to obtain a pyrimidine imine ligand L1/L2;
(2) Preparation of complex Ni-1/Ni-2: adding the pyrimidine imine ligand L1/L2 obtained in the step (1) (DME) into a reaction container under the nitrogen atmosphere, adding anhydrous methylene dichloride to obtain a reaction solution, wherein the mass concentration of the pyrimidine imine ligand L1/L2 in the reaction solution is 0.04-0.06 g/mL, the mass concentration of the (DME) NiBr 2 in the reaction solution is 0.5-0.6 g/mL, stirring for 10-14 hours at room temperature overnight, removing insoluble substances by a filter bulb, concentrating under reduced pressure, precipitating yellow-red powder by using normal hexane, filtering, washing a product, and drying in vacuum to obtain the complex Ni-1/Ni-2. The addition amount of the p-toluenesulfonic acid is 0.05-0.20% of the sum of the amounts of the acetyl pyrimidine and the 2, 6-benzhydryl aniline or the 2, 6-diisopropylaniline.
The inventor researches find that the diphenyl methyl with large steric hindrance is introduced at the ortho position of the aniline aromatic ring in the pyrimidine imine ligand, so that the thermal stability of the catalyst is improved, and the norbornene and the substituted vinyl monomer can be catalyzed to copolymerize at 50-80 ℃ with high activity to obtain a copolymer with high molecular weight; and when isopropyl with relatively smaller steric hindrance is introduced, the insertion of the comonomer is facilitated, and the insertion rate of the polar functional group is high.
Preferably, the preparation method of the cycloolefin polar copolymer specifically comprises the following steps: at the temperature of 20-80 ℃, taking Modified Methylaluminoxane (MMAO) as a cocatalyst, taking chlorobenzene as a solvent, carrying out polymerization for 60-120 min, wherein the molar ratio of Al to Ni of metal aluminum in the cocatalyst to metal nickel in the main catalyst is 600-1200:1, the metal nickel catalyst catalyzes norbornene and vinyl polar monomer to carry out copolymerization, the molar ratio of norbornene and vinyl polar monomer is 2:8-8:2, the norbornene and vinyl polar monomer are taken as reaction monomers, and the molar ratio of the reaction monomers to the metal nickel catalyst is 2000-3000:1, thus obtaining the cycloolefin polar copolymer.
The third object of the invention is to propose the use of the antioxidant functionalized cyclic olefin polar copolymer as a pellet additive for the antioxidant aspect of nonpolar cyclic olefin materials. The addition amount of the antioxidant functionalized cycloolefin polar copolymer is 0.3 to 1.0 weight percent of the nonpolar cycloolefin material.
The main chain side group of the cycloolefin polar copolymer prepared by the invention is hindered amine or hindered phenol substituted polar functional group, has photooxidation and thermal oxidation stability, and is used as a pellet type additive in the aspect of antioxidation of medical nonpolar cycloolefin materials.
The secondary amino group in the hindered amine antioxidant is oxidized under the conditions of light, high temperature, oxygen and the like, and is converted into a nitroxide free radical which can exist stably for a long time. These NO species are effective in capturing and inactivating the free radicals generated by the copolymer to form the corresponding esters and peroxyesters. The generated esters can react with peroxy radicals generated in the polymer, and in the process, the nitroxide radicals are regenerated and react with other radicals in the material again, so that the hindered amine light stabilizer has high-efficiency light stabilization performance, and the photo-oxidative aging speed of the polymer material is greatly reduced.
The action mechanism of the hindered phenol antioxidant is realized by breaking free radical autoxidation chain reaction through proton giving action. In the chain autoxidation growth reaction, the alkyl peroxy ROO.in the polymer is a reaction chain growth by hydrogen abstraction reaction. Phenolic antioxidants have more active hydrogens than the hydrogens in the polymer, and compounds that react to form stable free radicals can act as chain terminators.
Compared with the prior art, the invention has the beneficial effects that:
1. The invention utilizes the late transition metal catalyst to catalyze the direct copolymerization of norbornene and substituted vinyl monomer to obtain functionalized COC, develops a new COC polar copolymer material with antioxidant and non-migration behaviors, has good compatibility and dispersibility with non-polar COC cycloolefin resin, and has excellent migration resistance; and the medical nonpolar cycloolefin copolymer material has thermal oxygen and photooxygen stability, effectively blocks an oxidation passage of the medical nonpolar cycloolefin copolymer material, inhibits the oxidative degradation of a molecular chain under gamma ray irradiation, and can perfectly meet the antioxidant requirement of the medical COC material.
2. The invention adopts the mode of coordination polymerization of the post-transition metal catalyst to control the reaction temperature and the reaction time, or adjusts the structure of the catalyst and the proportion of the comonomer to change the molecular weight of the COC polar copolymer and the insertion rate of the polar functional group so as to meet the structure and the modification requirement of the copolymer matrix material.
Drawings
FIG. 1 is an infrared spectrum of a copolymer-9 of cycloolefin polarity obtained in example 9.
FIG. 2 is a gel permeation chromatography GPC comparison chart of the samples of example 16 and comparative examples 1 and 2.
FIG. 3 is a diagram showing a sample of the cycloolefin polar copolymer obtained in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental methods without specific conditions noted in the examples below are generally in accordance with conventional conditions in the art or in accordance with manufacturer's recommendations; the raw materials, reagents and the like used, unless otherwise specified, are considered to be commercially available through conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
For simplicity and clarity in the examples, the ligands and complexes are described below: the nickel pyrimidyl complex has a structure shown in a formula (III):
wherein R 1 is one of benzhydryl or isopropyl, and R 2 is one of methyl or hydrogen.
Specifically:
The nickel pyrimidyl complex Ni-1, R 1 is benzhydryl, R 2 is methyl; the nickel pyrimidyl complex Ni-2, R 1 is isopropyl, and R 2 is hydrogen.
The synthesis of the nickel pyrimidyl complex in the following examples comprises the following steps:
(1) Preparation of pyrimidine imine ligand L1
100ML of toluene, 1.00g (8.18 mmol) of acetyl pyrimidine, 3.59g (8.18 mmol) of 2, 6-benzhydryl aniline, and a catalytic amount of p-toluene sulfonic acid were added sequentially to a 150mL flask under nitrogen atmosphere at room temperature, and the water was heated at 110℃for refluxing for 24 hours. The reaction system gradually turns from dark brown to dark red and emits a large amount of heat. The solvent is removed by rotary evaporation of the mixture after the reaction, and the solid is recrystallized by ethanol to obtain yellow brown solid powder, and the yield is high ：83％.1H NMR(CDCl3,300MHz),δ(ppm)：2.25(s,3H),2.40(s,3H),5.49(s,2H),6.99-7.43(m,17H),8.12(m,2H).ESI-MS：543.98g/mol.
(2) Preparation of pyrimidine imine ligand L2
According to the synthesis method of the ligand L1, 2, 6-diisopropylaniline is used for replacing 2, 6-benzhydryl aniline, and other operation conditions are the same. To obtain yellow brown solid powder, yield ：89％.1H NMR(CDCl3,300MHz),δ(ppm)：1.16(m,6H),1.22(m,6H),2.43(s,3H),4.41(s,2H),6.79-7.23(m,4H),8.06(m,2H).ESI-MS：281.86g/mol.
(3) Preparation of Complex Ni-1
1.00G of ligand L1, (DME) NiBr 2 567.33mg was added to Sehlenk bottles under nitrogen atmosphere, 20mL of anhydrous dichloromethane was added, stirred at room temperature overnight for 12 hours, after insoluble matter was removed by using G4 filter beads, concentrated to 5mL of solvent under reduced pressure, 35mL of n-hexane was added to precipitate yellow red powder, filtered by using G4 filter beads, the product was washed 3 times with n-hexane solvent, and the complex Ni-L was obtained by vacuum drying, yield: 70%. Elemental analysis (C 39H33Br2N3 Ni,%) theory: c,61.46; h,4.36; n,5.51. Actual measurement value: c,61.58; h,4.21; n,5.57.
(4) Preparation of Complex Ni-2
According to the synthesis method of the complex Ni-1, L2 is used for replacing L1, and the yellow brown complex Ni-2 is obtained with the yield of 75%. Elemental analysis (C 18H23Br2N3 Ni,%) theory: c,43.25; h,4.64; n,8.41. Actual measurement value: c,43.12; h,4.72; n,8.35.
Copolymerization of norbornene with polar vinyl monomers:
The copolymerization reaction is carried out in a 100mL branched round bottom flask with a stirrer, and under the conditions of different temperatures, different cocatalysts and concentrations thereof, the concentration ratio of norbornene to polar vinyl monomer, the types of polar vinyl monomers and the like, complexes Ni-1 and Ni-2 are selected as representatives, and the influence of the complexes on copolymerization is explored. The catalytic activity (g copolymer/(mol. Ni. H)) is calculated from the final copolymer mass, the amount of metal nickel catalyst and the polymerization time; the number average molecular weight and molecular weight distribution index of the copolymer were determined by high temperature gel permeation chromatography; the insertion rate of the polar monomer was measured by nuclear magnetic resonance hydrogen spectrogram.
The polar vinyl monomer selected in the examples below is represented by the following formula (IV):
Example 1
The embodiment provides a cycloolefin polar copolymer obtained by copolymerizing norbornene and a hindered amine substituted vinyl monomer, and the preparation method comprises the following steps:
20mL of anhydrous chlorobenzene, 5 mu mol of complex Ni-1, 3mmol (Al/Ni=600) of modified methylaluminoxane MMAO, and the mol ratio of norbornene/hindered amine substituted vinyl monomer is 8:2, the total amount of substances is 0.01mol, the polymerization temperature T is 50 ℃, the total reaction volume is 30mL, and the polymerization time T is 60min are added into a 100mL branched polymerization bottle under the nitrogen atmosphere. After the polymerization was completed, the reaction was terminated with 200mL of 5% by volume ethanol hydrochloride solution, the polymer was filtered and washed 3 times with ethanol, and vacuum-dried at 50℃to obtain copolymer-1 having a catalytic efficiency of 1.35X10- 5 g copolymer/(mol Ni. Multidot. H), a polymer weight average molecular weight M w of 24950g/mol, a PDI of 1.54, and a polar monomer insertion of 0.85%.
Example 2
The difference between this embodiment and embodiment 1 is that: the molar ratio of norbornene/hindered amine-substituted vinyl monomer was 4:6, and the same conditions as in example 1 were followed to obtain copolymer-2 having a catalytic efficiency of 4.55X10 4 g PE/(mol Ni.h), a polymer weight average molecular weight M w of 14560g/mol, a PDI of 1.56 and a polar monomer insertion of 1.18%.
Example 3
The difference between this embodiment and embodiment 1 is that: the polymerization temperature T was 80℃and the other conditions were the same as in example 1, except that copolymer-3 was obtained, the catalytic efficiency was 1.42X10 5 g PE/(mol Ni.h), the weight-average molecular weight M w was 19760g/mol, the PDI was 1.86, and the polar monomer insertion rate was 1.09%.
Example 4
The difference between this embodiment and embodiment 1 is that: the polymerization time t was 120 minutes, and the other conditions were the same as in example 1, to obtain copolymer-4, the catalytic efficiency was 3.23X10 4 g PE/(mol Ni.h), the polymer weight-average molecular weight M w was 18450g/mol, the PDI was 1.96, and the polar monomer insertion rate was 0.93%.
Example 5
The difference between this embodiment and embodiment 1 is that: the cocatalyst MMAO was 5mmol (Al/ni=1000), and the other conditions were the same as in example 1, to give copolymer-5 having a catalytic efficiency of 1.36×10 5 g PE/(mol ni·h), a polymer weight average molecular weight M w of 24910g/mol, PDI of 1.56, and a polar monomer insertion of 1.01%.
Example 6
The difference between this embodiment and embodiment 1 is that: the copolymerization polar monomer was a hindered phenol-substituted vinyl monomer, and the same conditions as in example 1 were adopted to obtain copolymer-6, wherein the catalytic efficiency was 9.79X 10 4 g copolymer/(mol Ni.h), the weight average molecular weight M w was 26000g/mol, the PDI was 1.62, and the polar monomer insertion rate was 0.53%.
Example 7
The embodiment provides a cycloolefin polar copolymer obtained by copolymerizing norbornene and a hindered amine substituted vinyl monomer, and the preparation method comprises the following steps:
20mL of anhydrous chlorobenzene, 5 mu mol of complex Ni-2, 3mmol (Al/Ni=600) of modified methylaluminoxane MMAO, and the mol ratio of norbornene/hindered amine substituted vinyl monomer is 8:2, the total amount of substances is 0.01mol, the polymerization temperature T is 50 ℃, the total reaction volume is 30mL, and the polymerization time T is 60min are added into a 100mL branched polymerization bottle under the nitrogen atmosphere. After the polymerization was completed, the reaction was terminated with 200mL of ethanol solution of hydrochloric acid, the polymer was filtered and washed 3 times with ethanol, and vacuum-dried at 50℃to obtain copolymer-7 having a catalytic efficiency of 1.08X10- 5 g copolymer/(mol. Ni. H), a polymer weight average molecular weight M w of 21680kg/mol, a polydispersity of 1.51, and a polar monomer insertion of 0.68%.
Example 8
The difference between this embodiment and embodiment 7 is that: the molar ratio of norbornene/hindered amine-substituted vinyl monomer was 2:8, and the same conditions as in example 7 were employed to obtain copolymer-8 having a catalytic efficiency of 9.25X10 3 g copolymer/(mol. Ni. H), a polymer weight average molecular weight M w of 4510g/mol, a polydispersity of 2.03 and a polar monomer insertion of 1.57%.
Example 9
The difference between this embodiment and embodiment 7 is that: the polar monomer was a hindered phenol-substituted vinyl monomer, the molar ratio of norbornene/hindered phenol-substituted vinyl monomer was 8:2, the other conditions were the same as in example 7, and copolymer-9 was obtained, the catalytic efficiency was 0.94X10 5 g copolymer/(mol. Ni. H), the polymer weight average molecular weight M w was 19310g/mol, the polydispersity was 1.59, and the polar monomer insertion rate was 0.61%.
Example 10
The difference between this embodiment and embodiment 7 is that: the polar monomer was a hindered phenol-substituted vinyl monomer, the molar ratio of norbornene/hindered phenol-substituted vinyl monomer was 2:8, and the other conditions were the same as in example 7, to obtain copolymer-10, the catalytic efficiency was 0.82X 10 3 g copolymer/(mol. Ni. H), the polymer weight average molecular weight M w was 4200g/mol, the polydispersity was 2.13, and the polar monomer insertion rate was 1.49%. Preparation of antioxidant functional COC film
An appropriate amount of the cycloolefin polar copolymer or the antioxidant prepared in the above example was weighed, added to the nonpolar cycloolefin copolymer (available from Japanese Polyplastics Co.) in a certain proportion, and the mixture was stirred and dissolved in boiling cyclohexane, and cast into a film with a film thickness of about 0.5mm by natural cooling.
Gamma radiation and testing
And irradiating the COC film sample in an air environment at room temperature, wherein the total gamma-ray radiation dose is 25kGy and 75kGy. Testing the molecular weight of the sample; performing Soxhlet extraction on the irradiated sample for 24 hours by using a toluene solution, and testing the gel content of the sample; the content of antioxidant additives in the copolymer was determined on the irradiated film samples using a dissolution/precipitation method (radiation. Phys. Chem.2013, 84:223-231).
Example 11
The nonpolar COC is added with 0.5 percent of polar cycloolefin copolymer-1 with hindered amine antioxidant groups on side chains, hot-pressed into a film, and the radiation dose is 25kGy, and the test is carried out.
Example 12
The nonpolar COC is added with 0.5 percent of polar cycloolefin copolymer-3 with hindered amine antioxidant groups on side chains, hot-pressed into a film, and the radiation dose is 25kGy, and the test is carried out.
Example 13
The nonpolar COC is added with 0.5 percent of polar cycloolefin copolymer-3 with hindered amine antioxidant groups on side chains, hot-pressed into a film, and the radiation dose is 75kGy, and the test is carried out.
Example 14
The nonpolar COC is added with 0.5 percent of polar cycloolefin copolymer-9 with hindered phenol antioxidant groups on side chains, hot-pressed into a film, and the radiation dose is 25kGy, and the test is carried out.
Example 15
The nonpolar COC is added with 0.5 percent of polar cycloolefin copolymer-10 with hindered phenol antioxidant groups on side chains, hot-pressed into a film, and the radiation dose is 25kGy, and the test is carried out.
Example 16
The nonpolar COC is added with 0.5 percent of polar cycloolefin copolymer-10 with hindered phenol antioxidant groups on side chains, hot-pressed into a film, and the radiation dose is 75kGy, and the test is carried out.
Comparative example 1
An antioxidant 770 (CAS number: 52829-07-9) was added to the nonpolar COC in an amount of 0.5% by mass, and hot press film formation was performed at a radiation dose of 25kGy, and tested.
Comparative example 2
An antioxidant 770 with the mass fraction of 0.5% of the nonpolar COC is added into the nonpolar COC, hot-press film formation is carried out, the radiation dose is 75kGy, and the test is carried out.
Comparative example 3
An antioxidant 1076 (CAS number: 2082-79-3) was added to the nonpolar COC in an amount of 0.5% by mass, and the film was formed by hot pressing with a radiation dose of 25kGy, and tested.
Comparative example 4
An antioxidant 1076 with the mass fraction of 0.5% of that of the nonpolar COC is added into the nonpolar COC, hot-pressing film formation is carried out, the radiation dose is 75kGy, and the test is carried out.
Comparative example 5
Directly carrying out hot pressing film formation on the nonpolar COC material, and testing the nonpolar COC material with the radiation dose of 25 kGy.
The test results are shown in table 1:
TABLE 1 COC film Performance test after gamma radiation
As shown by the results of the above examples, the antioxidant functionalized cycloolefin polar copolymer is prepared by polymerization in a coordination polymerization mode of post-transition metal nickel catalyst, and the reaction temperature and reaction time of the copolymer can be controlled, or the molecular weight of the COC polar copolymer and the insertion rate of the antioxidant functional group can be changed by adjusting the structure of the catalyst and the proportion of the comonomer so as to meet the structure and modification requirements of the copolymer matrix material.
The invention utilizes the late transition metal catalyst to catalyze the direct copolymerization of norbornene and substituted vinyl monomer to obtain functionalized COC, develops a new COC polar copolymer material with antioxidant and non-migration behaviors, has good compatibility and dispersibility with non-polar COC cycloolefin resin, and has excellent migration resistance; and has thermo-and photo-oxygen stability. Examples 11-16 are compared with comparative examples 1-5, and the antioxidant functionalized cycloolefin polar copolymer provided by the invention has excellent antioxidant effect, and after being irradiated by gamma rays in a large dose, the molecular weight of the copolymer is kept unchanged, and no crosslinked polymer is generated. The hindered amine stabilizer 770 or the hindered phenol stabilizer 1076 is added, and the molecular weight of the auxiliary agent is small and is easy to migrate, so that the COC copolymer is degraded and the molecular weight is reduced under the condition of low dosage after gamma-ray radiation with different dosages; under high dose irradiation, the degraded molecular weight undergoes a crosslinking reaction again, and a high molecular weight fraction appears. Therefore, when the antioxidant functionalized cycloolefin polar copolymer is used in a nonpolar COC matrix material, the antioxidant functionalized cycloolefin polar copolymer can effectively block the oxidation passage of the medical nonpolar cycloolefin copolymer material, inhibit the oxidative degradation of molecular chains under gamma ray irradiation, and can perfectly meet the requirements of the medical COC material on antioxidant property and no addition (no precipitation).
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.

Claims (7)

1. An antioxidant functionalized cyclic olefin polar copolymer characterized by having a structure represented by formula (I):
Wherein: n is more than or equal to 32 and less than or equal to 240, FG is hindered phenol or hindered amine polar functional groups with different chain lengths, the weight average molecular weight M w of the cycloolefin polar copolymer is 4000-30000 g/mol, the molecular weight distribution coefficient PDI is 1.5-2.2, and the polar monomer insertion rate is 0.5-1.7%;
The preparation method of the antioxidant functionalized cycloolefin polar copolymer comprises the following steps: copolymerizing norbornene and a polar vinyl monomer under the action of a post-transition metal nickel catalyst to obtain a cycloolefin polar copolymer shown in a formula (I), wherein the polar vinyl monomer is selected from hindered phenol or hindered amine substituted polar vinyl monomer, the metal nickel catalyst comprises a main catalyst namely a pyrimidine imine nickel complex and a cocatalyst namely aluminum alkyl, and the pyrimidine imine nickel complex has a structure shown in a formula (III):
Wherein R 1 is benzhydryl or isopropyl, and R 2 is methyl or hydrogen.
2. The antioxidant functional cycloolefin polar copolymer according to claim 1, characterized in that the cycloolefin polar copolymer has a weight average molecular weight M w of 4100 to 27000g/mol, a molecular weight distribution coefficient PDI of 1.51 to 2.13 and a polar monomer insertion rate of 0.53% to 1.57%.
3. The antioxidant functionalized cyclic olefin polar copolymer according to claim 1 or 2, wherein the formula (I) has one of the following structures (II):
4. The antioxidant functionalized cyclic olefin polar copolymer according to claim 1, wherein the nickel pyrimidyl complex is nickel pyrimidyl complex Ni-1, R 1 is benzhydryl, and R 2 is methyl; or pyrimidine imine nickel complex Ni-2, R 1 is isopropyl, R 2 is hydrogen.
5. The antioxidant functionalized cyclic olefin polar copolymer according to claim 4, wherein the pyrimidine imine nickel complex Ni-1/Ni-2 is prepared by the following steps:
(1) Preparation of pyrimidine imine ligand L1/L2: sequentially adding toluene, acetyl pyrimidine, 2, 6-benzhydryl aniline or 2, 6-diisopropylaniline into a reaction container under the condition of nitrogen and room temperature, adding catalytic amount of p-toluenesulfonic acid to obtain a reaction solution, wherein the molar concentration of the 2, 6-benzhydryl aniline or 2, 6-diisopropylaniline in the reaction solution is 0.8-0.9 mol/L, the molar ratio of the acetyl pyrimidine to the 2, 6-benzhydryl aniline or 2, 6-diisopropylaniline is 1:1, heating and refluxing the reaction solution at 100-120 ℃ for 20-28 hours, removing the solvent by rotary evaporation of the reacted mixture, and recrystallizing the solid by ethanol to obtain a pyrimidine imine ligand L1/L2;
(2) Preparation of complex Ni-1/Ni-2: adding the pyrimidine imine ligand L1/L2 obtained in the step (1) (DME) into a reaction container under the nitrogen atmosphere, adding anhydrous methylene dichloride to obtain a reaction solution, wherein the mass concentration of the pyrimidine imine ligand L1/L2 in the reaction solution is 0.04-0.06 g/mL, the mass concentration of the (DME) NiBr 2 in the reaction solution is 0.5-0.6 g/mL, stirring for 10-14 hours at room temperature overnight, removing insoluble substances by a filter bulb, concentrating under reduced pressure, precipitating yellow-red powder by using normal hexane, filtering, washing a product, and drying in vacuum to obtain the complex Ni-1/Ni-2.
6. The antioxidant functionalized cyclic olefin polar copolymer according to claim 1, comprising in particular the steps of: at 20-80 ℃, modified methylaluminoxane is taken as a cocatalyst, chlorobenzene is taken as a solvent, the polymerization reaction time is 60-120 min, the Al/Ni molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the main catalyst is 600-1200:1, the metallic nickel catalyst catalyzes norbornene and vinyl polar monomer to carry out copolymerization reaction, the molar ratio of norbornene and vinyl polar monomer is 2:8-8:2, norbornene and vinyl polar monomer are taken as reaction monomers, the molar ratio of reaction monomers to metallic nickel catalyst is 2000-3000:1, and the cycloolefin polar copolymer is obtained through polymerization.
7. Use of the antioxidant functionalized cyclic olefin polar copolymer according to any of claims 1 to 3 as a pellet additive for the antioxidant aspect of nonpolar cyclic olefin materials.
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