CN102432597A - Benzotriazole light stabilizer containing hindered amine group - Google Patents
Benzotriazole light stabilizer containing hindered amine group Download PDFInfo
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- CN102432597A CN102432597A CN201110268902XA CN201110268902A CN102432597A CN 102432597 A CN102432597 A CN 102432597A CN 201110268902X A CN201110268902X A CN 201110268902XA CN 201110268902 A CN201110268902 A CN 201110268902A CN 102432597 A CN102432597 A CN 102432597A
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- benzotriazole
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- phenyl
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- 239000012964 benzotriazole Substances 0.000 title claims abstract description 14
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 title claims description 16
- 125000003277 amino group Chemical group 0.000 title abstract description 9
- 239000004611 light stabiliser Substances 0.000 title abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 33
- -1 benzotriazole compound Chemical class 0.000 claims abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229920002678 cellulose Polymers 0.000 claims abstract description 6
- 239000001913 cellulose Substances 0.000 claims abstract description 6
- 229920005989 resin Polymers 0.000 claims abstract description 5
- 239000011347 resin Substances 0.000 claims abstract description 5
- 150000003053 piperidines Chemical class 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 5
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 5
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 5
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 5
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 239000004640 Melamine resin Substances 0.000 claims description 4
- 229920002319 Poly(methyl acrylate) Polymers 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229920001228 polyisocyanate Polymers 0.000 claims description 3
- 239000005056 polyisocyanate Substances 0.000 claims description 3
- 229920003987 resole Polymers 0.000 claims description 3
- ACYXOHNDKRVKLH-UHFFFAOYSA-N 5-phenylpenta-2,4-dienenitrile prop-2-enoic acid Chemical compound OC(=O)C=C.N#CC=CC=CC1=CC=CC=C1 ACYXOHNDKRVKLH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002449 FKM Polymers 0.000 claims description 2
- 229930182556 Polyacetal Natural products 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001470 polyketone Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920002102 polyvinyl toluene Polymers 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 abstract 1
- 239000000835 fiber Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 abstract 1
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 229920006345 thermoplastic polyamide Polymers 0.000 abstract 1
- 239000001993 wax Substances 0.000 abstract 1
- 239000002585 base Substances 0.000 description 35
- 229910052760 oxygen Inorganic materials 0.000 description 34
- 239000001301 oxygen Substances 0.000 description 34
- 238000000921 elemental analysis Methods 0.000 description 26
- 238000004128 high performance liquid chromatography Methods 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 13
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 239000011368 organic material Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 6
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- SNASAWALQZEJGG-UHFFFAOYSA-N ethyl 2-[4-(5-chlorobenzotriazol-2-yl)-3-hydroxyphenoxy]acetate Chemical compound CCOC(=O)COC1=CC(=C(C=C1)N2N=C3C=CC(=CC3=N2)Cl)O SNASAWALQZEJGG-UHFFFAOYSA-N 0.000 description 4
- RJGWOBWUDDFTIY-UHFFFAOYSA-N ethyl 2-[4-(benzotriazol-2-yl)-3-hydroxyphenoxy]acetate Chemical compound OC1=CC(OCC(=O)OCC)=CC=C1N1N=C2C=CC=CC2=N1 RJGWOBWUDDFTIY-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- XULIXFLCVXWHRF-UHFFFAOYSA-N 1,2,2,6,6-pentamethylpiperidine Chemical class CN1C(C)(C)CCCC1(C)C XULIXFLCVXWHRF-UHFFFAOYSA-N 0.000 description 1
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical compound CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 0 CC(C)(C1)N(*)C(C)(C)CC1O Chemical compound CC(C)(C1)N(*)C(C)(C)CC1O 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 239000013036 UV Light Stabilizer Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MCDXZKVKTYGTBZ-UHFFFAOYSA-N ethyl 2-[4-(5-bromobenzotriazol-2-yl)-3-hydroxyphenoxy]acetate Chemical compound CCOC(=O)COC1=CC(=C(C=C1)N2N=C3C=CC(=CC3=N2)Br)O MCDXZKVKTYGTBZ-UHFFFAOYSA-N 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical group CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- AGAHNABIDCTLHW-UHFFFAOYSA-N moperone Chemical compound C1=CC(C)=CC=C1C1(O)CCN(CCCC(=O)C=2C=CC(F)=CC=2)CC1 AGAHNABIDCTLHW-UHFFFAOYSA-N 0.000 description 1
- 229960000758 moperone Drugs 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a benzotriazole compound containing a hindered amine group of the general formula I wherein the general symbols are as defined in claim 1. To a process for the preparation of such compounds; the use of the compounds of the invention or prepared according to the invention as light stabilizers is effective for stabilizing thermosetting resins, thermoplastic resins, polyamide or polyester fibers, organic dyes, cellulose paper preparations, photographic film papers, inks, white or pigmented waxes, etc., with very effective UV absorption activity and hindered amine light stability.
Description
The application is that application number is 200810167812.X, is entitled as the dividing an application of application of " benzotriazole light stabilizer that contains hindered amine group ".
Technical field
The present invention relates to a kind of benzotriazole light stabilizer that contains hindered amine group, belong to the photostabilizer field.
Background technology
Benzotriazole category UV light absorber and hindered amines radical scavenger are polymkeric substance two types of photostabilizers commonly used, can use separately also and can compositely use, and composite back makes effect better owing to having synergy.From molecular designing and atom economy angle, design contains benzotriazole and the structure of hindered amine simultaneously at same intramolecularly, and the research that makes compound have UVA and two kinds of functions of radical-trapping has more development potentiality.
The hindered amine group benzotriazole light stabilizer structure of having reported that contains is that its structural formula is following with connection piperidines alcohol structure on the phenyl ring of alkyl-substituted phenols:
Wherein, R
1, R
2Or R
3Have at least one to contain hindered amine group.
For example, directly introduce the structure of hindered amine through the benzotriazole compound that contains propionic ester functional group.Switzerland vapour Bagong department in its patent, introduced with 3-[5 '-(2H-benzotriazole)-3 '-tertiary butyl-4 '-hydroxyl-phenyl] methyl propionate or 3-[5 '-(5-chloro-2H-benzotriazole)-3 '-tertiary butyl-4 '-hydroxyl-phenyl] methyl propionate; With moperone; In the presence of toluene or xylene solvent and catalyzer, carry out the synthetic benzotriazole cpd that contains the structure of hindered amine of transesterification reaction (Ciba Specialty Chemicals Holding AG.Benzotriazoles and their use as UV light stabilizer [P] .WO 02/079173,2002-10-10.).The inventor also once to this compounds carried out studying (Shao Yuchang, a left side is loud and clear. contain benzotriazole light stabilizer synthetic of the structure of hindered amine and characterize. fine chemistry industry, 2007, (12), 1163-1167.).
The benzotriazole light stabilizer that this type contains hindered amine group is that its uv-absorbing intensity still usually can't be satisfactory with connection piperidines alcohol structure on the phenyl ring of alkyl-substituted phenols.
Summary of the invention
An object of the present invention is to provide further improved efficiency light stablizer of uv-absorbing intensity with UVA and radical-trapping function.The Resorcinol type benzotriazole cpd that we are surprised to find like the introducing hindered amine group of general formula I can achieve this end.
Wherein, R
1=H, Cl or Br,
N=1 or 2 wherein,
R
3=H, CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
8H
17, C
12H
25, OCH
3, OC
2H
5, OC
3H
7, OC
4H
9, OC
5H
11, OC
6H
13, OC
8H
17Or OC
12H
25, R
4=H, CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
8H
17Or C
12H
25
Preferred compound of the present invention is R wherein
1Be those compounds of H or Cl.
Special preferred compound is R
1Be H or Cl, and R
3, R
4Be H or CH independently
3Those compounds.
The instance of special preferred compound has:
Work as R
1=H and R
3During=H, i.e. 2-[2-hydroxyl-4-(2,2,6,6-tetramethyl piperidine-4-oxygen base) carbonyl p-methoxy-phenyl]-2H-benzotriazole (compound I I), its structural formula does
Work as R
1=Cl and R
3During=H, i.e. 5-chloro-2-[2-hydroxyl-4-(2,2,6,6-tetramethyl piperidine-4-oxygen base) carbonyl p-methoxy-phenyl]-2H-benzotriazole (compound III), its structural formula does
Work as R
1=H and R
3=CH
3The time, i.e. 2-[2-hydroxyl-4-(1,2,2,6,6-pentamethyl-piperidines-4-oxygen base) carbonyl p-methoxy-phenyl]-2H-benzotriazole (compound IV), its structural formula does
Work as R
1=Cl and R
3=CH
3The time, i.e. 5-chloro-2-[2-hydroxyl-4-(1,2,2,6,6-pentamethyl-piperidines-4-oxygen base) carbonyl p-methoxy-phenyl]-2H-benzotriazole (compound V), its structural formula does.
The present invention also provides the preparation method of formula I compound.
Compound with formula I of the present invention can be through the OR 10154 of following general formula
N=1 or 2 wherein, R
1Be H, Cl or Br;
Piperidines alcohol derivate with following general formula
R wherein
3Be H, CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
8H
17, C
12H
25, OCH
3, OC
2H
5, OC
3H
7, OC
4H
9, OC
5H
11, OC
6H
13, OC
8H
17, OC
12H
25And solvent, catalyzer add in the reactor drum, the reaction 3～8 hours down of 100～250 ℃ of temperature condition; Wherein the add-on of solvent is 0.5～50 times of OR 10154 quality, and the add-on of catalyzer is 0.1%～10% of an OR 10154 quality, and the mol ratio of OR 10154 and piperidines alcohol derivate is 0.3～1.0.
Employed OR 10154 can be 2-[2-hydroxyl-4-ethoxycarbonyl methoxy phenyl]-2H-benzotriazole, 5-chloro-2-[2-hydroxyl-4-ethoxycarbonyl methoxy phenyl]-2H-benzotriazole, 5-bromo-2-[2-hydroxyl-4-ethoxycarbonyl methoxy phenyl]-2H-benzotriazole etc.; Preferred 2-[2-hydroxyl-4-ethoxycarbonyl methoxy phenyl]-2H-benzotriazole, or 5-chloro-2-[2-hydroxyl-4-ethoxycarbonyl methoxy phenyl]-2H-benzotriazole.
The piperidines alcohol derivate can be
R wherein
3Be H, CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
8H
17, C
12H
25, OCH
3, OC
2H
5, OC
3H
7, OC
4H
9, OC
5H
11, OC
6H
13, OC
8H
17Or OC
12H
25, preferred 2,2,6,6-tetramethylpiperidinol or 1,2,2,6,6-pentamethyl-piperidines alcohol.
Wherein, the mol ratio of OR 10154 and piperidines alcohol derivate is generally 0.3～1.0, and is preferred 0.4～0.6, and most preferably about 0.5.
Employed catalyzer can be strong alkaline substance (like sodium methylate, sodium ethylate, sodium tert-butoxide, a potassium tert.-butoxide), tetrabutyl titanate, tosic acid, Dibutyltin oxide etc., preferred tetrabutyl titanate or Dibutyltin oxide, most preferably Dibutyltin oxide.Catalyst levels is generally 0.1%～10% of OR 10154 quality, and is preferred 0.5%～5%, and most preferably 0.8%～3%.
Employed solvent can be toluene, YLENE, chlorobenzene, solvent wet goods, preferred toluene or YLENE, most preferably YLENE.Solvent load is generally 0.5～50 times of OR 10154 quality, and preferred 1～20 times, most preferably 3～10 times.
Temperature of reaction is 100～250 ℃, preferred 120～200 ℃, and most preferably 130～180 ℃.
Another acquiring way of formula I compound of the present invention is the OR 10154 through following general formula
R wherein
1Be H, Cl or Br;
Piperidines alcohol derivate with following general formula
R wherein
3Be H, CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
8H
17, C
12H
25, OCH
3, OC
2H
5, OC
3H
7, OC
4H
9, OC
5H
11, OC
6H
13, OC
8H
17, OC
12H
25R
4Be H, CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
8H
17Or C
12H
25And solvent, alkali add in the reactor drum, the reaction 3～8 hours down of 0～100 ℃ of temperature condition; Wherein the add-on of solvent is 0.5～50 times of OR 10154 quality, and the mol ratio of OR 10154 and piperidines alcohol derivate is 1.0～1.2, and the mol ratio of alkali and piperidines alcohol derivate is 0.5～1.5.
Employed OR 10154 can be 2-[2; The 4-dihydroxy phenyl]-2H-benzotriazole, 5-chloro-2-[2, the 4-dihydroxy phenyl]-2H-benzotriazole, 5-bromo-2-[2, the 4-dihydroxy phenyl]-2H-benzotriazole etc.; Preferred 2-[2; The 4-dihydroxy phenyl]-the 2H-benzotriazole, or 5-chloro-2-[2, the 4-dihydroxy phenyl]-2H-benzotriazole.
The piperidines alcohol derivate can be
R wherein
3Be H, CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
8H
17, C
12H
25, OCH
3, OC
2H
5, OC
3H
7, OC
4H
9, OC
5H
11, OC
6H
13, OC
8H
17, OC
12H
25, R
4Be H, CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
8H
17Or C
12H
25
The mol ratio of OR 10154 and piperidines alcohol derivate is generally 1.0～1.2, and preferred 1.0～1.1, preferred especially about 1.05.
Employed alkaline matter can be KOH, NaOH, Ca (OH)
2, K
2CO
3, Na
2CO
3, MgCO
3, KHCO
3Or NaHCO
3Deng, preferred K
2CO
3, Na
2CO
3, KHCO
3Or NaHCO
3, preferred especially Na
2CO
3Or KHCO
3The alkali consumption generally is that the mol ratio of alkali and piperidines alcohol derivate is 0.5～1.5, and is preferred 1.0～1.2, most preferably 1.0～1.05.
Employed solvent can be acetone, THF, ETHYLE ACETATE, toluene, YLENE, chlorobenzene, solvent wet goods, preferred acetone, THF, ETHYLE ACETATE, most preferably acetone.Solvent load is generally 0.5～50 times of OR 10154 quality, and preferred 1～20 times, most preferably 3～10 times.
Temperature of reaction is 0～100 ℃, preferred 10～80 ℃, and most preferably 20～70 ℃.
Above-mentioned preparation method also further comprises the post-reaction treatment step.The reaction solution cooling, filtration, the drying that are about to obtain obtain thick product, and recrystallization obtains pure article again.
Said recrystallization generally adopts toluene, YLENE, chlorobenzene, ETHYLE ACETATE, N (DMF) or DMSO 99.8MIN. (DMSO) etc., ethyl acetate.
Compound of the present invention has the active and hindered amine light stability of highly effective uv-absorbing.Can adopt and anyly known photostabilizer and other additives sneaked into the equipment and the method for organic materials,, compound of the present invention or compound prepared in accordance with the present invention mixed with organic materials like Banbury mixer.Organic materials has thermosetting resin, thermoplastic resin, polymeric amide or trevira, organic dye, cellulose paper preparation, photographic film with paper, printing ink, white or coloured wax etc.Specific examples comprises:
Polyolefins is like Vilaterm (PE), Vestolen PP 7052 (PP), SE (PVC), PS (PS), polyvinyltoluene etc.; Polyester is like polyethyleneterephthalate (PET), PBT (PBT), polycarbonate (PC), polyarylester etc.; Polyamide-based, like polymeric amide, polyimide, polyamidoimide, polyetherimide etc.; Polyacetal, polyacrylonitrile, polyethers, polyketone, polyphenylene thioether; Polysulfones, polyethersulfone, ppe (PPO), resol, urea-formaldehyde resin; Synolac, urea resin, polymeric polyisocyanate, chlorinated isocyanurates, epoxy acid esters; ZGK 5, epoxy melamine resin, tree elastomer, viton, acrylonitrile-butadiene-styrene copolymer (ABS); Styrene-acrylonitrile copolymer (SAN), propenoate-styrene-acrylonitrile copolymer (ASA), amino resin crosslinked Vestolen PP 7052 and polyester, polyester that polymeric polyisocyanate is crosslinked and polyacrylic ester, cellulose acetate butyrate; Cellulose polymer compound, with the crosslinked vinyl resin of melamine resin, aliphatics cyclic aliphatic heterocycle and aromatics Racemic glycidol compound (crosslinked) deutero-cross-linked epoxy resin, organic dye, makeup with acid anhydrides or amine; The cellulose paper preparation, photographic film is used paper, printing ink, white or coloured wax; And the mixture of above-mentioned substance.
Joining by the compound concentrations according to the invention in the stable above-mentioned organic materials, is 0.1%～3% (massfraction), and preferred 0.1%～1.0% (massfraction) is based on the organic materials meter.
Can adopt any equipment and method of stablizer and other additives being sneaked into organic materials, compound of the present invention or compound prepared in accordance with the present invention are mixed with organic materials.
Embodiment
Further explain the present invention with the mode of embodiment below, but the present invention is not limited to these embodiment.
The preparation embodiment of The compounds of this invention
Embodiment 1
, 125mL adds 10.0g (0.03195mol) 2-[2-hydroxyl-4-ethoxycarbonyl methoxy phenyl]-2H-benzotriazole, 10.0g (0.0637mol) 2 in being equipped with the four-hole bottle of stirring, prolong and TM; 2; 6; 6-tetramethylpiperidinol, 0.2g Dibutyltin oxide and 50mL YLENE, 140 ℃ were reacted 6 hours.Cooling after reaction finishes, filtration, drying obtain white solid with re-crystallizing in ethyl acetate, i.e. 2-[2-hydroxyl-4-(2 again; 2; 6,6-tetramethyl piperidine-4-oxygen base) the carbonyl p-methoxy-phenyl]-2H-benzotriazole (compound I I) 8.1g, yield 59.3%; Performance liquid chromatography (HPLC) purity 99.2%, 160.8～161.0 ℃ of fusing points.
Results of elemental analyses:
Embodiment 2
, 125mL adds 10.0g (0.0288mol) 5-chloro-2-[2-hydroxyl-4-ethoxycarbonyl methoxy phenyl]-2H-benzotriazole, 10.0g (0.0637mol) 2 in being equipped with the four-hole bottle of stirring, prolong and TM; 2; 6; 6-tetramethylpiperidinol, 0.2g Dibutyltin oxide and 50mL solvent oil, reaction is 7 hours under 140 ℃ of conditions.Cooling after reaction finishes, filtration, drying obtain white solid with re-crystallizing in ethyl acetate, i.e. 5-chloro-2-[2-hydroxyl-4-(2 again; 2; 6,6-tetramethyl piperidine-4-oxygen base) the carbonyl p-methoxy-phenyl]-2H-benzotriazole (compound III) 7.7g, yield 57.8%; HPLC purity 99.1%, 167.1～167.4 ℃ of fusing points.
Results of elemental analyses:
Embodiment 3
, 125mL adds 10.0g (0.03195mol) 2-[2-hydroxyl-4-ethoxycarbonyl methoxy phenyl]-2H-benzotriazole, 10.0g (0.0585mol) 1 in being equipped with the four-hole bottle of stirring, prolong and TM; 2; 2; 6,6-pentamethyl-piperidines alcohol, 0.2g tetrabutyl titanate and 50mL YLENE, reaction is 6 hours under 140 ℃ of conditions.Cooling after reaction finishes, filtration, drying obtain white solid with re-crystallizing in ethyl acetate, i.e. 2-[2-hydroxyl-4-(1 again; 2,2,6; 6-pentamethyl-piperidines-4-oxygen base) carbonyl p-methoxy-phenyl]-2H-benzotriazole (compound IV) 7.8g; Yield 55.4%, HPLC purity 99.3%, 114.3～114.8 ℃ of fusing points.
Results of elemental analyses:
Embodiment 4
, 125mL adds 10.0g (0.0288mol) 5-chloro-2-[2-hydroxyl-4-ethoxycarbonyl methoxy phenyl]-2H-benzotriazole, 10.0g (0.0585mol) 1 in being equipped with the four-hole bottle of stirring, prolong and TM; 2; 2; 6,6-pentamethyl-piperidines alcohol, 0.2g Dibutyltin oxide and 50mL YLENE, reaction is 6 hours under 140 ℃ of conditions.Cooling after reaction finishes, filtration, drying obtain white solid with re-crystallizing in ethyl acetate, i.e. 5-chloro-2-[2-hydroxyl-4-(1 again; 2,2,6; 6-pentamethyl-piperidines-4-oxygen base) carbonyl p-methoxy-phenyl]-2H-benzotriazole (compound V) 7.5g; Yield 54.5%, HPLC purity 99.0%, 148.4～149.3 ℃ of fusing points.
Results of elemental analyses:
Embodiment 5
Remove piperidine derivative and use 15.7g (0.0585mol) 1-octyl group-(2,2,6; The 6-tetramethyl-) outside the piperidines alcohol, method prepares 2-{2-hydroxyl-4-[1-octyl group-(2,2 described in embodiment 1; 6; The 6-tetramethyl-) piperidines-4-oxygen base] the carbonyl p-methoxy-phenyl }-2H-benzotriazole 7.7g, yield 46.4%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 6
Remove piperidine derivative and use 15.7g (0.0585mol) 1-octyl group-(2,2,6; The 6-tetramethyl-) outside the piperidines alcohol, method prepares 5-chloro-2-{2-hydroxyl-4-[1-octyl group-(2,2 described in embodiment 2; 6; The 6-tetramethyl-) piperidines-4-oxygen base] the carbonyl p-methoxy-phenyl }-2H-benzotriazole 7.0g, yield 44.0%, HPLC purity 99.0%.
Results of elemental analyses:
Embodiment 7
Remove piperidine derivative and use 10.9g (0.0585mol) 1-methoxyl group-(2,2,6; The 6-tetramethyl-) outside the piperidines alcohol, method prepares 2-{2-hydroxyl-4-[1-methoxyl group-(2,2 described in embodiment 3; 6; The 6-tetramethyl-) piperidines-4-oxygen base] the carbonyl p-methoxy-phenyl }-2H-benzotriazole 7.9g, yield 56.4%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 8
Remove piperidine derivative and use 10.9g (0.0585mol) 1-methoxyl group-(2,2,6; The 6-tetramethyl-) outside the piperidines alcohol, method prepares 5-chloro-2-{2-hydroxyl-4-[1-methoxyl group-(2,2 described in embodiment 4; 6; The 6-tetramethyl-) piperidines-4-oxygen base] the carbonyl p-methoxy-phenyl }-2H-benzotriazole 7.0g, yield 51.1%, HPLC purity 99.0%.
Results of elemental analyses:
Embodiment 9
Remove piperidine derivative and use 16.7g (0.0585mol) 1-octyloxy-(2,2,6; The 6-tetramethyl-) outside the piperidines alcohol, method prepares 2-{2-hydroxyl-4-[1-octyloxy-(2,2 described in embodiment 3; 6; The 6-tetramethyl-) piperidines-4-oxygen base] the carbonyl p-methoxy-phenyl }-2H-benzotriazole 7.8g, yield 45.4%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 10
Remove piperidine derivative and use 16.5g (0.0585mol) 1-octyloxy-(2,2,6; The 6-tetramethyl-) outside the piperidines alcohol, method prepares 5-chloro-2-{2-hydroxyl-4-[1-octyloxy-(2,2 described in embodiment 4; 6; The 6-tetramethyl-) piperidines-4-oxygen base] the carbonyl p-methoxy-phenyl }-2H-benzotriazole 6.8g, yield 41.5%, HPLC purity 99.0%.
Results of elemental analyses:
Embodiment 11
, 250mL adds 11.4g (0.05mol) 2-(2 in being equipped with the four-hole bottle of stirring, prolong and TM; The 4-dihydroxy phenyl)-and 2H-benzotriazole, 21.3g (0.05mol) 1-chloro-3,5-two-(4-hydroxyl-2,2; 6,6-tetramethyl-piperidyl)-s-triazine, 5.3g anhydrous Na
2CO
3With 150mL acetone, reaction is 4 hours under 50～56 ℃ of conditions.Cooling after reaction finishes, filtration, drying obtain white solid with the YLENE recrystallization again, and promptly 2-{2-hydroxyl-4-[3; 5-two-(4-hydroxyl-2,2,6; The 6-tetramethyl-piperidyl)]-s-triazinyl phenyl }-2H-benzotriazole 20.1g, yield 65.4%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 12
, 250mL adds 13.1g (0.05mol) 5-chloro-2-2-(2 in being equipped with the four-hole bottle of stirring, prolong and TM; The 4-dihydroxy phenyl)-and 2H-benzotriazole, 21.3g (0.05mol) 1-chloro-3,5-two-(4-hydroxyl-2,2; 6,6-tetramethyl-piperidyl)-s-triazine, 5.3g anhydrous Na
2CO
3With the 150mL THF, reaction is 5 hours under 60～63 ℃ of conditions.Cooling after reaction finishes, filtration, drying obtain white solid with the YLENE recrystallization again, and promptly 5-chloro-2-{2-hydroxyl-4-[3; 5-two-(4-hydroxyl-2,2,6; The 6-tetramethyl-piperidyl)]-s-triazinyl base phenyl }-2H-benzotriazole 18.9g, yield 57.8%, HPLC purity 99.0%.
Results of elemental analyses:
Embodiment 13
, 250mL adds 13.1g (0.05mol) 5-chloro-2-(2 in being equipped with the four-hole bottle of stirring, prolong and TM; The 4-dihydroxy phenyl)-and 2H-benzotriazole, 22.7g (0.0585mol) 1-chloro-3,5-two-(4-methoxyl group-2,2; 6,6-tetramethyl-piperidyl)-s-triazine, 4.2g anhydrous Na HCO
3With 150mL acetone, reaction is 6 hours under 50～56 ℃ of conditions.Cooling after reaction finishes, filtration, drying obtain white solid with the YLENE recrystallization again, and promptly 5-chloro-2-{2-hydroxyl-4-[3; 5-two-(4-methoxyl group-2,2,6; The 6-tetramethyl-piperidyl)]-s-triazinyl phenyl }-2H-benzotriazole 18.1g, yield 53.2%, HPLC purity 99.0%.
Results of elemental analyses:
Embodiment 14
Remove piperidine derivative and use 22.7g (0.05mol) 1-chloro-3,5-two-(4-methoxyl group-2,2; 6,6-tetramethyl-piperidyl)-the s-triazine outside, method prepares 2-{2-hydroxyl-4-[3 described in embodiment 11; 5-two-(4-methoxyl group-2,2,6; The 6-tetramethyl-piperidyl)]-s-triazinyl phenyl }-2H-benzotriazole 19.0g, yield 58.8%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 15
Remove piperidine derivative and use 32.5g (0.05mol) 1-chloro-3,5-two-(4-octyloxy-2,2; 6,6-tetramethyl-piperidyl)-the s-triazine outside, method prepares 2-{2-hydroxyl-4-[3 described in embodiment 11; 5-two-(4-octyloxy-2,2,6; The 6-tetramethyl-piperidyl)]-s-triazinyl phenyl }-2H-benzotriazole 19.0g, yield 45.1%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 16
Remove OR 10154 and use 21.3g (0.05mol) 1-chloro-3,5-two-(2,2; 6,6-tetramethyl piperidine-4-oxygen base)-the s-triazine outside, method prepares 2-{2-hydroxyl-4-[3 described in embodiment 11; 5-two-(2,2,6; 6-tetramethyl piperidine-4-oxygen base)]-s-triazinyl phenyl }-2H-benzotriazole 20.7g, yield 67.1%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 17
Remove piperidine derivative and use 22.7g (0.05mol) 1-chloro-3,5-two-(1,2,2; 6,6-pentamethyl-piperidines-4-oxygen base)-the s-triazine outside, described in embodiment 11 method prepare 2-{2-hydroxyl-4-[3,5-two-(1; 2,2,6; 6-pentamethyl-piperidines-4-oxygen base)]-s-triazinyl phenyl }-2H-benzotriazole 20.7g, yield 64.3%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 18
Remove piperidine derivative and use 32.5g (0.05mol) 1-chloro-3,5-two-(1-octyl group-2,2; 6,6-tetramethyl piperidine-4-oxygen base)-the s-triazine outside, method prepares 2-{2-hydroxyl-4-[3 described in embodiment 11; 5-two-(1-octyl group-2,2,6; 6-tetramethyl piperidine-4-oxygen base)]-s-triazinyl phenyl }-2H-benzotriazole 19.8g, yield 47.2%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 19
Remove piperidine derivative and use 24.3g (0.05mol) 1-chloro-3,5-two-(1-methoxyl group-2,2; 6,6-tetramethyl piperidine-4-oxygen base)-the s-triazine outside, method prepares 2-{2-hydroxyl-4-[3 described in embodiment 11; 5-two-(1-methoxyl group-2,2,6; 6-tetramethyl piperidine-4-oxygen base)]-s-triazinyl phenyl }-2H-benzotriazole 22.6g, yield 67.1%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 20
Remove piperidine derivative and use 34.1g (0.05mol) 1-chloro-3,5-two-(1-octyloxy-2,2; 6,6-tetramethyl piperidine-4-oxygen base)-the s-triazine outside, method prepares 2-{2-hydroxyl-4-[3 described in embodiment 11; 5-two-(1-octyloxy-2,2,6; 6-tetramethyl piperidine-4-oxygen base)]-s-triazinyl phenyl }-2H-benzotriazole 18.7g, yield 42.9%, HPLC purity 99.3%.
Results of elemental analyses:
Embodiment 21
Remove piperidine derivative and use 32.5g (0.05mol) 1-chloro-3,5-two-(1-octyl group-2,2; 6,6-tetramethyl piperidine-4-oxygen base)-the s-triazine outside, method prepares 5-chloro-2-{2-hydroxyl-4-[3 described in embodiment 12; 5-two-(1-octyl group-2,2,6; 6-tetramethyl piperidine-4-oxygen base)]-s-triazinyl phenyl }-2H-benzotriazole 18.7g, yield 42.8%, HPLC purity 99.0%.
Results of elemental analyses:
Embodiment 22
Remove piperidine derivative and use 24.3g (0.05mol) 1-chloro-3,5-two-(1-methoxyl group-2,2; 6,6-tetramethyl piperidine-4-oxygen base)-the s-triazine outside, method prepares 5-chloro-2-{2-hydroxyl-4-[3 described in embodiment 12; 5-two-(1-methoxyl group-2,2,6; 6-tetramethyl piperidine-4-oxygen base)]-s-triazinyl phenyl }-2H-benzotriazole 19.8g, yield 56.1%, HPLC purity 99.0%.
Results of elemental analyses:
Embodiment 23
Remove piperidine derivative and use 34.1g (0.05mol) 1-chloro-3,5-two-(1-octyloxy-2,2; 6,6-tetramethyl piperidine-4-oxygen base)-the s-triazine outside, method prepares 5-chloro-2-{2-hydroxyl-4-[3 described in embodiment 12; 5-two-(1-octyloxy-2,2,6; 6-tetramethyl piperidine-4-oxygen base)]-s-triazinyl phenyl }-2H-benzotriazole 18.3g, yield 40.3%, HPLC purity 99.0%.
Results of elemental analyses:
Embodiment 24
Remove piperidine derivative and use 32.5g (0.05mol) 1-chloro-3,5-two-(4-octyloxy-2,2; 6,6-tetramethyl-piperidyl)-the s-triazine outside, method prepares 5-chloro-2-{2-hydroxyl-4-[3 described in embodiment 13; 5-two-(4-octyloxy 2,2,6; The 6-tetramethyl-piperidyl)]-s-triazinyl phenyl }-2H-benzotriazole 19.1g, yield 43.6%, HPLC purity 99.0%.
Results of elemental analyses:
Embodiment 25
Remove piperidine derivative and use 21.3g (0.05mol) 1-chloro-3,5-two-(2,2; 6,6-tetramethyl piperidine-4-oxygen base)-the s-triazine outside, method prepares 5-chloro-2-{2-hydroxyl-4-[3 described in embodiment 13; 5-two-(2,2,6; 6-tetramethyl piperidine-4-oxygen base)]-s-triazinyl phenyl }-2H-benzotriazole 18.8g, yield 57.7%, HPLC purity 99.0%.
Results of elemental analyses:
Embodiment 26
Remove piperidine derivative and use 22.7g (0.05mol) 1-chloro-3,5-two-(1,2,2; 6,6-pentamethyl-piperidines-4-oxygen base)-the s-triazine outside, described in embodiment 13 method prepare 5-chloro-2-{2-hydroxyl-4-[3,5-two-(1; 2,2,6; 6-pentamethyl-piperidines-4-oxygen base)]-s-triazinyl phenyl }-2H-benzotriazole 18.7g, yield 55.2%, HPLC purity 99.0%.
Results of elemental analyses:
The application implementation example
Embodiment 27: be used for Vestolen PP 7052
The Vestolen PP 7052 of every part 100 gram is restrained 2-[2-hydroxyl-4 benzoic acid ester group phenyl]-2H-benzotriazole (Dalian great achievement chemical industry ltd with 0.4 respectively; Call control compounds in the following text) or embodiment 1～4 synthetic compound I I～V; Add in the Banbury mixer mixing; Mixed 10 minutes down at 180 ℃, obtain polypropylene masterbatch.Masterbatch is put into vulcanizer be pressed into the sheet that thickness is 1mm, pass through coldmoulding again.Cut into the sample strip of 2cm * 5cm, press GB/T16422-1999 plastics laboratory light source exposure test method, place xenon lamp to tan by the sun the light aging test case and shine, press GB2409-80 then and survey its yellowness index, it is as shown in the table to obtain its yellowness index Δ YI.
Embodiment 28: be used for polymethyl acrylate
With the polymethyl acrylate of every part 100 gram respectively with the control compounds or embodiment 1～4 synthetic compound I I～V of 0.4 gram, add in the Banbury mixer mixingly, mixed 10 minutes down at 180 ℃, obtain the polymethyl acrylate masterbatch.Masterbatch is put into vulcanizer be pressed into the sheet that thickness is 1mm, pass through coldmoulding again.Cut into the sample strip of 2cm * 5cm, press GB/T 16422-1999 plastics laboratory light source exposure test method, place xenon lamp to tan by the sun the light aging test case and shine, press GB2409-80 then and survey its yellowness index, obtain shown in its yellowness index Δ YI institute following table.
Embodiment 29: be used for polycarbonate
With the polycarbonate of every part 100 gram respectively with the control compounds or embodiment 1～4 synthetic compound I I～V of 0.4 gram, add in the Banbury mixer mixingly, mixed 10 minutes down at 180 ℃, obtain the polycarbonate masterbatch.Masterbatch is put into vulcanizer be pressed into the sheet that thickness is 1mm, pass through coldmoulding again.Cut into the sample strip of 2cm * 5cm, press GB/T16422-1999 plastics laboratory light source exposure test method, place xenon lamp to tan by the sun the light aging test case and shine, press GB2409-80 then and survey its yellowness index, obtain shown in its yellowness index Δ YI following table.
Embodiment 30～40
1～4 synthetic compound of embodiment is applied to PS (PS) respectively, polyethyleneterephthalate (PET), polyoxymethylene (POM) according to the method for embodiment 27; Nylon (PA), polysulfones (PSF), urea-formaldehyde resin (PF); Acrylonitrile-butadiene-styrene copolymer (ABS), resol (PF), epoxy resin (EP); Polyether-ether-ketone resin (PEEK), TKK 021 (EC), as shown in the table.
Sample of the present invention tans by the sun the light aging test result through xenon lamp to be proved, is not connected the stable control sample of piperidines alcohol structural compounds on the phenyl ring of sample according to the present invention and unstable or conventional alkyl-substituted phenols and compares, and has better light stability.
Claims (17)
1. hindered amine benzotriazole cpd like general formula I
Wherein, R
1Be H, Cl or Br, R
2Be
N=1 or 2 wherein,
R
3Be H, CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
8H
17, C
12H
25, OCH
3, OC
2H
5, OC
3H
7, OC
4H
9, OC
5H
11, OC
6H
13, OC
8H
17Or OC
12H
25
2. formula I compound as claimed in claim 1, wherein R
1Be H, R
3Be H.
3. formula I compound as claimed in claim 1, wherein R
1Be Cl, R
3Be H.
4. formula I compound as claimed in claim 1, wherein R
1Be H, R
3Be CH
3
5. formula I compound as claimed in claim 1, wherein R
1Be Cl, R
3Be CH
3
6. each the method for formula I compound for preparing according to claim 1～5 comprises the OR 10154 with following general formula
R wherein
1Be H, Cl or Br;
Piperidines alcohol derivate with following general formula
R wherein
3Be H, CH
3, C
2H
5, C
3H
7, C
4H
9, C
5H
11, C
6H
13, C
8H
17, C
12H
25, OCH
3, OC
2H
5, OC
3H
7, OC
4H
9, OC
5H
11, OC
6H
13, OC
8H
17, OC
12H
25And solvent, alkali add in the reactor drum, the reaction 3～8 hours down of 0～100 ℃ of temperature condition; Wherein the add-on of solvent is 0.5～50 times of OR 10154 quality, and the mol ratio of OR 10154 and piperidines alcohol derivate is 1.0～1.2, and the mol ratio of alkali and piperidines alcohol derivate is 0.5～1.5.
7. according to the method for claim 6, said OR 10154 is 2-[2, the 4-dihydroxy phenyl]-2H-benzotriazole, 5-chloro-2-[2, the 4-dihydroxy phenyl]-2H-benzotriazole, or 5-bromo-2-[2, the 4-dihydroxy phenyl]-2H-benzotriazole.
8. according to the method for claim 6, the mol ratio of said OR 10154 and piperidines alcohol derivate is 1.0～1.1.
9. according to the method for claim 6, said solvent is acetone, THF, ETHYLE ACETATE, toluene, YLENE, chlorobenzene or solvent oil.
10. according to the method for claim 9, said solvent is an acetone.
11. according to the method for claim 6, said alkali is KOH, NaOH, Ca (OH)
2, K
2CO
3, Na
2CO
3, MgCO
3, KHCO
3Or NaHCO
3
12. according to the method for claim 9, said alkali is Na
2CO
3Or KHCO
3
13. according to the method for claim 6, the mol ratio of said alkali and piperidines alcohol derivate is 1.0～1.05.
14. according to the method for claim 6, the add-on of said solvent is 3～10 times of OR 10154 quality.
15. according to the method for claim 6, said temperature of reaction is 20～70 ℃.
16. each described formula I compound of claim 1～5 is as the application of photostabilizer.
17. each described formula I compound of claim 1～5 is at Vestolen PP 7052, polycarbonate, polymethyl acrylate, Vilaterm, SE, PS, polyvinyltoluene; Polyethyleneterephthalate, PBT, polymeric amide, polyimide, polyamidoimide, polyetherimide, polyacetal; Polyacrylonitrile, polyethers, polyketone, polysulfones, ppe, resol; Urea-formaldehyde resin, Synolac, urea resin, polymeric polyisocyanate, epoxy acid esters, ZGK 5; The epoxy melamine resin, tree elastomer, viton, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, propenoate-styrene-acrylonitrile copolymer; Cellulose polymer compound, with the crosslinked vinyl resin of melamine resin, cellulose paper preparation, photographic film is used paper, printing ink, in white or the coloured wax as the application of photostabilizer.
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| CN103255501A (en) * | 2013-05-31 | 2013-08-21 | 中国科学院长春应用化学研究所 | Preparation method of polyimide fibers |
| JP2014141487A (en) * | 2012-12-26 | 2014-08-07 | Shipro Kasei Kaisha Ltd | Benzotriazole compound, and cosmetic ultraviolet absorber and skin external preparation using the same |
| CN105452243A (en) * | 2013-07-30 | 2016-03-30 | 科莱恩国际有限公司 | Novel sterically hindered cyclic amines |
| CN105712981A (en) * | 2016-04-15 | 2016-06-29 | 佛山市聚成生化技术研发有限公司 | Hindered-amine light stabilizing agent and synthesizing method thereof |
| CN105801561A (en) * | 2016-04-15 | 2016-07-27 | 佛山市聚成生化技术研发有限公司 | Novel hindered amine light stabilizer and synthesis method thereof |
| CN109964175A (en) * | 2016-11-15 | 2019-07-02 | 东友精细化工有限公司 | Photosensitive polymer combination, colour filter and image display device |
| CN112608516A (en) * | 2020-12-15 | 2021-04-06 | 沈阳化工研究院有限公司 | Multifunctional light-stable composition and preparation method thereof |
| CN113149963A (en) * | 2021-04-19 | 2021-07-23 | 宿迁联盛科技股份有限公司 | Benzotriazole-hindered amine composite light stabilizer and preparation process thereof |
| CN115947719A (en) * | 2022-12-07 | 2023-04-11 | 宿迁市振兴化工有限公司 | Tetramethyl piperidine derivative light stabilizer and preparation method thereof |
| JP7450400B2 (en) | 2019-03-14 | 2024-03-15 | ダイセルミライズ株式会社 | Light-resistant thermoplastic resin composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367792A (en) * | 2008-10-13 | 2009-02-18 | 大连化工研究设计院 | Benzotriazole light stabilizer containing hindered amine group |
-
2011
- 2011-09-13 CN CN201110268902XA patent/CN102432597A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367792A (en) * | 2008-10-13 | 2009-02-18 | 大连化工研究设计院 | Benzotriazole light stabilizer containing hindered amine group |
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| JP2014141487A (en) * | 2012-12-26 | 2014-08-07 | Shipro Kasei Kaisha Ltd | Benzotriazole compound, and cosmetic ultraviolet absorber and skin external preparation using the same |
| CN103255491A (en) * | 2013-05-31 | 2013-08-21 | 中国科学院长春应用化学研究所 | Preparation method of polyimide fibers |
| CN103255501A (en) * | 2013-05-31 | 2013-08-21 | 中国科学院长春应用化学研究所 | Preparation method of polyimide fibers |
| CN103255491B (en) * | 2013-05-31 | 2015-05-20 | 中国科学院长春应用化学研究所 | Preparation method of polyimide fibers |
| CN105452243A (en) * | 2013-07-30 | 2016-03-30 | 科莱恩国际有限公司 | Novel sterically hindered cyclic amines |
| CN105712981A (en) * | 2016-04-15 | 2016-06-29 | 佛山市聚成生化技术研发有限公司 | Hindered-amine light stabilizing agent and synthesizing method thereof |
| CN105801561A (en) * | 2016-04-15 | 2016-07-27 | 佛山市聚成生化技术研发有限公司 | Novel hindered amine light stabilizer and synthesis method thereof |
| CN105712981B (en) * | 2016-04-15 | 2018-06-19 | 双键化工（泰兴）有限公司 | A kind of hindered amine light stabilizer and its synthetic method |
| CN109964175A (en) * | 2016-11-15 | 2019-07-02 | 东友精细化工有限公司 | Photosensitive polymer combination, colour filter and image display device |
| CN109964175B (en) * | 2016-11-15 | 2023-06-20 | 东友精细化工有限公司 | Photosensitive resin composition, color filter and image display device |
| JP7450400B2 (en) | 2019-03-14 | 2024-03-15 | ダイセルミライズ株式会社 | Light-resistant thermoplastic resin composition |
| CN112608516A (en) * | 2020-12-15 | 2021-04-06 | 沈阳化工研究院有限公司 | Multifunctional light-stable composition and preparation method thereof |
| CN112608516B (en) * | 2020-12-15 | 2022-04-08 | 沈阳化工研究院有限公司 | Multifunctional light-stable composition and preparation method thereof |
| CN113149963A (en) * | 2021-04-19 | 2021-07-23 | 宿迁联盛科技股份有限公司 | Benzotriazole-hindered amine composite light stabilizer and preparation process thereof |
| CN113149963B (en) * | 2021-04-19 | 2022-06-03 | 宿迁联盛科技股份有限公司 | Benzotriazole-hindered amine composite light stabilizer and preparation process thereof |
| CN115947719A (en) * | 2022-12-07 | 2023-04-11 | 宿迁市振兴化工有限公司 | Tetramethyl piperidine derivative light stabilizer and preparation method thereof |
| CN115947719B (en) * | 2022-12-07 | 2024-02-20 | 宿迁市振兴化工有限公司 | Tetramethyl piperidine derivative light stabilizer and preparation method thereof |
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