CN115947719B - Tetramethyl piperidine derivative light stabilizer and preparation method thereof - Google Patents
Tetramethyl piperidine derivative light stabilizer and preparation method thereof Download PDFInfo
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- 239000004611 light stabiliser Substances 0.000 title claims abstract description 64
- YAXWOADCWUUUNX-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidine Chemical class CC1CCCN(C)C1(C)C YAXWOADCWUUUNX-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 29
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012964 benzotriazole Substances 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000012970 tertiary amine catalyst Substances 0.000 claims abstract description 17
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000002250 absorbent Substances 0.000 claims abstract description 10
- 230000002745 absorbent Effects 0.000 claims abstract description 10
- 238000005935 nucleophilic addition reaction Methods 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 4
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- PNDMRFPOLBDAJX-UHFFFAOYSA-N 3,3,4-trimethylpentane-1,4-diamine Chemical compound CC(C)(N)C(C)(C)CCN PNDMRFPOLBDAJX-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 abstract description 18
- 206010051246 Photodermatosis Diseases 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 150000003254 radicals Chemical class 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000010525 oxidative degradation reaction Methods 0.000 abstract description 5
- 230000008845 photoaging Effects 0.000 abstract description 5
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 230000009977 dual effect Effects 0.000 abstract description 3
- 230000002000 scavenging effect Effects 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 6
- -1 2-phenyl-4, 6-bis [ 2-hydroxy-4- (methylpiperidinyloxycarbonylmethoxy) phenyl ] -1,3, 5-triazine Chemical compound 0.000 description 5
- 230000001588 bifunctional effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000012667 polymer degradation Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- NIZBFFOETCKGBI-UHFFFAOYSA-N 1-hydroxy-2,2,3,3,4-pentamethylpiperidine Chemical compound CC1CCN(O)C(C)(C)C1(C)C NIZBFFOETCKGBI-UHFFFAOYSA-N 0.000 description 1
- UFCONGYNRWGVGH-UHFFFAOYSA-N 1-hydroxy-2,2,3,3-tetramethylpiperidine Chemical compound CC1(C)CCCN(O)C1(C)C UFCONGYNRWGVGH-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical compound FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 description 1
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PDWJJJRPZTZWDE-UHFFFAOYSA-N 4-(5-chlorobenzotriazol-2-yl)benzene-1,3-diol Chemical compound OC1=CC(O)=CC=C1N1N=C2C=C(Cl)C=CC2=N1 PDWJJJRPZTZWDE-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001587 Wood-plastic composite Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- MXMOTZIXVICDSD-UHFFFAOYSA-N anisoyl chloride Chemical compound COC1=CC=C(C(Cl)=O)C=C1 MXMOTZIXVICDSD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ARBOVOVUTSQWSS-UHFFFAOYSA-N hexadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCC(Cl)=O ARBOVOVUTSQWSS-UHFFFAOYSA-N 0.000 description 1
- UCQQHIZRIQSXEM-UHFFFAOYSA-N hexane-1,6-diamine piperidine Chemical compound N1CCCCC1.NCCCCCCN UCQQHIZRIQSXEM-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical compound ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229940124543 ultraviolet light absorber Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011155 wood-plastic composite Substances 0.000 description 1
Landscapes
- Hydrogenated Pyridines (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a tetramethyl piperidine derivative light stabilizer and a preparation method thereof, belonging to the field of synthesis of difunctional hindered amine light stabilizers, wherein the tetramethyl piperidine derivative is prepared by nucleophilic addition reaction between 2, 6-tetramethyl piperidine amine and benzotriazole ultraviolet absorbers containing epoxy groups, and the preparation method comprises the following steps: s1: adding 2, 6-tetramethyl piperidine amine into tetrahydrofuran solvent, stirring to dissolve, adding stannous octoate and tertiary amine catalyst, magnetically stirring for 20-30min to obtain mixed solution; s2: adding benzotriazole ultraviolet absorbent containing epoxy groups into the mixed solution, stirring at 45-65 ℃ for reaction for 6-12h, removing tetrahydrofuran solvent, separating and purifying to obtain the product. The light stabilizer prepared by the invention has the dual functions of absorbing ultraviolet rays and capturing and scavenging free radicals, has high effective functional group density, and improves the photo-aging resistance by utilizing the synergy of the tetramethyl piperidine group and the benzotriazole group, inhibits photo-oxidative degradation reaction and further obviously improves the photo-stability.
Description
Technical Field
The invention belongs to the field of synthesis of bifunctional hindered amine light stabilizers, and particularly relates to a tetramethyl piperidine derivative light stabilizer and a preparation method thereof.
Background
The light stabilizer is an additive of organic high molecular material, and can shield or absorb ultraviolet energy, quench singlet oxygen and decompose hydroperoxide into inactive substances, etc., so that the high molecular polymer can eliminate or slow down the possibility of photochemical reaction under the irradiation of light, and prevent or delay the photo-aging process, thereby achieving the purpose of prolonging the service life of the high molecular polymer product. The mechanism of action can be generally divided into: light shielding agents, ultraviolet light absorbers, quenchers and hindered amine light stabilizers.
The hindered amine light stabilizer is a 2, 6-tetramethylpiperidine derivative with a steric hindrance structure, and a functional structural unit tetramethylpiperidine is excited by photoelectrons to be oxidized into nitroxide free radicals NO, so that the R, RO, ROO and other free radicals in the polymer degradation chain reaction can be further effectively captured and eliminated, and the polymer degradation chain reaction is converted into relatively inert compounds, thereby interrupting the reaction process. In addition, the hindered amine light stabilizer also has the function of quenching singlet oxygen, so that the hindered amine light stabilizer is converted from an excited state to a ground state, and the photoaging reaction is interfered. With the continuous and deep research and application of hindered amine light stabilizers, the incorporation or chemical bonding of other functional groups in the molecular structure of hindered amine to impart multiple functions thereto is a hotspot in the development of novel hindered amine light stabilizers.
In the prior art, the synthesis and characterization of 2-phenyl-4, 6-bis [ 2-hydroxy-4- (methylpiperidinyloxycarbonylmethoxy) phenyl ] -1,3, 5-triazine are disclosed in fine chemical engineering, wherein hindered amine is combined with triazine ultraviolet absorbent, firstly, the triazine ultraviolet absorbent is prepared as an intermediate, tetramethyl piperidinol or pentamethylpiperidinol is introduced through transesterification, and the ultraviolet absorption intensity of two novel compounds is characterized, which is obviously enhanced compared with Tinuvin-1577; the synthesis, characterization and performance evaluation of difunctional hindered amine light stabilizer [ J ]. Chemical industry and engineering, the reaction of 2, 4-dihydroxybenzophenone and chloroacetyl chloride to produce intermediate, and the condensation with tetramethyl piperidine amine to synthesize new light stabilizer with stronger ultraviolet absorption capacity than 2, 4-dihydroxybenzophenone. The invention patent number CN110283116B discloses a hindered amine light stabilizer, preparation and application, and discloses a method for synthesizing the hindered amine light stabilizer by utilizing the reaction of hexamethylenediamine piperidine with benzoyl chloride, o-fluorobenzoyl chloride, p-methoxybenzoyl chloride or palmitoyl chloride, so that the hindered amine light stabilizer has the functions of ultraviolet absorption and thermal oxidation resistance, and is multipurpose; the invention patent number CN104231187B discloses an amphiphilic comb-shaped composite polymer light stabilizer and a preparation method thereof, wherein methyl fumarate polyethylene glycol monomethyl ether diester is utilized to react with 2, 6-tetramethyl piperidinol or 1,2, 6-pentamethyl piperidinol to synthesize an intermediate I, then an ultraviolet absorber benzophenone compound is utilized to react with triethylamine and allyl chloride compound to synthesize an intermediate II, finally alkyl acrylate or styrene monomer compound, the intermediate I and the intermediate II are subjected to ternary polymerization to synthesize the amphiphilic comb-shaped composite polymer light stabilizer, the prepared product has multiple light stabilization functions of absorbing ultraviolet rays, capturing free radicals and the like, hydrophilic groups and lipophilic groups are simultaneously introduced into a molecular chain, and the problem of poor compatibility of the traditional oil-soluble light stabilizer in a wood-plastic composite material is solved. The invention patent No. CN110922389B discloses a preparation method of a hindered amine light stabilizer, which comprises the steps of reacting cyanuric chloride with N, N' -bis (3-aminopropyl) ethylenediamine at the temperature of minus 10-20 ℃ to obtain an intermediate I, reacting the intermediate I with N-butyl-2, 6-tetramethyl-4-piperidylamine to obtain an intermediate II, and finally carrying out methylation reaction on the intermediate II with paraformaldehyde or formaldehyde and formic acid at the reflux temperature by taking water as a solvent to obtain a target product, so that the density of hindered amine functional groups of the product is improved, and further the anti-photoaging effect is improved. Therefore, how to develop a novel bifunctional tetramethylpiperidine derivative light stabilizer with both hindered amine groups and benzotriazole groups is of great importance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a tetramethylpiperidine derivative light stabilizer and a preparation method thereof.
The technical scheme of the invention is summarized as follows:
a tetramethylpiperidine derivative light stabilizer is characterized in that: the tetramethylpiperidine derivative is prepared by nucleophilic addition reaction between 2, 6-tetramethylpiperidine amine and benzotriazole ultraviolet absorbent containing epoxy group, and the chemical structural formula is shown in formula I:
preferably, the tetramethylpiperidine derivative comprises the following preparation raw materials: 2, 6-tetramethyl piperidine amine, benzotriazole ultraviolet absorber containing epoxy group, stannous octoate, tertiary amine catalyst and tetrahydrofuran solvent.
Preferably, the dosage ratio of the 2, 6-tetramethylpiperidine amine, the benzotriazole ultraviolet absorber containing epoxy groups, stannous octoate, the tertiary amine catalyst and the tetrahydrofuran solvent is (0.05-0.1) mol (0.05-0.1) g (0.1-0.5) g (0.05-0.25) g/100 mL.
Preferably, the dosage ratio of the 2, 6-tetramethylpiperidine amine, the benzotriazole ultraviolet absorber containing epoxy groups, stannous octoate, the tertiary amine catalyst and the tetrahydrofuran solvent is 0.075mol:0.075mol:0.3g:0.15g:100mL.
Preferably, the benzotriazole ultraviolet absorber containing epoxy groups is 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole, and the chemical structural formula of the benzotriazole ultraviolet absorber is shown as formula II:
preferably, the tertiary amine catalyst is one or more of triethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, dimethylaminoethyl ether, N-dimethylcyclohexylamine and tetramethyl-1, 4-butanediamine.
The preparation method of the tetramethylpiperidine derivative light stabilizer is characterized by comprising the following steps of:
s1: adding 2, 6-tetramethyl piperidine amine into tetrahydrofuran solvent, stirring to dissolve, adding stannous octoate and tertiary amine catalyst, magnetically stirring for 10-50min to obtain mixed solution;
s2: adding benzotriazole ultraviolet absorbent containing epoxy groups into the mixed solution, stirring and reacting for 3-12 hours at 40-65 ℃, removing tetrahydrofuran solvent, separating and purifying to obtain the tetramethylpiperidine derivative light stabilizer.
Preferably, the preparation method of the tetramethylpiperidine derivative light stabilizer comprises the following steps:
s1: adding 2, 6-tetramethyl piperidine amine into tetrahydrofuran solvent, stirring to dissolve, adding stannous octoate and tertiary amine catalyst, magnetically stirring for 25-35min to obtain mixed solution;
s2: adding 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole into the mixed solution, stirring at 50-60 ℃ for reaction for 6-10h, removing tetrahydrofuran solvent by rotary evaporation under reduced pressure, and separating and purifying by column chromatography to obtain the tetramethylpiperidine derivative light stabilizer.
The invention has the beneficial effects that:
1. according to the invention, the nucleophilic addition reaction of 2, 6-tetramethyl piperidine amine and benzotriazole ultraviolet absorbent containing epoxy groups is utilized for the first time to prepare the difunctional tetramethyl piperidine derivative light stabilizer, the prepared hindered amine light stabilizer has the dual functions of absorbing ultraviolet rays and capturing and scavenging free radicals, the effective functional group density is high, the synergistic effect of tetramethyl piperidine groups and benzotriazole groups is utilized to improve the photo-aging resistance, the photo-oxidative degradation reaction is inhibited, and the photo-stability performance is further obviously improved.
2. The preparation method is simple, has few side reactions and high yield, can realize the chemical bonding of 2, 6-tetramethyl piperidine amine and 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole by directly utilizing the addition reaction of the two by a one-step method, does not need to activate a reaction monomer to form an intermediate, and then further reacts with another reaction monomer, thereby simplifying the synthesis process.
3. The light stabilizer of the tetramethyl piperidine derivative prepared by the invention has active hydroxyl and secondary amino, and can be grafted to a polymer main chain such as polyurethane, epoxy resin and the like, so that the defects of poor compatibility with polymer materials, easy volatilization, migration, escape and the like are overcome, and the heat resistance and extraction resistance of the light stabilizer are effectively improved.
Drawings
FIG. 1 shows the chemical structural formula of a tetramethylpiperidine derivative light stabilizer prepared by the present invention;
FIG. 2 is a flow chart of the preparation method of the tetramethylpiperidine derivative light stabilizer.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
The invention provides an embodiment of a tetramethylpiperidine derivative light stabilizer: the tetramethylpiperidine derivative is prepared by nucleophilic addition reaction between 2, 6-tetramethylpiperidine amine and benzotriazole ultraviolet absorbent containing epoxy group, and the chemical structural formula is shown in formula I:
the tetramethylpiperidine derivative comprises the following preparation raw materials: 2, 6-tetramethyl piperidine amine, benzotriazole ultraviolet absorber containing epoxy group, stannous octoate, tertiary amine catalyst and tetrahydrofuran solvent; and the dosage proportion of the 2, 6-tetramethyl piperidine amine, the benzotriazole ultraviolet absorber containing epoxy groups, stannous octoate, the tertiary amine catalyst and the tetrahydrofuran solvent is (0.05-0.1) mol (0.05-0.1) g (0.1-0.5) g (0.05-0.25) g and 100mL.
The benzotriazole ultraviolet absorber containing epoxy groups is 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole, and the chemical structural formula is shown as formula II:
the tertiary amine catalyst is one or more of triethylamine, 2,4, 6-tri (dimethylaminomethyl) phenol, dimethylaminoethyl ether, N-dimethylcyclohexylamine and tetramethyl-1, 4-butanediamine.
The preparation method of the tetramethylpiperidine derivative light stabilizer comprises the following steps:
s1: adding 2, 6-tetramethyl piperidine amine into tetrahydrofuran solvent, stirring to dissolve, adding stannous octoate and tertiary amine catalyst, magnetically stirring for 10-50min to obtain mixed solution;
s2: adding benzotriazole ultraviolet absorbent containing epoxy groups into the mixed solution, stirring and reacting for 3-12 hours at 40-65 ℃, removing tetrahydrofuran solvent, separating and purifying to obtain the tetramethylpiperidine derivative light stabilizer.
Further, the preparation method of the tetramethylpiperidine derivative light stabilizer comprises the following steps:
s1: adding 2, 6-tetramethyl piperidine amine into tetrahydrofuran solvent, stirring to dissolve, adding stannous octoate and tertiary amine catalyst, magnetically stirring for 25-35min to obtain mixed solution;
s2: adding 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole into the mixed solution, stirring at 50-60 ℃ for reaction for 6-10h, removing tetrahydrofuran solvent by rotary evaporation under reduced pressure, and separating and purifying by column chromatography to obtain the tetramethylpiperidine derivative light stabilizer.
Example 1
A preparation method of a tetramethylpiperidine derivative light stabilizer comprises the following steps:
s1: mixing 0.2mol of 2- (2 ',4' -dihydroxyphenyl) -5-chlorobenzotriazole with 0.2mol of epichlorohydrin, adding into 200mL of tetrahydrofuran solvent, stirring uniformly, adding 4g of sodium hydroxide, stirring at 65 ℃ for reaction for 6 hours, removing the tetrahydrofuran solvent by decompression rotary evaporation, washing, drying, separating and purifying by column chromatography to obtain 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole;
s2: adding 0.05mol of 2, 6-tetramethyl piperidine amine into tetrahydrofuran solvent, stirring and dissolving, adding 0.1g of stannous octoate and 0.05g of triethylamine, and magnetically stirring for 25-35min to obtain a mixed solution;
s3: and (3) adding 0.05mol of 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole into the mixed solution obtained in the step (S2), stirring at 50 ℃ for reaction for 6 hours, removing tetrahydrofuran solvent by rotary evaporation under reduced pressure, and then passing through the column chromatography for separation and purification to obtain the tetramethylpiperidine derivative light stabilizer, wherein the product yield is 85.5%.
Example 2
A preparation method of a tetramethylpiperidine derivative light stabilizer comprises the following steps:
s1: as in example 1;
s2: adding 0.075mol of 2, 6-tetramethyl piperidine amine into tetrahydrofuran solvent, stirring and dissolving, adding 0.3g stannous octoate and 0.15g of 2,4, 6-tris (dimethylaminomethyl) phenol, magnetically stirring for 30min, and obtaining a mixed solution;
s3: and (3) adding 0.075mol of 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole into the mixed solution obtained in the step (S2), stirring at 55 ℃ for reaction for 8 hours, removing tetrahydrofuran solvent by rotary evaporation under reduced pressure, and separating and purifying by column chromatography to obtain the tetramethylpiperidine derivative light stabilizer, wherein the product yield is 89.2%.
Example 3
A preparation method of a tetramethylpiperidine derivative light stabilizer comprises the following steps:
s1: as in example 1;
s2: adding 0.1mol of 2, 6-tetramethylpiperidine amine into tetrahydrofuran solvent, stirring and dissolving, adding 0.5g of stannous octoate and 0.25g of dimethylaminoethyl ether, and magnetically stirring for 35min to obtain a mixed solution;
s3: and (3) adding 0.1mol of 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole into the mixed solution obtained in the step (S2), stirring at 60 ℃ for reaction for 10 hours, removing tetrahydrofuran solvent by rotary evaporation under reduced pressure, and separating and purifying by column chromatography to obtain the tetramethylpiperidine derivative light stabilizer with the product yield of 87.6 percent.
Comparative example is a mixture of 0.1mol 2, 6-tetramethylpiperidinamine with 0.1mol 2- (2 '-hydroxy-4' - (2 ",3" -glycidoxy) phenyl) -5-chlorobenzotriazole.
Light stability was measured: after heating 4 groups of equivalent polyethylene substrates to be completely melted at 150 ℃, respectively adding 0.3% of the mass of the substrate of the tetramethylpiperidine derivative light stabilizer of examples 1-3 or the light stabilizer of the mixture of comparative examples to each group, tabletting, cooling, forming, weighing the mass of each formed product, marking as M, radiating the formed product by using an ultraviolet lamp with the power of 250W, keeping the distance between the product and the ultraviolet lamp at 15cm, weighing the mass of each group when radiating for 100h, marking as M1, weighing the mass of each group when radiating for 250h, marking as M2, and expressing the mass retention rate by using 100% M1/M and 100% M2/M, wherein the test results are shown in the following table:
| mass retention/% | Example 1 | Example 2 | Example 3 | Comparative example |
| Ultraviolet radiation for 100h | 98.8 | 99.1 | 98.7 | 86.3 |
| Ultraviolet radiation for 250h | 97.1 | 97.5 | 96.9 | 80.5 |
From the above table, the photo-oxidative degradation resistance of the tetramethylpiperidine derivative light stabilizer of examples 1-3 is significantly better than that of the equimolar mixture of comparative example 2, 6-tetramethylpiperidine amine and 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole, which proves that examples 1-3 chemically bond hindered amine molecules with benzotriazole molecules to form a novel bifunctional light stabilizer with higher ultraviolet light resistance and photo-oxidative degradation resistance, and synergistically improve the light stabilizer.
Examples 1-3 were prepared by first utilizing the nucleophilic addition reaction of 2, 6-tetramethylpiperidine amine and an epoxy-containing benzotriazole ultraviolet absorber to prepare a bifunctional tetramethylpiperidine derivative light stabilizer, and the prepared hindered amine light stabilizer has the dual functions of absorbing ultraviolet rays and capturing and scavenging free radicals, has high effective functional group density, and utilizes the synergy of tetramethylpiperidine groups and benzotriazole groups to improve the photo-aging resistance, inhibit the photo-oxidative degradation reaction and further obviously improve the photo-stability.
The preparation method of the embodiment 1-3 is simple, has few side reactions and high yield, can realize the chemical bonding of 2, 6-tetramethyl piperidine amine and 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole by directly utilizing the addition reaction of the two by a one-step method, does not need to activate the reaction monomers to form intermediates, and then further reacts with another reaction monomer, thereby simplifying the synthesis process.
The tetramethylpiperidine derivative light stabilizer prepared in the embodiment 1-3 has active hydroxyl and secondary amino, can be grafted on a polymer main chain such as polyurethane, epoxy resin and the like, further overcomes the defects of poor compatibility with polymer materials, easy volatilization, migration, escape and the like, and effectively improves the heat resistance and extraction resistance of the tetramethylpiperidine derivative light stabilizer.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (6)
1. A tetramethylpiperidine derivative light stabilizer is characterized in that: the tetramethylpiperidine derivative is prepared by nucleophilic addition reaction between 2, 6-tetramethylpiperidine amine and benzotriazole ultraviolet absorbent containing epoxy group, and the chemical structural formula is shown in formula I:
2. a process for the preparation of a tetramethylpiperidine derivative light stabilizer according to claim 1 comprising the steps of:
s1: adding 2, 6-tetramethyl piperidine amine into tetrahydrofuran solvent, stirring to dissolve, adding stannous octoate and tertiary amine catalyst, magnetically stirring for 10-50min to obtain mixed solution;
s2: adding benzotriazole ultraviolet absorbent containing epoxy groups into the mixed solution, stirring and reacting for 3-12 hours at 40-65 ℃, removing tetrahydrofuran solvent, and separating and purifying to obtain the tetramethylpiperidine derivative light stabilizer; the benzotriazole ultraviolet absorber containing epoxy groups is 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole, and the chemical structural formula is shown as formula II:
3. the method for preparing a light stabilizer of a tetramethylpiperidine derivative according to claim 2, wherein the ratio of the amount of the 2, 6-tetramethylpiperidine amine, the benzotriazole ultraviolet absorber containing an epoxy group, stannous octoate, the tertiary amine catalyst, and the tetrahydrofuran solvent is (0.05-0.1) mol (0.1-0.5) g (0.05-0.25) g:100mL.
4. The method for preparing a light stabilizer of a tetramethylpiperidine derivative according to claim 3, wherein the ratio of the amount of the 2, 6-tetramethylpiperidine amine, the benzotriazole ultraviolet absorber containing an epoxy group, stannous octoate, the tertiary amine catalyst, and the tetrahydrofuran solvent is 0.075mol:0.3g:0.15g:100mL.
5. The method for preparing a light stabilizer of a tetramethylpiperidine derivative according to any one of claims 2 to 4, wherein said tertiary amine catalyst is one or more of triethylamine, 2,4, 6-tris (dimethylaminomethyl) phenol, dimethylaminoethyl ether, N-dimethylcyclohexylamine, tetramethyl-1, 4-butanediamine.
6. The method for preparing the tetramethylpiperidine derivative light stabilizer according to claim 5, comprising the steps of:
s1: adding 2, 6-tetramethyl piperidine amine into tetrahydrofuran solvent, stirring to dissolve, adding stannous octoate and tertiary amine catalyst, magnetically stirring for 25-35min to obtain mixed solution;
s2: adding 2- (2 '-hydroxy-4' - (2 ', 3' -glycidoxy) phenyl) -5-chlorobenzotriazole into the mixed solution, stirring at 50-60 ℃ for reaction for 6-10h, removing tetrahydrofuran solvent by rotary evaporation under reduced pressure, and separating and purifying by column chromatography to obtain the tetramethylpiperidine derivative light stabilizer.
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