CN1273241A - Hydroxy substituted N-alkoxy hindered amine - Google Patents

Hydroxy substituted N-alkoxy hindered amine Download PDF

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CN1273241A
CN1273241A CN00106515A CN00106515A CN1273241A CN 1273241 A CN1273241 A CN 1273241A CN 00106515 A CN00106515 A CN 00106515A CN 00106515 A CN00106515 A CN 00106515A CN 1273241 A CN1273241 A CN 1273241A
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carbon atom
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acid
methyl
hydrogen
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CN1230424C (en
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J·P·加波
G·A·卡波西
N·N·克利夫
R·E·德特勒夫森
M·P·迪法兹奥
R·拉维钱德兰
P·S·索勒拉
H·C·格拉斯
C·基尔
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BASF Schweiz AG
Ciba SC Holding AG
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Ciba Spezialitaetenchemie Holding AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/94—Oxygen atom, e.g. piperidine N-oxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/92—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with a hetero atom directly attached to the ring nitrogen atom
    • C07D211/98—Nitrogen atom

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Abstract

Hindered amines substituted on the N-atom with an -O-E-OH moiety are particularly effective in stabilizing polyolefin and automotive coating compositions against the deleterious effects of oxidative, thermal and actinic radiation where the presence of the OH group on the compounds adds important properties not attainable by the use of normal -O-E moieties.

Description

The N-alkoxy hindered amine that hydroxyl replaces
The present invention relates on nitrogen-atoms the hindered amine compound that replaces by the N-alkoxyl group that contains 1-3 hydroxyl.These materials are in stabilization of polyolefins TPO particularly, with anti-oxidant, the light and heat radiation is effective especially.These compounds also are effective in the vanish system of acid catalysis and ambient cure stablizing.
People such as S.Nigam are at J.Chem.Soc., Trans.Faraday Soc.1,1976, in 72,2324 and people such as K.-D.Asmus at Int.J.Radiat.Biol., 1976,29, reported 4-hydroxyl-1-oxygen base-2,2 in 211,6,6-tetramethyl piperidine and 4-oxo-1-oxygen base-2,2,6, it is the atomic group at center with carbon that the 6-tetramethyl piperidine can be used for capturing what formed by methyl alcohol, ethanol, Virahol and sec-butyl alcohol.
United States Patent (USP) 5627248 and european patent application 135280A2 have described difunctionality and simple function active free radical polymerization initiator respectively, and some of them contain the amidogen ether that is obstructed that is replaced by hydroxyl.There are the difference of essence in these compounds and compound of the present invention on structure and performance.
European patent application 427672A1 and United States Patent (USP) 4972009 have been mentioned the structure of azanol and nitrone respectively, but not for example, some of them contain C 1-C 42,2,6 of hydroxyl alkoxyl group replacement, 6-tetramethyl piperidine derivative.These structures are not within the scope of the invention.
United States Patent (USP) 5204473 has been described N--oxyl hindered amine derivative, and it is only made by the organic compound of carbon containing and hydrogen atom only.These compounds structurally have very big-difference with compound of the present invention.
United States Patent (USP) 5004770 has been described the hindered amine compound that is replaced by alkoxyl group on nitrogen-atoms, these alkoxyl groups itself do not have substituting group.These compounds are particularly useful in the polymkeric substance that comprises polyhutadiene, polystyrene, ABS, polyacetal, polymeric amide, polyester, polyurethane(s) and polycarbonate.
United States Patent (USP) 5096950 has also been described on nitrogen-atoms by the hindered amine compound that itself does not have substituent alkoxyl group to replace.These compounds have been found in the polyolefine useful.
Compound of the present invention is 2,2,6 of the replacement of N-alkoxyl group, 6-tetramethyl piperidine derivative, and this alkoxyl group is replaced by 1-3 hydroxyl.Compound of the present invention also comprise by two hindered amine molecules share 2,2,6, the N-alkoxyl group bridge derivative of 6-tetramethyl piperidine, wherein alkoxyl group is replaced by 1-3 hydroxyl.Free hydroxyl in these compounds can form simple ester or polyester with carboxylic acid, chloride of acid or ester reaction, perhaps forms urethane or polyurethane with isocyanate reaction.
Their basicity is low because compound of the present invention is shared by the simple unsubstituted N-alkoxy compound of being quoted as proof in above-mentioned two patents, therefore compound of the present invention is effective especially in stabilization of polyolefins and car paint composition, wherein owing to maybe need to solidify the acid catalysis system interaction of these matrix with polymeric matrix, the activity of the hindered amine stabilizer that basicity is bigger will reduce greatly.
The example of The compounds of this invention efficient polyolefin composition comprises the fire retardant polyolefine, wherein the acidic residues of being decomposed by halogenated fire-retardants makes and does not have the hindered amine of N-OR group inactivation, disturb the activity of " normally " hindered amine stabilizer in the grow seedlings acidic residues in the sterilant in the film of greenhouse films and agricultural, and the interaction of pigment and alkaline hindered amine stabilizer has been disturbed to stromal surface and has been painted in TPO.The example of the effective coating composition of The compounds of this invention comprises melamine cross-linked thermal set acrylic resin, and it uses the strong acid curing with alkaline hindered amine stabilizer reaction.The compounds of this invention is in vinylformic acid Synolac that has isocyanate crosslinking or vibrin and to have in the Resins, epoxy of carboxylic acid, acid anhydrides or amine crosslinker also be effective.
Therefore, The compounds of this invention is useful to be used for containing equally steady altogether agent, fire retardant (three (3-bromo-2 for example, two (brooethyl) propyl group of 2-) phosphoric acid ester, decabromodiphynly oxide, ethylenebis-(tetrabromo phthalimide) or ethylenebis-(dibromo norborneol connection carboxylic imide)), in the composition of catalyzer (for example :), weighting agent, perhaps in sterilant and the agricultural application that stabilization of polymer contacts as acid, metal drier or the amine of toluenesulphonic acids.Preferably, the component in the composition (a) is polypropylene, polyethylene, TPO (TPO), ABS or anti-high impact polystyrene (HIPS), and component (b) is following effectively collaborative mixture:
(i) compound of formula (1)-(30);
(ii) a fire retardant is selected from halo, phosphorus, boron, silicon and antimony compounds, metal hydroxides, metal hydrate, metal oxide and its mixture.
Although the N-OR compound of describing in United States Patent (USP) 5004770 and 5096950 that is unsubstituted shows in the described composition of epimere well, yet compound of the present invention is that at the maximum difference of structure and aspect of performance and previous technical compound 1-3 free hydroxyl arranged on the N-alkoxyl group.In compound of the present invention these hydroxyls give described compound provide the excellent antistatic energy, as be the multipole environment of base-material and the compatibility good and stable tide of motorism plasticity alkene structures of painting in the water-borne car paint system with the polyurethane.
The compounds of this invention is suitable especially:
(a) compare with the N-OE compound of previous technology, the good compatibility in polycarbonate and polycarbonate/ABS blend is provided; With
(b) compare with the N-OE compound of previous technology, compatibility good in polyester and polymeric amide is provided.
The present invention has two purposes:
1, have the novel cpd of one-O-E-OH on the 1-position of hindered amine, wherein hydroxyl plays an important role;
2, by above-mentioned novel cpd stable composition; With
3, the method for synthetic this novel cpd.
The present invention relates to have the novel cpd of the hindered amine derivative that the 1-alkoxyl group replaces, described suc as formula (1)-(15), wherein alkoxyl group is replaced by 1-3 hydroxyl; Perhaps the present invention relates to have the novel cpd of 1-alkoxyl group bridge hindered amine derivative, wherein the alkoxyl group part that is replaced by 1-3 hydroxyl is shared by two hindered amine molecules, and is described suc as formula (16)-(28); Perhaps the present invention relates to by dialkyl or isocyanic ester and 4-hydroxyl-2,2,6, the N-alkoxy derivative reaction that the hydroxyl of 6-tetraalkyl piperidines replaces makes oligomeric or polymerization hindered amine molecule, and is described suc as formula (29); Perhaps the present invention relates to 4-hydroxyl-2,2,6, the simple diester or the urethane derivatives of the N-alkoxy derivative that the hydroxyl of 6-tetramethyl piperidine replaces, described suc as formula (30)
Figure A0010651500261
Figure A0010651500271
Figure A0010651500291
Figure A0010651500301
Figure A0010651500321
Figure A0010651500341
Figure A0010651500351
G 1And G 2Be respectively the alkyl of 1-4 carbon atom, perhaps G 1And G 2Be pentamethylene together; Preferred G 1And G 2It all is methyl;
E is the ring alkylidene group, 5-18 carboatomic ring thiazolinyl of straight or branched alkylidene group, the 5-18 carbon atom of 1-18 carbon atom, by phenyl or the 1-4 carbon atom straight chain or the branched alkylidene that replace by the phenyl that the alkyl of 1 or 2 1-4 carbon atom replaces;
B is 1,2 or 3, as long as b is no more than the carbonatoms among E or the L, when b was 2 or 3, each hydroxyl was connected on the different carbon atoms of E or L; Two hindered amine groups are common, but not always, are connected on two different carbon atoms of L;
In formula (1)-(15):
M is 0 or 1;
R 1Be hydrogen atom, hydroxyl or methylol;
R 2Be the alkyl of hydrogen atom, 1-12 carbon atom or the thiazolinyl of 2-12 carbon atom;
N is 1-4;
When n is 1,
R 3Alkyl, the carbalkoxy alkylene carbonyl of 4-18 carbon atom, 2-18 carbon atom thiazolinyl, glycidyl, 2 for the 1-18 carbon atom, the 3-12 carbon atom alkyl that 3-dihydroxypropyl, 2-hydroxyl or 2-(methylol) replace, wherein alkyl is interrupted by Sauerstoffatom, contains the acyl group of the aliphatics of 2-18 carbon atom or unsaturated aliphatic carboxylic acid or carbamic acyl group, the cycloaliphatic carboxylic acid that contains the 7-12 carbon atom or aminocarboxylic acid or contains the acyl group of 7-15 carbon atom fragrance carboxylic acid;
When n is 2,
R 3For the divalence acyl group of the divalence acyl group of the alkylidene group of 2-18 carbon atom, the aliphatics that contains the 2-18 carbon atom or unsaturated aliphatic dicarboxylic acid or diamino acid, the cycloaliphatic dicarboxylic acid that contains the 7-12 carbon atom or diamino acid or contain the divalence acyl group of 8-15 carbon atom fragrance dicarboxylic acid;
When n is 3,
R 3For containing the trivalent acyl group of 6-18 carbon atom aliphatic series, unsaturated aliphatic or cycloaliphatic tricarboxylic acid or triamino formic acid, perhaps contain the trivalent acyl group of 9-18 carbon atom fragrance tricarboxylic acid or triamino formic acid, perhaps R 3Be the trivalent acyl group of three (alkylamino formic acid) derivative of containing 12-24 carbon atom cyanuric acid, for example 1,3,5-three [the amino hexyl of 6-carboxylic]-2,4,6-trioxy-S-triazine;
When n is 4, R 3Be aliphatic series or unsaturated aliphatic tetracarboxylic acid, especially 1,2,3,4-BTCA, 1,2,3,4-fourth (but)-2-ene tetracarboxylic acid (enetetracarboxylic acid), 1,2,3,5-pentane tetracarboxylic acid and 1,2,4, the tetravalence acyl group of 5-pentane tetracarboxylic acid; Or R 3Be the tetravalence acyl group that contains the fragrant four carboxylic acid of 10-18 carbon atom,
P is 1-3,
R 4Be the alkyl of hydrogen atom, 1-18 carbon atom or the acyl group of 2-6 carbon atom;
When p is 1,
R 5For the alkyl of hydrogen atom, 1-18 carbon atom, the aliphatics that contains the 2-18 carbon atom or unsaturated aliphatic carboxylic acid or carbamic acyl group, the cycloaliphatic carboxylic acid that contains the 7-12 carbon atom or amino acyl group with acid, contain the acyl group or the R of the fragrant carboxylic acid of 7-15 carbon atom 4And R 5All be-(CH 2) 5The divalence acyl group of CO-, phthaloyl or maleic acid;
When p is 2,
R 5For the divalence acyl group of the divalence acyl group of the alkylidene group of 2-12 carbon atom, the aliphatics that contains the 2-18 carbon atom or unsaturated aliphatic dicarboxylic acid or diamino acid, the cycloaliphatic dicarboxylic acid that contains the 7-12 carbon atom or diamino acid or contain the divalence acyl group of 8-15 carbon atom fragrance dicarboxylic acid;
When p is 3,
R 5For the aliphatics or the tricarboxylic trivalent acyl group of unsaturated aliphatic that contain the 6-18 carbon atom or contain the tricarboxylic trivalent acyl group of 9-15 carbon atom fragrance;
When n is 1,
R 6For the alkenyloxy of the alkoxyl group of 1-18 carbon atom, 2-18 carbon atom, 1-18 carbon atom-NH alkyl or 2-36 carbon atom-N (alkyl) 2
When n is 2,
R 6For the alkene dioxy base of the alkylene dioxo base of 2-18 carbon atom, 2-18 carbon atom, 2-18 carbon atom-NH-alkylene-NH-, perhaps 2-18 carbon atom-N (alkyl)-alkylene-N (alkyl), or R 6Be the 4-methyl isophthalic acid, the inferior phenyl diamino of 3-;
When n is 3,
R 6For containing the trivalent alkoxyl group of the saturated of 3-18 carbon atom or unsaturated aliphatic triol;
When n is 4,
R 6For containing the tetravalence alkoxyl group of the saturated of 4-18 carbon atom or unsaturated aliphatic tetrol;
R 7And R 8Be respectively chlorine, 1-18 carbon atom alkoxyl group ,-O-T 1, the amino, the 1-18 carbon atom that are replaced by the 2-hydroxyethyl-NH (alkyl), have the 1-18 carbon atom alkyl-N (alkyl) T 1, or the 2-36 carbon atom-N (alkyl) 2,
R 9Be bivalent oxygen atom or R 9For by the alkyl or the T of hydrogen atom, 1-12 carbon atom 1The bivalent atom that replaces;
Figure A0010651500371
R 10Be hydrogen atom or methyl,
Q is 2-8, R 11And R 12Be respectively hydrogen atom or group T 2,
Figure A0010651500372
R 13Be hydrogen atom, phenyl, the straight or branched alkyl of 1-12 carbon atom, the alkoxyl group of 1-12 carbon atom, the straight or branched alkyl of the 1-4 carbon atom that is replaced by phenyl, the cycloalkyl of 5-8 carbon atom, the cycloalkenyl group of 5-8 carbon atom, the thiazolinyl of 2-12 carbon atom, glycidyl, allyloxy, the straight or branched hydroxyalkyl of 1-4 carbon atom, or respectively by hydrogen atom, phenyl, the alkoxyl group of the alkyl of 1-4 carbon atom or 1-4 carbon atom replaces three times silyl or siloxy-;
R 14For hydrogen atom or replaced three times silyl respectively by the alkoxyl group of hydrogen atom, phenyl, 1-4 carbon atom alkyl or 1-4 carbon atom;
D is 0 or 1;
H is 0-4;
K is 0-5;
X is 3-6;
Y is 1-10;
Z is that to make the molecular weight of compound be 1000-4000g/mol (=atomic unit, integer amu);
R 15For example uncle is hot amino, alkyl with 1-8 carbon atom-N (alkyl) T for the branched alkylamino of alkylamino, particularly the 3-8 carbon atom of morpholinyl, piperidino-(1-position only), piperidino (piperizinyl), 1-8 carbon atom 1, or the 2-16 carbon atom-N (alkyl) 2
R 16For the acyl group of hydrogen atom, 2-4 carbon atom, by the formamyl of the alkyl of 1-4 carbon atom replacement, by the chlorine atom with by R 15Replace once the S-triazinyl or by R 15Replace twice S-triazinyl, two R 15Can be different.
R 17Atom, by the alkyl of 1-8 carbon atom or T 1The amino that replaces, have the 1-8 carbon atom alkyl-N (alkyl) T 1, the 2-16 carbon atom-N (alkyl) 2Or group T 3:
R 18The formamyl that replaces for the acyl group of hydrogen atom, 2-4 carbon atom, by the alkyl of 1-4 carbon atom, by the 2-16 carbon atom-N (alkyl) 2Replace twice the S-triazinyl or with the alkyl with 1-8 carbon atom-N (alkyl) T 1Replace twice S-triazinyl;
L is the alkenyl of cycloalkenyl group, the 3-18 carbon atom of ring alkylidene group, the 5-8 carbon atom of straight or branched alkenyl, the 5-8 carbon atom of 1-18 carbon atom, the straight or branched alkylidene group of the 1-4 carbon atom that phenyl replaced that replaces by phenyl or by the alkyl of one or two 1-4 carbon atom;
In formula (16)-(28),, R 1, R 2, R 7, R 8, R 9, R 10, R 13, R 14, d, h, k, m, q and T 1Identical with in formula (1)-(15);
R 19Alkyl, the thiazolinyl of 2-18 carbon atom, glycidyl, 2 for hydrogen atom, 1-18 carbon atom, the alkyl of 3-dihydroxypropyl, the 3-12 carbon atom that replaces through 2-hydroxyl or 2-(methylol), wherein alkyl is interrupted by Sauerstoffatom, contains aliphatic series or unsaturated aliphatic carboxylic acid or carbamic acyl group, the cycloaliphatic carboxylic acid who contains the 7-12 carbon atom or the carbamic acyl group of 2-18 carbon atom or contains the sour acyl group of 7-15 carbon atom fragrance;
R 20For the divalence acyl group of the divalence acyl group of the alkylidene group of 2-18 carbon atom, the aliphatic series that contains the 2-18 carbon atom or unsaturated aliphatic dicarboxylic acid or diamino acid, the cycloaliphatic dicarboxylic acid who contains the 7-12 carbon atom or diamino acid or contain the divalence acyl group of the aromatic dicarboxilic acid of 8-15 carbon atom;
R 21Be the alkyl of hydrogen atom, 1-18 carbon atom or the acyl group of 2-6 carbon atom;
R 22For the alkyl of hydrogen atom, 1-18 carbon atom, the aliphatic series that contains the 2-18 carbon atom or unsaturated aliphatic carboxylic acid or carbamic acyl group, the cycloaliphatic carboxylic acid who contains the 7-12 carbon atom or carbamic acyl group, contain the acyl group or the R of the aromatic carboxylic acid of 7-15 carbon atom 4And R 5Be together-(CH 2) 5The divalence acyl group of CO-, phthaloyl or maleic acid;
R 23Be the alkyl of hydrogen atom, 1-4 carbon atom or the acyl group of 2-6 carbon atom;
R 24For the divalence acyl group of the divalence acyl group of the alkylidene group of 2-18 carbon atom, the aliphatic series that contains the 2-18 carbon atom or unsaturated aliphatic dicarboxylic acid or diamino acid, the cycloaliphatic dicarboxylic acid who contains the 7-12 carbon atom or diamino acid or contain the divalence acyl group of the aromatic dicarboxilic acid of 8-15 carbon atom;
R 25For the alkenyloxy of the alkoxyl group of 1-18 carbon atom, 2-18 carbon atom, 1-18 carbon atom-NH alkyl or 2-36 carbon atom-N (alkyl) 2
R 26For the NH-alkylene-NH-of the alkene dioxy base of the alkylene dioxo base of 2-18 carbon atom, 2-18 carbon atom, 2-18 carbon atom or 3-18 carbon atom-N (alkyl)-alkylene-N (alkyl)-,
In formula (29) and (30), G for from primary, the second month in a season or tertiary alcohol G-OH deutero-be the biradical at center with the carbon atom, wherein
Z is with defined above identical, and
G is the alkenyl of cycloalkenyl group, the 3-18 carbon atom of ring alkylidene group, the 5-8 carbon atom of straight or branched alkylidene group, the 5-8 carbon atom of 1-18 carbon atom, by phenyl or the straight or branched 1-4 carbon atom alkylidene group that phenyl replaced that replaced by the alkyl of one or two 1-4 carbon atom, in the solemnity (29) successive hindered amine molecule can be head to head or head to the mode orientation of tail;
T 4For hydrogen atom or
T 4Be
Figure A0010651500401
R 27For ring alkylidene group or cycloalkenyl group, the phenylene of the straight or branched alkylidene group of 1-18 carbon atom, 5-8 carbon atom or comprise 5-amino-1-aminomethyl-1,3, the 3-trimethyl-cyclohexane and-the 2-18 carbon atom of NH-xylylene-NH--NH-alkylidene group-NH-;
R 28For the alkyl of 1-4 carbon atom,
Figure A0010651500402
R 29For straight or branched alkyl or 1-18 carbon atom-NH-alkyl or 5-8 carbon atom-the NH-cycloalkyl; With
As long as in formula (1) and (2), when b was 1, E was not methyl, ethyl, 2-propyl group or 2-methyl-2-propyl group.
Preferably, G 1And G 2It all is methyl.
Preferably, in formula (1)-(28), b is 1 or 2, more preferably 1.
Particularly importantly in the compound of formula (1) and (2) when b is 1, E is methylene radical, ethylidene, 2-propylidene or 2-methyl-2-propylidene.
When b is 1, it is the radical or the biradical at center that E-OH and L-OH are respectively with the carbon atom, preferably by 2-methyl-2-propyl alcohol, 2-propyl alcohol, 2,2-dimethyl-1-propyl alcohol, 2-methyl-2-butanols, ethanol, 1-propyl alcohol, 1-butanols, 1-amylalcohol, 1-hexanol, 1 nonyl alcohol, 1-decanol, 1-dodecanol, 1-Stearyl alcohol, 2-butanols, 2-amylalcohol, 2-ethyl-1-hexanol, hexalin, ring octanol, vinylcarbinol, phenylethyl alcohol or 1-phenyl-1-ethanol forms; More preferably E-OH and L-OH are formed by 2-methyl-2-propyl alcohol or hexalin.
When b was 2, it was the radical or the biradical at center that E-OH and L-OH are respectively with the carbon atom, preferably by 1,2-ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2,2-dimethyl-1, ammediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1, the 4-cyclohexanediol forms; More preferably E-OH and L-OH be by 1,4-butyleneglycol, 2,1, and 2-cyclohexanediol, 1,3-cyclohexanediol or 1, the 4-cyclohexanediol forms.
When b was 3, E-OH and L-OH were respectively by glycerine, 1,1, and 1-three (methylol) methane, 2-ethyl-2-(methylol-1, ammediol, 1,2,4-trihydroxybutane or 1,2, what the 6-hexanetriol formed is the radical or the biradical at center with carbon; More preferably E-OH and L-OH are by glycerine, 1,1, and (methylol-1, ammediol forms for 1-three (methylol) methane, 2-ethyl-2-.
In formula (29) and (30) ,-G-O-preferably is made of ethanol, phenylethyl alcohol, hexalin or 2-methyl-2-propyl alcohol (=trimethyl carbinol).
In formula (3), preferably, m is 0, R 1Be hydrogen atom or methylol, R 2Be hydrogen atom; Perhaps m is 1, R 1Be hydroxyl or methylol, R 2Be hydrogen atom, methyl or ethyl;
Preferred R in formula (5) 2Be hydrogen atom or dodecyl.
Preferably, in formula (6), n is 1-3, and when n is 1, R 3Be allyl group, glycidyl, acryl, methacryloyl, octadecanoyl, hexadecanoyl, tetradecanoyl, methoxyl group phosphinylidyne propionyl, methoxyl group phosphinylidyne butyryl radicals, methoxyl group phosphinylidyne pentanoyl or methoxyl group phosphinylidyne nonanoyl; Perhaps when n is 2, R 3Be succinyl, glutaryl-, adipyl, sebacoyl, 1, the own diamino formyl radical of 6-, anti-or suitable-5-formamyl-1-(carbamyl methyl)-1,3,3-trimethyl-cyclohexane or Toluene-2,4-diisocyanate, 4-diamino formyl radical; Perhaps when n is 3, R 3Be 1,3,5-three (6-formamyl hexyl)-2,4,6-trioxy--S-triazinyl.
In formula (7), preferred p is 1 or 2, when p is 1, and R 4Be hydrogen atom and R 5Be butyl; Perhaps R 4And R 5It all is the divalence free acyl radical of toxilic acid; Perhaps when p is 2, R 4Be hydrogen atom or ethanoyl and R 5Be 1, the 6-dihexyl.
In formula (8), preferred n is 1 or 2, and when n is 1, R 6For oxyethyl group, 6-methyl isophthalic acid-heptan oxygen base, ethylamino, fourth is amino or hot amino; Perhaps when n is 2, R 6Be 1,2-ethylenedioxy, 1,4-fourth dioxy base, second diamino, own first diamino or 4-methyl isophthalic acid, 3-phenyl diamino.
In formula (9), preferred R 7And R 8Be respectively chlorine atom, hot amino, the hot amino of uncle or by T 1Amino with ethyl, butyl or dodecyl replacement; And R 9Be the divalence nitrogen-atoms that is replaced by ethyl, butyl or dodecyl.
In formula (10), preferred q is 2,4 or 6, R 7For the chlorine atom, hot amino, octadecane is amino or by T 1Amino with ethyl, butyl or dodecyl replacement; And R 10Be hydrogen atom.
In formula (11), preferred n is 3, and p is 2, R 2Be ethyl, butyl or dodecyl; And R 11And R 12One of be T 2, another is a hydrogen atom.
In formula (12), preferred k is 3, R 9For bivalent oxygen atom or by the divalence nitrogen-atoms of ethyl, butyl or dodecyl replacement, R 13Be hydrogen atom or methyl, when d was 0, x was 5 or 6, and when d was 1, x was 3 or 4.
In formula (13), preferred d is 0 or 1, and h is 0-2, and k is 0 or 3, and y is 1-8, R 9For bivalent oxygen atom or by the divalence nitrogen-atoms of ethyl, butyl or dodecyl replacement, R 13Be hydrogen atom, methyl, ethyl, methoxy or ethoxy, and R 14Be hydrogen atom or trimethyl silyl.
In formula (14), preferred R 9Be bivalent oxygen atom, R 10Be hydrogen atom or methyl, m is 0, and z is that to make the molecular weight of compound be the integer of 1500-3000amu.
In formula (15), preferred q is 6, and y is 1-7, R 15For the hot amino of uncle, morpholinyl, by T 1With the amino that butyl replaces, it also can be designated as T 1-butyl amino, R 16Be hydrogen atom, ethanoyl, ethylamino formyl radical, 2, two (the dibutylamino)-S-triazinyls, 2 of 4-, two (diethylin)-S-triazinyls of 4-, by T 1-butyl is amino to be replaced twice S-triazinyl or is replaced once and by T by diethylin or dibutylamino 1Amino S-triazinyl, the R that replaces once of-butyl 17Be dibutylamino, diethylin, T 1-butyl amino or R 17Be T 3, R wherein 18Be ethanoyl or ethylamino formyl radical.
In formula (17), preferred m is 0, R 1Be hydrogen atom or methylol, R 2Be hydrogen atom, perhaps m is 1, R 1Be hydroxyl or methylol, and R 2Be hydrogen atom or methyl.
In formula (19), preferred R 2Be hydrogen atom or dodecyl.
In formula (20), preferred R 19Be hydrogen atom, allyl group, acryl, methacryloyl, octadecanoyl or hexadecanoyl.
In formula (21), preferred R 20Being succinyl, glutaryl-, adipyl, sebacoyl, 1, the own diamino formyl radical of 6-is anti-or suitable-5-formamyl-1-(carbamoyl methyl)-1,3, the 3-trimethyl-cyclohexane.
In formula (22), preferred R 21Be hydrogen atom, R 22Be hydrogen atom or butyl; Perhaps R 21And R 22It all is the biradical of toxilic acid.
In formula (23), preferred R 23Be hydrogen atom or ethanoyl, R 24Be ethylidene or cyclohexyl.
In formula (24), preferred R 25For oxyethyl group, 6-methyl isophthalic acid-heptan oxygen base, ethylamino, fourth is amino or hot amino.
In formula (25), preferred R 26Be 1,2-ethylenedioxy, 1,4-fourth dioxy base, second diamino or cyclohexyl diamino.
In formula (26), preferred R 7And R 8Be respectively chlorine atom, hot amino, the hot amino of uncle, octadecane amino, T 1-ethylamino, T 1-Ding amino or T 1-dodecane amino, and R 9Be the divalence nitrogen-atoms that is replaced by ethyl, butyl or dodecyl.
In formula (27), preferred q is 2,4 or 6, R 7Be chlorine atom, hot amino, amino, the T of octadecane 1-ethylamino, T 1-Ding amino or T 1-dodecane amino and R 10Be hydrogen atom.
In formula (28), preferred d is 0 or 1, and h is 0-2, and k is 0 or 3, R 9For bivalent oxygen atom or by the divalence nitrogen-atoms of ethyl, butyl or dodecyl replacement, R 13Be hydrogen atom, methyl, ethyl, methoxy or ethoxy, and R 14Be hydrogen atom or trimethyl silyl.
In formula (29), preferred R 27Be ethylidene, cyclopropane, butylidene, octamethylene, 1 or 5-amino-1-aminomethyl-1,2,3,3-trimethyl-cyclohexane; Z is that to make the molecular weight of compound be the integer of 1500-3000amu, R 28Be methyl or ethyl, and G is ethylidene, 1,2-encircles dihexyl, 1, and 3-encircles dihexyl, 1,4-ring dihexyl ,-CH (C 6H 5) CH 2-or-CH 2C (CH 3) 2-.
In formula (30), preferred R 29Be pentadecyl, heptadecyl, fourth amino or hexamethylene amino.
Preferred embodiment of the present invention is the compound of formula (1)-(30), and wherein E-OH, L-OH and G-O-are formed by 2-methyl-2-the propyl alcohol (=trimethyl carbinol) or hexalin.
In formula (6), most preferably when n is 1, R 3Be acryl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxyl group phosphinylidyne propionyl, methoxyl group phosphinylidyne butyryl radicals, methoxyl group phosphinylidyne pentanoyl or methoxyl group phosphinylidyne nonanoyl; Perhaps when n is 2, R 3Be succinyl, glutaryl-, adipyl, sebacoyl, 1, the own diamino formyl radical of 6-, anti-or suitable-5-formamyl-1-(carbamoyl methyl)-1,3,3-trimethyl-cyclohexane or Toluene-2,4-diisocyanate, 4-diamino formyl radical; Perhaps when n is 3, R 3Be 1,3,5-three (6-formamyl hexyl)-2,4,6-trioxy--S-triazine.
In formula (7), most preferably p is 1 or 2, when p is 1, and R 4Be hydrogen atom and R 5Be hydrogen atom or butyl; Perhaps when p is 2, R 4Be hydrogen atom and R 5Be 1, the 6-dihexyl.
In formula (9), R most preferably 7Be chlorine atom, hot amino or T 1-Ding amino; R 8Be chlorine atom or T 1-Ding amino: and R 9Be the divalence nitrogen-atoms that is replaced by butyl.
In formula (10), most preferably q is 6, R 7Be T 1-Ding amino; And R 10Be hydrogen atom.
In formula (11), most preferably n is 3, and p is 2, and R 11And R 12One of be T 2, another is a hydrogen atom.
In formula (12), most preferably k is 3, R 9Be bivalent oxygen atom, R 13Be hydrogen atom or methyl, and d is 0, x is 5 or 6, and when d was 1, x was 3 or 4.
In formula (13), most preferably d is 0 or 1, and h is 0-2, and k is 0 or 3, and y is 1-8, R 9Be bivalent oxygen atom, R 13Be hydrogen atom, methyl, ethyl, methoxy or ethoxy, and R 14Be hydrogen atom or trimethyl silyl.
In formula (15), most preferably q is 6, and y is 1-7, R 15Be T 1-Ding amino, R 16Be hydrogen atom, ethanoyl, ethylamino formyl radical, 2, two (the dibutylamino)-S-triazinyls, 2 of 4-, two (diethylin)-S-triazinyls of 4-, by T 1-Ding is amino to be replaced twice S-triazinyl or is replaced once and by T by diethylin or dibutylamino 1Amino S-triazinyl, the R that replaces once of-Ding 17Be dibutylamino, diethylin, T 1-Ding amino or R 17Be T 3, R wherein 18Be ethanoyl or ethylamino formyl radical.
In formula (20), R most preferably 19Be hydrogen atom, octadecanoyl or hexadecanoyl.
In formula (22), R most preferably 21Be hydrogen atom, R 22Be hydrogen atom or butyl.
In formula (23), R most preferably 23Be hydrogen atom, R 24Be cyclohexyl.
In formula (26), R most preferably 7Be chlorine atom, hot amino or T 1-Ding amino, R 8Be chlorine atom or T 1-Ding amino, and R 9Be the divalence nitrogen-atoms that is replaced by butyl.
In formula (27), most preferably q is 6, R 7Be T 1-Ding amino, and R 9Be the divalence nitrogen-atoms that is replaced by butyl.
In formula (29), R most preferably 27Be ethylidene, propylidene, butylidene or octylene; Z is that to make the molecular weight of compound be the integer of 1500-2000amu, R 28Be methyl.
In formula (30), R most preferably 29Be pentadecyl or heptadecyl.
Preferred embodiment of the present invention is the compound of formula (1)-(30), and wherein E-OH, L-OH and G-O-are formed by 2-methyl-2-propyl alcohol (=trimethyl carbinol).
The particularly preferred compound of formula (6) is that n is 1, R 3Be those of acryl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxyl group phosphinylidyne propionyl or methoxyl group phosphinylidyne butyryl radicals or methoxycarbonyl pentanoyl; N is 2, R 3Be those of succinyl, glutaryl-, adipyl or sebacoyl.
The particularly preferred compound of formula (7) is R 4Be those of hydrogen atom, and when p is 1, R 4Be hydrogen atom or butyl; Perhaps when p is 2, R 5Be cyclohexyl.
The particularly preferred compound of formula (9) is R 7Be chlorine atom, hot amino or T 1-Ding amino; R 8Be T 1-Ding amino; And R 9Be those of the divalence nitrogen-atoms that replaced by butyl.
The particularly preferred compound of formula (10) is that q is 6, R 7Be T 1-Ding amino; And R 10Be those of hydrogen atom.
The particularly preferred compound of formula (11) is that n is 3, and p is 2, and R 11And R 12One of be T 2, another is hydrogen atom those.
The particularly preferred compound of formula (12) is that d is 1, and k is 3, and x is 3 or 4, R 9Be bivalent oxygen atom, R 13Be those of methyl.
The particularly preferred compound of formula (13) is that k is 3, and y is 4-8, R 9Be bivalent oxygen atom, R 13Be hydrogen atom or methyl, d and h are 0, R 14Be hydrogen atom, or d be 1 and h be 0, R 14Be those of trimethyl silyl.
The particularly preferred compound of formula (14) is that m is 0, R 9Be bivalent oxygen atom, R 10Be hydrogen atom or methyl, z is that to make the molecular weight of compound be those of integer of 1500-3000amu.
The particularly preferred compound of formula (15) is that q is 6, and y is 1-7, R 15Be T 1-Ding amino, R 16Be hydrogen atom, ethanoyl, ethylamino formyl radical, 2, two (the dibutylamino)-S-triazinyls, 2 of 4-, two (diethylin)-S-triazinyls of 4-, by T 1-Ding is amino to be replaced twice S-triazinyl or is replaced once and by T by diethylin or dibutylamino 1Amino S-triazinyl, the R that replaces once of-Ding 17Be dibutylamino, diethylin or T 3, R wherein 18Be those of ethanoyl or ethylamino formyl radical.
The particularly preferred compound of formula (20) is R 19Be those of hydrogen atom, octadecanoyl or hexadecanoyl.
The particularly preferred compound of formula (21) is R 20Be those of succinyl, glutaryl-, adipyl or sebacoyl.
The particularly preferred compound of formula (30) is R 29For heptadecyl,
The present invention also relates to a kind of polymer composition or a kind of recording materials (a), the compound of (b) described formula (1) above one or more that contain effective stable quantity are selected from-(30) compound, comprise the middle b in formula (1) and (2) be 1 and E be the compound of methyl, ethyl, 2-propyl group or 2-methyl-2-propyl group.Usually, based on component (a), effective stable quantity of compound of the present invention is the 0.01-10%, particularly 0.05-5wt% of the stablizer of component (b).
Preferably, treat that stable organic materials is natural semi-synthetic or synthetic polymer or color photographic materials, particularly thermoplastic polymer or coating composition.
More preferably, this polymkeric substance is a polyolefine, is the car paint of base-material especially for the TPO of car paint and purposes or with the urethane.
Good anti-extraction performance when compound of the present invention has good stability to hydrolysis, operation and storage stability and appears in the stable composition.
Usually, can comprise by stable organic materials:
1. the polymkeric substance of monoolefine and diolefine, polypropylene for example, polyisobutene, poly-but-1-ene, poly--4-methylpent-1-alkene, polyisoprene or polyhutadiene, and cycloolefin for example cyclopentenes or norbornylene, the polymkeric substance of polyethylene (optionally can through crosslinked), for example high density polyethylene(HDPE) (HDPE), high-density and High molecular weight polyethylene (HDPE-HMW), the polyethylene of high-density and ultra-high molecular weight (HDPE-UHMW), medium-density polyethylene (MDPE), new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefine, monoolefine preferably polyethylene of promptly giving an example in hypomere and polyacrylic polymkeric substance can pass through different methods, and particularly Xia Mian method makes:
A) radical polymerization (under high temperature and high pressure, carrying out usually).
B) catalyzed polymerization, catalyst system therefor contain the metal of IVb, Vb, VIb or the VIII family of one or more periodictables usually.These metals have one or more parts usually, and typical oxide compound, halogenide, alcoholate, ester, ether, amine, alkide, chain alkylene thing and/or aromatize thing can be π-or σ-coordinations.These metal complexs can be free form, also can be fixed on the substrate, typically at active magnesium chloride, titanium chloride (III), aluminum oxide or silicon-dioxide.These catalyzer can be dissolved in also and can not be dissolved in the polymerisation medium.This catalyzer self can be used for polymerization or can use other activators, metal alkide, metal hydride, metal alkyl halogen, metal alkyl oxygen or metal alkyl oxyethane typically, described metal is the element of periodictable Ia, IIa and/or IIIa family.This activator can be easily with other esters, ether, amine or the modification of silicomethane ether group.These catalyst systems are commonly called Phillips, (Natta), catalyzer (SSC) is put by TNZ (DuPont), metallocenes or unit for Standard Oil Indiana, Ziegler.
2. following 1) described mixture of polymers, for example mixture of polypropylene and polyisobutene, polypropylene and polyethylene (for example PP/HDPE, PP/LDPE) mixture and dissimilar polyethylene (for example LDPE/HDPE).
Monoolefine and diolefine each other or with the multipolymer of other vinyl monomers, for example ethylene/propene copolymer, the mixture of linear low density polyethylene (LLDPE) and itself and new LDPE (film grade) (LDPE), propylene/but-1-ene multipolymer, propylene/isobutylene copolymers, ethene/but-1-ene multipolymer, the ethylene/hexene multipolymer, ethene/methylpentene multipolymer, ethene/heptene multipolymer, ethylene/octene, propylene/butadienecopolymer, iso-butylene/isoprene copolymer, the ethylene/acrylic acid alkyl ester copolymer, the ethylene/methacrylic acid alkyl ester copolymer, the multipolymer of ethylene/vinyl acetate copolymer and they and carbon monoxide or ethylene/acrylic acid copolymer and their salt (ionomer polymers) and ethene and propylene and for example hexadiene, the terpolymer of the diene of Dicyclopentadiene (DCPD) or second diene-norbornylene; With these multipolymers each other and with top 1) described mixture of polymers, for example polypropylene/ethylene-propylene copolymer, LDPE/ ethylene-vinyl acetate copolymer (EVA), LDPE/ ethylene-acrylic acid copolymer (EAA), LLDPE/EVA, LLDPE/EAA and selection or the mixture of polyalkenes/carbon monoxide multipolymer and itself and other polymkeric substance such as polymeric amide at random.
4. hydrocarbon resin (C for example 5-C 9), comprise that its hydrogenation modifier is (for example: tackifier) and the mixture of polyalkenes and starch.
5. polystyrene, poly-(p-methylstyrene), poly-(alpha-methyl styrene).
6. the multipolymer of vinylbenzene or alpha-methyl styrene and diene or acrylic acid derivative, for example phenylethylene/butadiene, styrene/acrylonitrile, styrene/methacrylic acid alkane ester, phenylethylene/butadiene/alkyl acrylate, phenylethylene/butadiene/alkyl methacrylate, phenylethylene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; The mixture of anti-high impact strength of styrene multipolymer and another polymkeric substance such as polyacrylic ester, diene polymer or ethylene/propylene/diene terpolymers; With the segmented copolymer of benzene styrene, for example styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.
7. the graft copolymer of vinylbenzene or alpha-methyl styrene, for example vinylbenzene is at polyhutadiene, the multipolymer of vinylbenzene on Polybutadiene-styrene or Polybutadiene-acrylonitrile; Vinylbenzene and vinyl cyanide (or methacrylonitrile) are on polyhutadiene; Vinylbenzene, vinyl cyanide or methyl methacrylate are on polyhutadiene; Vinylbenzene and maleic anhydride are on polyhutadiene; Vinylbenzene, vinyl cyanide and maleic anhydride or maleimide are on polyhutadiene; Vinylbenzene and maleimide are on polyhutadiene; Vinylbenzene and alkyl acrylate or methacrylic ester are on polyhutadiene; Vinylbenzene and vinyl cyanide are on ethylene/propylene/diene terpolymers; Vinylbenzene and vinyl cyanide on polyacrylic acid alkane ester or polymethyl acrylic acid alkane ester, vinylbenzene and vinyl cyanide on acrylate/butadiene copolymers, with and with following 6) multipolymer listed such as known as ABS, MBS, ASA or AES mixture of polymers.
8. the multipolymer of the chlorination of the polymkeric substance of halogen atom such as sovprene chlorinated rubber, isobutylene-isoprene and brominated copolymer (halogen butyl rubber), chlorination or chlorosulfonated polyethylene, ethene and ethylene chloride, the S-of epoxy chloropropane and multipolymer, the particularly polymkeric substance of the vinyl compound of halogen atom, for example polyvinyl chloride, polyvinylidene dichloride, fluorinated ethylene propylene, poly(vinylidene fluoride) and their multipolymer such as vinylchlorid/vinylidene chloride, vinylchlorid/vinyl acetate or vinylidene chloride/vinyl acetate copolymer.
9. by α, the polymkeric substance that beta-unsaturated acid obtains and their derivative such as polyacrylic ester and polymethacrylate; Polymethylmethacrylate, polyacrylamide and polyacrylonitrile, impact-resistant modified with the butyl acrylate structure.
10. following 9) described monomer each other or with the multipolymer of other unsaturated monomers, for example multipolymer or the vinyl cyanide/alkyl methacrylate/butadiene terpolymer of acrylonitrile/butadiene multipolymer, vinyl cyanide/alkyl acrylate ester copolymer, vinyl cyanide/vinylformic acid alcoxyl base alkane ester or vinyl cyanide/ethylene halide.
11. the polymkeric substance that obtains by unsaturated alkohol and amine or acyl derivative or its acetal, for example polyvinyl alcohol, polyvinyl acetate (PVA), polyvinyl stearate, polyvinyl benzoate, polymaleic acid vinyl acetate, poly-butyral (butyral) vinyl acetate, poly-O-phthalic allyl propionate or polyene propyl group melamine; With they and top 1) multipolymer of the alkene mentioned.
12. the multipolymer of the homopolymer of cyclic ethers and multipolymer such as polyalkylene glycol, polyethylene oxide, poly(propylene oxide) or itself and diglycidylether.
13. polyacetal such as polyoxymethylene and these contain the polyoxymethylene of oxyethane as comonomer; Polyacetal with thermoplastic polyurethane, acrylate or MBS modification.
14. polyphenylene oxide and polyphenylene sulfide, and the mixture of polyphenylene oxide and styrene polymer or polymeric amide.
15. by polyethers with hydroxyl ending, the urethane that polyester or polyhutadiene at one end obtain at the other end and its precursor with aliphatic series or aromatic poly-isocyanate.
16. by diamine and dicarboxylic acid and/or aminocarboxylic acid is arranged or polymeric amide and copolyamide that corresponding lactan obtains, the m-xylene diamine and the hexanodioic acid that cause of polymeric amide 4, polyamide 6, polyamide 6/6,6/10,6/9,6/12,4/6,12/12, polymeric amide 11, polymeric amide 12, aromatic polyamides for example; Or/and the polymeric amide that terephthalic acid makes, can have can not have elastomerics as properties-correcting agent yet by cyclohexyl diamines and m-phthalic acid, for example poly--2,4,4 ,-trimethylcyclohexyl terephthaloyl amine or poly-metaphenylene isophthaloyl amine; With aforementioned polymeric amide and polyolefine, olefin copolymer, ionomer or chemical bonding or grafted elastomerics, or with polyethers such as polyoxyethylene glycol, polypropylene glycol or poly-1,4-butyleneglycol segmented copolymer; With polymeric amide or with the copolyamide of EPDM or ABS modification; Polymeric amide with polycondensation when processing (RIM polymeric amide system).
17. polyureas, polyimide, polyamide-imide, polyetherimide, polyester-imide, poly-glycolylurea and polybenzimidazole.
18. by dicarboxylic acid and glycol and/or the polyester that obtains by hydroxycarboxylic acid or corresponding lactone, for example poly terephthalic acid diethyl ester, polybutyl terapthalate, poly--1,4-Dimethylcyclohexyl terephthalate and poly-hydroxybenzoate and by the block copolyether ester that obtains with hydroxyl ending polyethers with the polyester of polycarbonate or MBS modification.
19. polycarbonate and polyestercarbonate.
20. polysulfones, polyethersulfone and polyetherketone.
21. by one side is that acid anhydrides and the other side are the cross-linked polymer that phenol, urea and melamine obtain, for example phenol/formaldehyde resins, urea/formaldehyde resin and melamine/formaldehyde resin.
22. dry and undried Synolac.
23. the unsaturated polyester resin that obtains as the flammable low properties-correcting agent of linking agent and halogen atom by saturated and unsaturated dicarboxylic acid and polyvalent alcohol and vinyl mixture.
24. the crosslinkable acrylic resin that obtains by substituted acrylate such as epoxy acrylate, vinylformic acid urethane ester or polyester acrylate.
25. Synolac, vibrin and acrylate resin with melamine resin, urea resin, isocyanic ester, chlorinated isocyanurates, polymeric polyisocyanate or cross linking of epoxy resin.
26. by the cross-linked epoxy resin of the 2-glycidyl ether product of aliphatic series, cyclic aliphatic, heterocycle or fragrant glycidyl compound such as dihydroxyphenyl propane and Bisphenol F, they are crosslinked as acid anhydrides or amine with common stiffening agent, can contain or not contain accelerator.
27. natural polymer such as Mierocrystalline cellulose, rubber, gelatin and through the filiation of chemical modification, for example acetyl cellulose, cellulose propionate ester and cellulose butyrate, or as ether of cellulose and the rosin and the derivative thereof of Walsroder MC 20000S.
28. the mixture of aforementioned polymer (polyblend), for example PP/EPDM, polymeric amide/EPDM or ABS, PVC/ABS, PVC/EVA, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/ acrylate, POM/ thermoplasticity PUR, PC/ thermoplasticity PUR, POM/ acrylate, POM/MBS, PPO/HIPS, PPO/PA6.6 and multipolymer, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
29. natural generation and synthetic organic materials, they are mixtures of pure single polyacetylene compound or these compounds, for example mineral oil, animal and plant fat, oil and wax, or to synthesize oil, fat and the wax of ester (for example phthalic ester, adipic acid ester, phosphoric acid ester or benzenetricarboxylic acid ester), synthetic ester and mineral oil are with the mixture of any weight ratio, typically these are used as spinning component, and the water miscible liquid of these materials.
30. natural or elastomeric water miscible liquid, for example natural emulsion or the latex of cinnamic carboxylicesters/butadienecopolymer.
31. polysiloxane is for example at soft, hydrophilic polysiloxane described in the United States Patent (USP) 4259467 and United States Patent (USP) 43555147 described hard organopolysiloxane.
32. with the poly-ethyl acetate resin of unsaturated vinylformic acid or with the polyketone imines of unsaturated acrylic resin combination.This unsaturated acrylic resin comprises vinylformic acid urethane ester, polyether acrylate, the vinyl with side unsaturated group or acryl multipolymer and acroleic acid esterification melamine.This polyketone imines is made by polyamine and ketone under the acid catalyst condition.
33. radiation curable compositions contains unsaturated vinyl monomer or oligomer and poly-unsaturated aliphatic oligomer.
34. the epoxy melamine resin, for example the stable Resins, epoxy of light is consolidated melamine resin such as crosslinked the forming of LSE-4103 (Monsanto) by epoxy functionalized common etherificate height.
Although the usage quantity of compound of the present invention is according to specific substrates and purposes and change, its common usage quantity is the about 5wt% of about 0.01-of stable composition.Preferred range is that about 0.05-is about 3%, and particularly 0.05-about 1%.
Stablizer of the present invention can be easily be added in the organic polymer by any convenience of routine techniques before making its moulded products the time.For example, this stablizer can be with dry powder form and mixed with polymers, and perhaps the suspension of stablizer or emulsion can be mixed with solution, suspension or the emulsion of polymkeric substance.It is about 5% that gained stable composition of the present invention also can optionally contain the 0.01-that has an appointment, and preferably about 0.025-is about 2%, the various typical additives of the about 1wt% of particularly about 0.1-, for example below listed material or its mixture.
1. antioxidant
1.1. alkanisation monophenol, for example 2,6-two-tertiary butyl-4-methylphenol, the 2-tertiary butyl-4, the 6-xylenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,6-di-t-butyl-4-isobutyl-phenol 2,6-two cyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4, the 6-xylenol, 2,6-two-octadecyl-4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-di-t-butyl-4-methoxymethyl phenol, nonylphenol, in side chain for linear or side chain arranged, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methyl isophthalic acid '-undecyl) phenol, 2,4-dimethyl-6-(1 '-methyl isophthalic acid '-heptadecyl) phenol, 2,4-dimethyl-6-(1 '-methyl isophthalic acid '-tridecyl) phenol and its mixture.
1.2. the alkylthio methylphenol, for example 2,4-two hot sulfenyl methyl-6-tert butyl phenol, 2,4-two hot sulfenyl methyl-6-methylphenols, 2,4-two hot sulfenyl methyl-6-ethylphenols, 2,6-two-dodecane sulfenyl methyl-4-nonylphenol.
1.3. quinhydrones and alkanisation quinhydrones, for example 2,6-di-t-butyl-4-methoxyphenol, 2,5 di tert butylhydroquinone, 2,5 di tert amlyl hydroquinone, 2,6-phenylbenzene-4-18 epoxy phenol 2,6-di-tert-butyl hydroquinone, 2,5-di-t-butyl-4-hydroxyanisol, 3,5-di-t-butyl-4-hydroxyanisol, 3,5-di-t-butyl-4-hydroxyphenyl stearate, two-(3,5-di-t-butyl-4-hydroxyphenyl) adipic acid ester.
1.4. tocopherol, for example alpha-tocopherol, 5,8-dimethyl tocol, Gamma-Tocopherol, Delta-Tocopherol and its mixture (vitamin-E).
1.5. hydroxylation sulfo-phenyl ether, for example 2,2 '-thiobis (the 6-tertiary butyl-4-methylphenol), 2,2 '-thiobis (4-octyl phenol) 4,4 '-thiobis (the 6-tertiary butyl-3-methylphenol), 4,4 '-thiobis (the 6-tertiary butyl-2-methylphenol), 4,4 '-thiobis (3,6-di-sec-amyl phenol), 4,4 '-two (2,6-dimethyl-4-hydroxyphenyl) disulphide.
1.6. alkylidene bisphenols, for example 2,2 '-methylene-bis (the 6-tertiary butyl-4-methylphenol), 2,2 '-methylene-bis (the 6-tertiary butyl-4-ethylphenol), 2,2 '-methylene-bis [4-methyl-6-(Alpha-Methyl cyclohexyl)-phenol], 2,2 '-methylene-bis(4-methyl-6-cyclohexyl phenol), 2,2 '-methylene-bis (6-nonyl-4-methylphenol), 2,2 '-methylene-bis (4, the 6-DI-tert-butylphenol compounds), 2,2 '-ethylenebis (4, the 6-DI-tert-butylphenol compounds), 2,2 '-ethylenebis (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene-bis [6-(α-Jia Bianji)-4-nonylphenol], 2,2 '-methylene-bis [6-(α, the alpha, alpha-dimethyl benzyl)-the 4-nonylphenol], 4,4 '-methylene-bis (2, the 6-DI-tert-butylphenol compounds), 4,4 '-methylene-bis (the 6-tertiary butyl-2-methylphenol), 1, two (5-tertiary butyl-4-hydroxy-2-tolyl) butane of 1-, 2, two (the 3-tertiary butyl-5-methyl-2-acrinyl)-4-cresols of 6-, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-tolyl) butane, 1, the two positive ten dimercapto butane of (5-tertiary butyl-4-hydroxy-2-tolyl)-3-of 1-, ethylene glycol bis [3, two (3 '-tertiary butyl-4 '-hydroxyphenyl) butyric esters of 3-], two (3-tertiary butyl-4-hydroxy-5-methyl-phenyl) Dicyclopentadiene (DCPD), two [2-(3 '-tertiary butyl-2 '-hydroxyl-5 ' the xylyl)-6-tertiary butyl-4-tolyl] terephthalate, 1,1 '-two (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-two-(3,5-dual-tert-butyl-4-hydroxyphenyl) propane, 2,2-pair-the positive ten dimercapto butane of (5-tertiary butyl-4-hydroxy-2-tolyl)-4-, 1,1,5,5-four-(the 5-tertiary butyl-4-sulfydryl-2-tolyl) pentane.
1.7.O-, N-and S-benzyl compounds, for example 3,5,3 ', 5 ' tetra-tert-4,4 '-dihydroxy dibenzyl ether, octadecyl-4-hydroxyl-3,5-dimethylbenzyl thioglycollate, tridecyl-4-hydroxyl-3,5-di-t-butyl benzyl-mercapto acetic ester, three (3,5-di-t-butyl-4-acrinyl) amine, two (4-tertiary butyl-3-hydroxyl-2,6 dixylyls) dithio terephthalate, two (3,5-dual-tert-butyl-4-acrinyl) sulfide, iso-octyl-3,5-di-t-butyl-4-hydroxyl benzyl-mercapto acetic ester.
1.8. acrinyl malonic ester, two-octadecyl-2 for example, 2-is two-(3,5-di-t-butyl-2-acrinyl) malonic ester, two-octadecyl-2-(3-tertiary butyl-4-hydroxy-5-xylyl)-malonic ester, two-dodecane mercapto ethyl-2, and 2-two-(3,5-di-t-butyl-4-acrinyl) malonic ester, it is two that [4-(1,1,3, the 3-tetramethylbutyl) phenyl]-2, two (3, the 5-di-t-butyl-4-acrinyl) malonic esters of 2-.
1.9. fragrant acrinyl compound, for example 1,3,5-three-(3,5-di-t-butyl-4-acrinyl)-2,4,6-trimethylbenzene, 1, two (3,5-di-t-butyl-4-acrinyl)-2,3,5 of 4-, 6-durene, 2,4,6-three (3,5-di-t-butyl-4-acrinyl) phenol.
1.10. triaizine compounds, for example 2, two (hot the sulfydryl)-6-(3,5-di-t-butyl-4-oxybenzene amino)-1 of 4-, 3, the 5-triazine, the hot sulfydryl-4 of 2-, two (3,5-di-t-butyl-4-oxybenzene amino)-1 of 6-, 3, the 5-triazine, the hot sulfydryl-4 of 2-, 6-two (3,5-di-t-butyl-4-hydroxyl phenoxy group)-1,3,5-triazines, 2,4,6-three (3,5-di-t-butyl-4-hydroxyl phenoxy group)-1,2, the 3-triazine, 1,3,5-three (3,5-di-t-butyl-4-acrinyl) chlorinated isocyanurates, 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dixylyl) chlorinated isocyanurates, 2,4,6-three (3,5-di-t-butyl-4-oxybenzene ethyl)-1,3, the 5-triazine, 1,3,5-three (3,5-di-t-butyl-4-oxybenzene propionyl)-hexahydro--1,3,5-triazines, 1,3,5-three (3,5-dicyclohexyl-4-acrinyl) chlorinated isocyanurates.
1.11. benzyl phosphoric acid ester, dimethyl-2 for example, 5-di-t-butyl-4-acrinyl phosphoric acid ester, diethyl-3,5-di-t-butyl-4-acrinyl phosphoric acid ester, two-octadecyl-3,5-di-t-butyl-4-acrinyl phosphoric acid ester, two-octadecyl-5-tertiary butyl-4-hydroxy-3-xylyl phosphoric acid ester, 3, the calcium salt of 5-di-t-butyl-4-acrinyl monoethyl-phosphate.
1.12. acid amides phenol, for example 4-hydroxyl lauroyl aniline (hydroxylauranilide), 4-hydroxyl stearanilide, N-(3,5-di-t-butyl-4-hydroxyphenyl) carboxylamine monooctyl ester.
1.13. β-(3,5-di-t-butyl-4-hydroxyphenyl) ester of propionic acid and monobasic or polyvalent alcohol, for example with methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, thiodiglycol, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) chlorinated isocyanurates, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-hendecanol, 3-sulfo-pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phosphoric acid-2,6,7-trioxa two ring [2.2.2] octanes.
1.14. the ester of β-(5-tertiary butyl-4-hydroxy-3-tolyl) propionic acid and monobasic or polyvalent alcohol, for example with methyl alcohol, ethanol, n-Octanol, isooctyl alcohol, Stearyl alcohol, 1, the 6-hexylene glycol, 1, the 9-nonanediol, ethylene glycol, 1, the 2-propylene glycol, neopentyl glycol, thiodiglycol, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) chlorinated isocyanurates, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-hendecanol, 3-sulfo-pentadecylic alcohol, the trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phosphoric acid-2,6,7-trioxa two ring [2.2.2] octanes.
1.15. β-(3,5-dicyclohexyl-4-hydroxyphenyl) ester of propionic acid and monobasic or polyvalent alcohol, for example with methyl alcohol, ethanol, n-Octanol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiglycol, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) chlorinated isocyanurates, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-hendecanol, 3-sulfo-pentadecylic alcohol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phosphoric acid-2,6,7-trioxa two ring [2.2.2] octanes.
1.16.3, the ester of 5-di-t-butyl-4-hydroxyphenyl acetic acid and monobasic or polyvalent alcohol, for example with methyl alcohol, ethanol, n-Octanol, Stearyl alcohol, 1,6-hexylene glycol, 1,9-nonanediol, ethylene glycol, 1,2-propylene glycol, neopentyl glycol, thiodiglycol, glycol ether, triglycol, tetramethylolmethane, three (hydroxyethyl) chlorinated isocyanurates, N, N '-two (hydroxyethyl) oxamide, 3-sulfo-hendecanol, 3-sulfo-pentadecylic alcohol, trimethylammonium hexylene glycol, TriMethylolPropane(TMP), 4-methylol-1-phosphoric acid-2,6,7-trioxa two ring [2.2.2] octanes.
1.17. the acid amides of β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid, N for example, N '-two (3,5-di-t-butyl-4-hydroxyphenyl propionyl) hexa-methylene diamide, N, N '-two (3,5-di-t-butyl-4-hydroxyphenyl propionyl) trimethylene diamide, N, N '-two (3,5-di-t-butyl-4-hydroxyphenyl propionyl) hydrazides, N, N '-two [2-(3-[3,5-di-t-butyl-4-hydroxyphenyl] propionyloxy] oxamide is (by the Nau of Uniroyal supply -Gard  XL-1).
1.18. xitix (vitamins C).
1.19. imines antioxidant, N for example, N '-two-sec.-propyl-to inferior phenylenediamine, N, N '-two-tertiary butyl-to inferior phenylenediamine, N, N '-two (1, the 4-pendimethalin base)-to inferior phenylenediamine, N, N '-two (1-ethyl-3-first amyl group)-to inferior phenylenediamine, N, N '-two (1-first heptyl)-to inferior phenylenediamine, N, N '-dicyclohexyl-to inferior phenylenediamine, N, N '-phenylbenzene-to inferior phenylenediamine, N, N '-two (2-naphthyl)-to inferior phenylenediamine, N-sec.-propyl-N '-phenyl-to inferior phenylenediamine, N-(1,3-diformazan butyl)-N '-phenyl-to inferior phenylenediamine, N-(1-first heptyl)-N '-phenyl-to inferior phenylenediamine, N-cyclohexyl-N '-phenyl-to inferior phenylenediamine, 4-(tolysulfonyl) pentanoic; N, N '-dimethyl-N, N '-two sec-butyl-to inferior phenylenediamine, pentanoic, N-allyl group pentanoic, 4-isopropyl diphenyl amine, the N-phenyl-1-naphthylamine, N-(the hot phenyl of uncle 4-)-naphthalidine, N-phenyl-2-naphthylamines, octylated diphenylamine, p for example, p '-two-uncle octyl diphenylamine, 4-n-butyl amine base phenol, the 4-acylamino phenol, 4-nonanoyl amino-phenol, the amino phenol of 4-lauroyl, 4-stearoyl amino-phenol, two (4-p-methoxy-phenyl) amine, 2,6-two-tertiary butyl-4-dimethylamino cresols, 2,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylmethane, N, N, N ', N '-tetramethyl--4,4 '-diaminodiphenylmethane, 1, two [(2-tolyl) amino] ethane of 2-, 1, two (phenylamino) propane of 2-, o-tolyl-biguanide, it is two that [4-(1 ', 3 '-diformazan butyl) phenyl] amine, uncle's octyl group N-phenyl-1-naphthylamine, the mixture of the hot pentanoic of one and the dialkyl group tertiary butyl/uncle, one and the mixture of dialkyl group nonyl diphenylamine, one and the mixture of dialkyl group lauryl pentanoic, one and the mixture of dialkyl group sec.-propyl/isohexyl pentanoic, one and the mixture of the tertiary butyl pentanoic of dialkyl groupization, 2,3-dihydro-3,3-dimethyl-4H-1, the 4-benzothiazine, thiodiphenylamine, one and the mixture of the tertiary butyl/uncle's octyl group thiodiphenylamine of dialkyl groupization, one and the mixture of dialkyl group uncle octyl group thiodiphenylamine, N-allyl group thiodiphenylamine, N, N, N ', N '-tetraphenyl-1,4-diamino 2-butylene, N, N-two (2,2,6,6-tetramethyl--piperidines-4)-hexamethylene-diamine, two (2,2,6,6-tetramethyl piperidine-4) sebate, 2,2,6,6-tetramethyl piperidine-4-ketone, 2,2,6,6-tetramethyl piperidine-4-alcohol.
2. ultraviolet absorbers and photostabilizer
(2.1.2-2 '-hydroxyphenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-tolyl) benzotriazole for example, 2-(3 ', 5 '-di-t-butyl-2 '-hydroxyphenyl) benzotriazole, 2-(5 '-tertiary butyl-2 '-hydroxyphenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-(1,1,3, the 3-tetramethylbutyl) benzotriazole phenyl), 2-(3 ', 5 '-di-t-butyl-2 '-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-tolyl)-5-chloro-benzotriazole, 2-(3 '-sec-butyl-the 5 '-tertiary butyl-2 '-hydroxyphenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(3 ', 5 '-two tert-pentyls-2 '-hydroxyphenyl) benzotriazole, 2-(3 ', 5 '-two (α, the alpha, alpha-dimethyl benzyl)-2 '-hydroxyphenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the hot oxygen phosphinylidyne of 2-ethyl) phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy)-phosphinylidyne ethyl]-2 '-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxyl group phosphinylidyne ethyl) phenyl)-5-chloro-benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-methoxyl group phosphinylidyne ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(2-octyloxy phosphinylidyne ethyl) phenyl) benzotriazole, 2-(3 '-tertiary butyl-5 '-[2-(2-ethyl hexyl oxy) phosphinylidyne ethyl]-2 '-hydroxyphenyl) benzotriazole, 2-(3 '-Lauroguadine '-hydroxyl-5 '-tolyl) benzotriazole, 2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-(the different octyloxy phosphinylidyne of 2-ethyl) phenyl benzotriazole, 2, [4-(1 for 2 '-methylene radical-two, 1,3, the 3-tetramethyl butyl)-6-benzotriazole-2-phenol], the transesterification goods of 2-(3 '-tertiary butyl-5 '-(2-methoxyl group phosphinylidyne ethyl)-2 '-hydroxyphenyl)-2H-benzotriazole and Liquid Macrogol, [R-CH 2CH 2-COO-CH 2CH 2] 2Wherein R=3 '-tertiary butyl-4 '-hydroxyl-5 '-2H-benzotriazole-2-benzene, 2-[2 '-hydroxyl-3 '-(α, the alpha, alpha-dimethyl benzyl)-5 '-(1,1,3,3-tetramethyl butyl)-phenyl]-benzotriazole, 2-[2 '-hydroxyl-3 '-(1,1,3, the 3-tetramethyl butyl)-5 '-(α, alpha, alpha-dimethyl benzyl)-phenyl]-benzotriazole.
2.2.2-hydroxy benzophenone, for example 4-hydroxyl, 4-methoxyl group, 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base, 4-bay oxygen base, 4-benzyloxy, 4,2 ', 4 '-trihydroxy-and 2 '-hydroxyl-4,4 '-dimethoxy derivative.
2.3. the benzoic ether that replaces and be unsubstituted; for example the Whitfield's ointment 4-tertiary butyl-phenyl ester, salol, Whitfield's ointment octyl octylphenyl, dibenzoyl resorcinols, two (4-tert.-butylbenzene formyl radical) Resorcinol, benzoyl Resorcinol, 2; 4-di-tert-butyl-phenyl 3; 5-di-tert-butyl-4-hydroxybenzoic acid ester, 3; 5-di-tert-butyl-4-hydroxybenzoic acid n-Hexadecane ester, 3; 5-di-tert-butyl-4-hydroxybenzoic acid octadecane ester, 2-methyl-4; 6-di-tert-butyl-phenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid ester.
2.4. acrylate, alpha-cyano-β for example, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenyl 2-Propenoic acid-2-ethylhexyl ester, α-methoxycarbonyl methyl cinnamate, alpha-cyano-Beta-methyl-p-p-Methoxymethylcinnamate, alpha-cyano-Beta-methyl-p-methoxy cinnamic acid butyl ester, α-methoxycarbonyl-p-p-Methoxymethylcinnamate and N-(beta-carbomethoxy-3-β-acrylonitrile base)-2 methyl indole spirit.
2.5. nickel compound; for example 2; 2 ' sulfo--two-[4-(1; 1; 3; the 3-tetramethyl butyl) phenol] nickel complex; for example 1: 1 or complexing in 1: 2; can add and also can not add part such as n-Butyl Amine 99, trolamine or N-hexamethylene diethanolamine, nickel dithiocarbamic acid dibutylester, mono alkyl ester such as methyl esters or ethyl ester, 4-hydroxyl-3; the nickel salt of 5-di-t-butyl benzyl phosphoric acid; the nickel complex of ketoxime such as 2-hydroxy-4-methyl benzyl undecyl ketoxime, the nickel complex of 1-benzyl-4-lauroyl-5-hydroxypyrazoles can add also and can not add part.
2.6. sterically hindered amines, for example two (2,2; 6,6-tetramethyl piperidine-4-yl) sebate; two (2,2; 6,6-tetramethyl--4-piperidyl) succinate; two (1,2; 2,6,6-pentamethyl--4-piperidyl) sebate; two (1-octyloxies-2; 2,6,6-tetramethyl piperidine-4-yl) sebate; two (1; 2,2,6; 6-pentamethyl-piperidin-4-yl) normal-butyl-3,5-di-tert-butyl-4-hydroxyl benzyl malonic ester; 1-(2-hydroxyethyl)-2,2; 6, the polycondensate of 6-tetramethyl--4-hydroxy piperidine and succsinic acid; N, N '-two (2; 2,6,6-tetramethyl piperidine-4-yl) hexamethylene-diamine and uncle 4-hot amino-2; the linearity or the cyclic condensation polymer of 6-two chloro-1,3,5-triazines; three (2; 2,6,6-tetramethyl piperidine-4-yl) inferior amino triacetate; four (2; 2,6,6-tetramethyl piperidine-4-yl)-1; 2,3,4-butane-tetracarboxylic ester; 1; 1 '-(1, the 2-ethanetetrayl) (ethanediyl)-two (3,3; 5,5-tetramethyl-piperazine ketone); 4-benzoyl group-2,2; 6, the 6-tetramethyl piperidine; 4-stearoyl-oxy-2,2; 6, the 6-tetramethyl piperidine; two (1,2; 2,6,6-pentamethyl-piperidyl)-2-normal-butyl-2-(2-hydroxyl-3; 5-di-t-butyl benzyl) malonic ester; 3-n-octyl-7,7,9; 9-tetramethyl--1,3,8-three nitrogen spiral shells [4; 5] last of the ten Heavenly stems-2, the 4-diketone; two (1-octyloxies-2,2; 6, the 6-tetramethyl-piperidyl) sebate; two (1-octyloxies-2,2; 6, the 6-tetramethyl-piperidyl) succinate; N, N '-two (2; 2,6,6-tetramethyl piperidine-4-yl) hexamethylene-diamine and 4-morpholinyl-2; the linearity or the cyclic condensation polymer of 6-two chloro-1,3,5-triazines; 2-chloro-4; 6-two (4-normal-butyl amino-2; 2,6, the 6-tetramethyl-piperidyl)-1; 3; 5-triazine and 1, the polycondensate of 2-two (amino third amino of 3-) ethane; 2-chloro-4,6-two (4-normal-butyl amino-1; 2; 2,6,6-pentamethyl-piperidyl)-1; 3; 5-triazine and 1, the polycondensate of 2-two (amino third amino of 3-) ethane; 8-ethanoyl-3-lauroyl-7,7; 9; 9-tetramethyl--1,3,8-three nitrogen spiral shells [4; 5] last of the ten Heavenly stems-2; the 4-diketone; 3-lauroyl-1-(2,2,6; 6-tetramethyl piperidine-4-yl) pyrroles-2; the 5-diketone; 3-lauroyl-1-(1,2,2; 6; 6-pentamethyl-piperidin-4-yl) pyrroles-2, the 5-diketone; 4-n-Hexadecane oxygen base-and 4-stearoyl-oxy-2,2; 6; the mixture of 6-tetramethyl piperidine; N, N '-two (2,2; 6; 6-tetramethyl piperidine-4-yl) hexamethylene-diamine and 4-hexamethylene amino-2,6-two chloro-1,3; the polycondensate of 5-triazine; 1; 2-two (amino third amino of 3-) ethane and 2,4,6-three chloro-1; 3; 5-triazine and 4-fourth amino-2,2,6; the polycondensate of 6-tetramethyl piperidine (CAS registration number [136504-96-6]); N-(2; 2,6,6-tetramethyl piperidine-4-yl)-positive lauroyl succinimide; N-(1; 2; 2,6,6-pentamethyl-piperidin-4-yl)-positive lauroyl succinimide; 2-undecanoyl-7; 7; 9,9-tetramethyl--1-oxa--3,8-phenodiazine-4-oxo-spiral shell [4; 5] decane; 7; 7,9,9-tetramethyl--2-encircles undecyl-1-oxa--3; 8-phenodiazine-4-oxo-spiral shell [4; 5] product of decane and epichlorohydrin reaction; 1,1-two (1,2; 2; 6,6-pentamethyl--4-piperidines acyl-oxygen carbonyl)-2-(4-p-methoxy-phenyl) ethane; N, N '-two-formyl radical-N; N '-two (2; 2,6,6-tetramethyl piperidine-4-yl) hexamethylene-diamine; 4-methoxyl group-methylene radical-propanedioic acid and 1; 2; 2,6, the diester of 6-pentamethyl--4-hydroxy piperidine; poly-[methyl-propyl-3-oxygen base-4-(2; 2; 6,6-tetramethyl piperidine-4-yl)] siloxanes; maleic anhydride-alpha-olefin-multipolymer and 2,2; 6; 6-tetramethyl--4-amino piperidine or 1,2,2; 6, the reaction product of 6-pentamethyl--4-amino piperidine.
2.7 oxamide, for example 4,4 '-two octyloxy oxalyl pentanoic, 2,2 '-diethoxy oxalyl pentanoic, 2,2 '-two octyloxies-5,5 '-di-t-butyl oxalyl pentanoic, 2,2 '-two bay acyloxy-5,5 '-di-t-butyl oxalyl pentanoic, 2-oxyethyl group-2 '-ethyl oxalyl pentanoic, N, N '-two (3-dimethylamino-propyl) oxalic acid diamide, 2-oxyethyl group-5-the tertiary butyl-2 '-ethyl oxalyl pentanoic and it and 2-oxyethyl group-2 '-ethyl-5, the mixture of 4 '-di-t-butyl oxalyl pentanoic, adjacent-and the mixture of right-methoxyl group-dibasic oxalyl pentanoic and neighbour-and the mixture of right-dibasic oxalyl pentanoic.
(2.8.2-2-hydroxyphenyl)-1,3, the 5-triazine, for example 2,4,6-three (2-hydroxyl-4-octyloxyphenyl)-1,3,5 triazines, 2-(2-hydroxyl-4-octyloxyphenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5 triazines, 2-(2, the 4-dihydroxy phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5 triazines, 2,4-two (2-hydroxyl-4-propoxy-phenyl)-6-(2, the 4-3,5-dimethylphenyl)-1,3,5 triazines, 2-(2-hydroxyl-4-octyloxyphenyl)-4,6-two (4-aminomethyl phenyl)-1,3,5 triazines, 2-(2-hydroxyl-4-bay oxygen base phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5 triazines, 2-(2-hydroxyl-4-tridecane oxygen base phenyl)-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5 triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-butoxy-propoxy-) phenyl]-4,6-two (2, the 4-dimethyl)-1,3,5 triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-octyloxy-propoxy-) phenyl]-4,6-two (2, the 4-dimethyl)-1,3,5 triazines, 2-[4-(dodecyloxy/tridecane oxygen base-2-propoxyl)-2-hydroxyl-phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5 triazines, 2-[2-hydroxyl-4-(2-hydroxyl-3-bay oxygen base-propoxy-) phenyl]-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5 triazines, 2-(2-hydroxyl-4-hexyloxy) phenyl-4,6-phenylbenzene-1,3,5 triazines, 2-(2-hydroxyl-4-p-methoxy-phenyl)-4,6-phenylbenzene-1,3,5 triazines, 2,4,6-three [2-hydroxyl-4-(3-butoxy-2-hydroxyl-propoxy-) phenyl]-1,3,5 triazines, 2-(2-hydroxyphenyl-4-(4-p-methoxy-phenyl)-6-phenyl-1,3,5 triazines, 2-{2-hydroxyl-4-[3-(2-ethylhexyl-1-oxygen)-2-propoxyl] phenyl }-4,6-two (2, the 4-3,5-dimethylphenyl)-1,3,5 triazines.
3. metal deactivator, N for example, N '-phenylbenzene oxamide, N-salicylic aldehyde-N '-salicylyl hydrazine, N, N '-two (salicylyl) hydrazine, N, N '-two (3,5-di-t-butyl-4-hydroxyphenyl propionyl) hydrazine, 3-salicylyl amino-1,2,4-triazine, two (benzylidene) oxalyl two hydrazides, oxalyl pentanoic, isophthaloyl two hydrazides, sebacoyl phenylbenzene hydrazides, N, N '-diacetyl hexanedioyl two hydrazides, N, N '-two (salicylyl) oxalyl two hydrazides, N, N '-two (salicylyl) sulfo-propionyl two hydrazides.
4. phosphorous acid ester and phosphonic acid ester, triphenyl phosphite for example, alkyl phosphorous acid diphenyl ester, dialkyl group phosphorous acid one phenyl ester, three (nonyl phenyl) phosphorous acid ester, trilauryl phosphite, tricresyl phosphite-octadecyl ester, tetramethylolmethane diphosphorous acid distearyl ester, three (2, the 4-di-tert-butyl-phenyl) diphosphites, tetramethylolmethane diphosphorous acid two isodecyl esters, two (2, the 4-di-tert-butyl-phenyl)-pentaerythritol diphosphites, two (2,6-di-t-butyl-4-aminomethyl phenyl)-pentaerythritol diphosphites, two isodecyl epoxy pentaerythritol diphosphites, two (2,4-di-t-butyl-6-aminomethyl phenyl) pentaerythritol diphosphites, two (2,4,6-tri-tert phenyl) pentaerythritol diphosphites, sorbyl alcohol three tricresyl phosphite stearyl esters, four (2, the 4-di-tert-butyl-phenyl) 4,4 '-diphenylene bisphosphonates (diphosphonite), 6-different octyloxy-2,4,8,10-tetra-tert-12H-hexichol [d, g]-1,3,2-two oxa-phosphoric acid essences, two (2,4-di-t-butyl-6-aminomethyl phenyl) methyl phosphorous acid ester, two (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester, 6-fluoro-2,4,8,10-tetra-tert-12-methyl-hexichol [d, g]-1,3,2-two oxa-phosphoric acid essences, 2,2 '; 2 "-inferior amino [triethyl three (3,3 ', 5,5 '-tetra-tert-1,1 '-biphenyl-2,2 '-two bases) phosphorous acid ester], 2-ethylhexyl (3,3 ', 5,5 '-tetra-tert-1,1 ' biphenyl-2,2 '-two bases) phosphorous acid ester], 5-butyl-5-ethyl-2-(2,4, the 6-tri-butyl-phenoxy)-1,3,2-two oxa-phosphoric acid alkane (phosph irane).
Preferred especially following phosphorous acid ester:
Three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester (Irgafos  168, Ciba-Geigy), three (nonyl phenyl) phosphorous acid ester:
Figure A0010651500571
5. azanol, N for example, N-dibenzyl hydroxylamine, N, N-diethyl hydroxylamine, N, N-dioctyl azanol, N, N-dilauryl azanol, N, N-two-tetradecyl azanol, N, N-two-hexadecyl azanol, N, N-two-octadecyl azanol, N-hexadecyl-N-octadecyl azanol, N-heptadecyl-N-octadecyl azanol, the N that derives and obtain by hydrogenated tallow amine, N-dialkyl group azanol.
6. nitrone, for example N-benzyl-alpha-phenyl-nitrone, N-ethyl-Alpha-Methyl-nitrone, N-octyl group-α-heptyl-nitrone, N-lauryl-α-undecyl-nitrone, N-tetradecyl-α-tridecyl-nitrone, N-hexadecyl-α-pentadecyl-nitrone, N-octadecyl-α-heptadecyl-nitrone, N-hexadecyl-α-heptadecyl-nitrone, N-octadecyl-α-pentadecyl-nitrone, N-heptadecyl-α-heptadecyl-nitrone, N-octadecyl-α-hexadecyl-nitrone, by N, N-dialkyl group azanol or the nitrone that obtains from hydrogenated tallow amine.
7. sulfo-synergistic agent, for example Tyox B or distearyl thiodipropionate.
8. peroxide scavenger; the for example ester of β-sulfo-two propylene, for example zinc salt of the ester of lauryl, stearyl-, tetradecyl or tridecyl, mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, two-octadecyl disulphide, tetramethylolmethane four (β-bay sulfydryl) propionic ester.
9. polymeric amide stablizer is for example with the mantoquita and the manganous salt of iodide and/or phosphide combination.
10. alkalescence steady agent altogether, the for example an alkali metal salt of melamine, Povidone, dicyan diamide, triallyl cyanurate, urethane derivatives, hydrazine derivative, amine, polymeric amide, urethane, higher fatty acid and alkaline earth salt such as calcium stearate, Zinic stearas, behenic acid magnesium, Magnesium Stearate, sodium ricinoleate and potassium palmitate, phthalic acid antimony or phthalic acid zinc.
11. nucleator, for example talcous inorganics, as the metal oxide of titanium dioxide or magnesium dioxide, phosphoric acid salt, carbonate or the vitriol of preferred bases earth metals; As single or polycarboxylic organic compound and its salt, for example 4-p t butylbenzoic acid, hexanodioic acid, phenylbenzene acetic acid, sodium succinate or Sodium Benzoate; Polymkeric substance as ionic copolymer (ionomer).Particularly preferably be 1,3:2,4-two (3 ', 4 '-dimethyl benzylidene) sorbyl alcohol, 1,3:2,4-two (to the methyl dibenzylidene) sorbyl alcohol and 1,3:2,4-two (benzylidene) sorbyl alcohol.
12. weighting agent and toughener, for example, lime carbonate, silicate, glass fibre, glass sphere, asbestos, talcum, kaolin, mica, barium sulfate, metal oxide and oxyhydroxide, carbon black, graphite, wood powder and other natural product powder or fiber, synthon.
13. other additives, for example softening agent, lubricant, emulsifying agent, pigment, rheological additives, catalyzer, flow control agent, white dyes, flame-proofing agent, static inhibitor and whipping agent.
14. benzofuranone and indolone, for example at United States Patent (USP) 4325863,4338244,5175312,5216052,5252643, DEA4316611, DE-A4316622, DE4316876A, those that describe among EP0589839A or the EP0591102A, perhaps 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-t-butyl-benzofuran-2-ones, 5,7-di-t-butyl-3-[4-(2-stearoyl keto base oxethyl) phenyl] benzofuran-2-ones, 3,3 '-two [5,7-di-t-butyl-3-(the 4-[2-hydroxyl-oxethyl] phenyl) benzofuran-2-ones], 5,7-di-t-butyl-butyl-3-(4-ethoxyl phenenyl) benzofuran-2-ones, 3-(4-acetoxy-3, the 5-3,5-dimethylphenyl)-5,7-di-t-butyl-benzofuran-2-ones, 3-(3,5-dimethyl-4-new pentane acyloxy phenyl)-5,7-di-t-butyl-benzofuran-2-ones, 3-(3, the 4-3,5-dimethylphenyl)-5,7-di-t-butyl-benzofuran-2-ones, 3-(2, the 3-3,5-dimethylphenyl)-5,7-di-t-butyl-benzofuran-2-ones.
15. amine oxide, for example the amine oxide derivative described in the United States Patent (USP) 5844029 and 5882191, didecyl methyl oxidation amine, three decyl amine oxides, three lauryl amine oxides and three-hexadecyl amine oxide.United States Patent (USP) 5844029 and 5880191 discloses the purposes of stable hydrocarbon amine oxide on the stabilising thermoplastic resin.Disclose as follows: thermoplastic compounds can also contain a stablizer or stabilizer blend, and these stablizers are selected from phenolic antioxidant, hindered amine as light stabilizer, ultraviolet absorbers, Organophosphorous compounds, fatty acid alkali metal salt and sulfo-synergistic agent.But for example amine oxide and other stablizers together the time to the common use of stabilization of polyolefins.
The steady altogether agent of amine oxide is as shown in the formula (I)
Wherein
E 1And E 2Be respectively the straight or branched alkyl of 6-36 carbon atom, the aromatic base of 6-12 carbon atom, the aralkyl of 7-36 carbon atom, the alkaryl of 7-36 carbon atom, the cycloalkyl of 5-36 carbon atom, the alkane cycloalkyl of 6-36 carbon atom or the alkyl naphthene of 6-36 carbon atom.
E 3Be the straight or branched alkyl of 1-36 carbon atom, the aromatic base of 6-12 carbon atom, the aralkyl of 7-36 carbon atom, the alkaryl of 7-36 carbon atom, the cycloalkyl of 5-36 carbon atom, the alkane cycloalkyl of 6-36 carbon atom or the alkyl naphthene of 6-36 carbon atom, as long as E 1, E 2And E 3In at least one contains a c h bond; And
Wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkane cycloalkyl and alkyl naphthene can by 1-16-O-,-S-,-SO 2-,-COO-,-OCO-,-CO-,-NE 4-,-CONE 4-and-NE 4The CO-group interrupts, and perhaps wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkane cycloalkyl and alkyl naphthene can be selected from-OE by 1-16 4,-SE 4,-COOE 4,-OCOE 4,-COE 4,-N (E 4) 2,-CON (E 4) 2,-NG 4COE 4With contain 5-and 6-unit ring-C (CH 3) (CH 2R x) NL 1(CH 2R x) (CH 3) group of C-replaces, perhaps described alkyl, aralkyl, alkaryl, cycloalkyl, alkane cycloalkyl and alkyl naphthene had not only been interrupted by above-mentioned group but also by being replaced by above-mentioned group; And
Wherein
E 4For being the alkyl of hydrogen atom or 1-18 carbon atom independently;
R xBe hydrogen atom or methyl, preferred hydrogen atom;
L 1Be C 1-30The straight or branched alkyl ,-C (O) R 30, R wherein 30Be C 1-30The straight or branched alkyl, perhaps-OR 30, R wherein 30Be C 1-30The straight or branched alkyl; And
Wherein said aryl can be replaced by the alkoxyl group of the alkyl of 1-3 halogen atom, 1-8 carbon atom, 1-8 carbon atom or its combination.
The preferred structure of formula (1) is E wherein 1And E 2The benzyl that is respectively benzyl or is substituted.E 1, E 2And E 3Can be identical residue each other.E 1And E 2Also be preferably the alkyl of 8-26 carbon atom, most preferably be the alkyl of 10-26 carbon atom, and E 3Be preferably the alkyl of 1-22 carbon atom, the methyl that most preferably is methyl or is substituted.Equally, preferably amine oxide comprises E 1, E 2And E 3Be those of the identical alkyl of 6-36 carbon atom.Preferably, for aforementioned E 1, E 2And E 3All residues all be the stable hydrocarbon residue or contain at least one aforementioned-O-,-S-,-SO-,-CO 2-,-CO-or-the stable hydrocarbon residue of CON-group.To each E 1, E 2And E 3Other useful residues, those skilled in the art can expect, and not depart from the present invention.
Saturated amine oxide can also comprise poly-(amine oxide).Poly-(amine oxide) meaning is the tertiary amine oxide that contains two tertiary amine oxides in each molecule at least.Described poly-(amine oxide) is also referred to as " poly-(tertiary amine oxide) ", comprises the oxidation book amine analogs of aliphatic series or alicyclic diamine, for example 1,4-two Frucoters, 1,6-diamino hexane, 1,10-diamino decane and 1,4-diamino hexanaphthene and aromatic base diamines such as diamino-anthraquinone and diamino anisole.
Equally also comprise the tertiary amine oxide that oligopolymer and polymkeric substance by above-mentioned diamines obtain.Useful amine oxide also comprises the amine oxide that sticks on polymkeric substance such as polyolefine, polyacrylic ester, polyester, polymeric amide, polystyrene etc.When amine oxide sticked on the polymkeric substance, the mean number of the amine oxide on each polymkeric substance can have very big variation, and polymer chain that needn't be all contains amine oxide.All aforementioned amine oxides can optionally contain at least one-O-,-S-,-SO-,-CO 2-,-CO-or-CONE 4-.In a preferred embodiment, each tertiary amine oxide contains a C in the polymerization oxidation tertiary amine 1Residue.
Group E in the formula (I) 1, E 2And E 3Can adhere on the molecule that contains hindered amine.Hindered amine is known in the art, and amine oxide of the present invention can adhere on this hindered amine with locations of structures in any way.When useful hindered amine adds jointly when the compound of its partial oxidation amine, comprise general formula (II) and (III) those;
L wherein 1And R xAs mentioned above.Also comprise the amine oxide that contains a plurality of hindered amines and a plurality of saturated amine oxides in each molecule.Hindered amine can stick to poly-(tertiary amine oxide) discussed above or stick on the polymeric matrix.
Except following 11 listed benzofuranones (benzofuranones), treat the gross weight of stable material mutually, steady agent is altogether added with the concentration of 0.01-10%.
Except component (a) with (b), preferred composition comprises other additives, particularly phenolic antioxidant, photostabilizer or processing stabilizers.
Particularly preferred additive is phenolic antioxidant (numbering 1), space hindered amine (numbering 2,6), phosphorous acid ester and phosphinate (phosphonites) (numbering 4) and peroxide breakdown compound (numbering 5).
Same particularly preferred other additives (stablizer) are benzofuran-2-ones, described in United States Patent (USP) 4325863,4338244 or 5 1,753 12.
Useful especially phenolic antioxidant is selected from 3,5-di-t-butyl-4-hydroxyl hydrogen TRANSCINNAMIC ACID Octadecane ester, neopentane four bases four (3,5-di-t-butyl-4-hydroxyl hydrogen cinnamic acid ester), 3,5-di-t-butyl-4-acrinyl di(2-ethylhexyl)phosphate-Octadecane ester.1,3,5-three (3,5-di-t-butyl-4-acrinyl) chlorinated isocyanurates, sulfo-diethylidene two (3,5-di-t-butyl-4-hydroxyl hydrogen cinnamic acid ester), 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 3, octylene two (the 3-methyl-5-tertiary butyl-4-hydroxy benzylacetic acid ester) of 6 two oxa-s, 2,6-di-t-butyl-p-cresol, 2,2 '-ethylidene-two (4, the 6-DI-tert-butylphenol compounds), 1,3,5-three (2,6-dimethyl-4-the tertiary butyl-3-acrinyl) chlorinated isocyanurates, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3, [2-(3 for 5-three, 5-di-t-butyl-4-hydroxyl hydrogenation cassia bark acyloxy) ethyl] chlorinated isocyanurates, 3,5-two-(3,5-di-t-butyl-4-acrinyl) front three phenol, cyclohexyl two (3,5-di-t-butyl-4-hydroxyl benzylacetic acid ester), 1-(3,5-di-t-butyl-4-oxybenzene amino)-3,5-two (hot sulfenyl)-S-triazine, N, N '-cyclohexyl-two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide), two (3,5-di-t-butyl-4-acrinyl-etherophosphoric acid) calcium, ethylene [3,3-two (the 3-tertiary butyl-4-hydroxyphenyl) butyric ester], 3,5-di-t-butyl-4-acrinyl mercaptoacetic acid monooctyl ester, two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide) hydrazides and N, N '-two [2-(3,5-di-t-butyl-4-hydroxyl hydrocinnamamide oxygen base)-ethyl]-oxamide.
Most preferred phenolic antioxidant is neopentane four bases four (3,5-di-t-butyl-4-hydroxyl hydrogenation cinnamic acid ester), 3,5-di-t-butyl-4-hydroxyl hydrogen TRANSCINNAMIC ACID Octadecane ester, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-three (3,5-di-t-butyl-4-acrinyl) chlorinated isocyanurates, 2,6-di-t-butyl-p-cresol or 2,2 '-ethylidene-two (4, the 6-DI-tert-butylphenol compounds).
Useful especially hindered amine compound is selected from two (2,2,6,6-tetramethyl piperidine-4-yl) sebate, two (1,2,2,6,6-pentamethyl-piperidin-4-yl) sebate, two (1,2,2,6,6-pentamethyl-piperidin-4-yl) (3,5-di-t-butyl-4-acrinyl) butyl malonic acid ester, 4-benzyloxy-2,2,6, the 6-tetramethyl piperidine, 4-stearoyl-oxy-2,2,6, the 6-tetramethyl piperidine, 3-n-octyl-7,7,9,9-tetramethyl--1,3,8-three nitrogen spiral shells [4,5] last of the ten Heavenly stems-2, the 4-diketone, three (2,2,6,6-tetramethyl piperidine-4-yl) inferior amino triacetate, 1,2-two (2,2,6,6-tetramethyl--3-oxo-piperidine-4-yl) ethane, 2,2,4,4-tetramethyl--7-oxa--3,20-phenodiazine-21-oxa-two spiral shells [5.1.11.2] eicosane, 2, the hot amino of 4-two chloro-uncles 6--S-triazine and 4,4 '-hexylidene two (amino-2,2,6,6-tetramethyl piperidine) polycondensate, 1-(2-hydroxyethyl)-2,2,6, the polycondensate of 6-tetramethyl--4-hydroxy piperidine and succsinic acid, 4,4 '-hexylidene two (amino-2,2,6, the 6-tetramethyl piperidine) and the polycondensate of glycol dibromide, four (2,2,6,6-tetramethyl piperidine-4-yl)-1,2,3,4-butane-tetracarboxylic ester, four (1,2,2,6,6-pentamethyl-piperidin-4-yl)-1,2,3,4-butane-tetracarboxylic ester, 2,4-two chloro-6-morpholinyl-S-triazines and 4,4 '-hexylidene two (amino-2,2,6,6-tetramethyl piperidine) polycondensate, N, N; N ", N -four [(4,6-two (butyl-1,2,2,6,6-pentamethyl-piperidin-4-yl)-and amino-S-triazine-2-yl]-1,10-diamino-4,7-phenodiazine nonane, 2,4-two chloro-6-morpholinyl-S-triazines and 4,4 '-hexylidene two (amino-1,2,2,6,6-pentamethyl-piperidines) polycondensate, through blended [2,2,6,6-tetramethyl piperidine-4-base/β, β, β ', β '-tetramethyl--3,9-(2,4,8,10-four oxaspiros [5,5]-undecane diethyl] 1,2,3,4-butanetetra-carboxylic acid ester, through [1,2 of compound, 2,6,6-pentamethyl-piperidin-4-yl/β, β, β ', β '-tetramethyl--3,9-(2,4,8,10-four oxaspiros [5,5]-undecane diethyl] 1,2,3,4-butanetetra-carboxylic acid ester, octylene two (2,2,6,6-tetramethyl piperidine-4-yl carboxylic acid ester), 4,4 '-methylene radical two (2,2,6,6-tetramethyl-piperazine-3-ketone), N-2,2,6,6-tetramethyl piperidine-4-base-positive lauryl cinnyl imines, N-1,2,2,6,6-pentamethyl-piperidin-4-yl-positive lauryl cinnyl imines, N-1-ethanoyl-2,2,6,6-tetramethyl piperidine-4-base-lauryl cinnyl imines, 1-ethanoyl-3-lauryl-7,7,9,9-tetramethyl--1,3,8-three nitrogen spiral shells [4,5] last of the ten Heavenly stems-2, the 4-diketone, two (1-octyloxies-2,2,6,6-tetramethyl piperidine-4-yl) sebate, two (1-cyclohexyloxies-2,2,6,6-tetramethyl piperidine-4-yl) sebate, 1-octyloxy-2,2,6,6-tetramethyl--4-hydroxy-piperdine, poly--{ [uncle's 6-octyl group amino-S-triazinyl-2,4-two bases] [2-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) imino--hexylidene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl] imino-, 2,4,6-three [N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) the n-butyl amine base]-the S-triazine, 2-(2-hydroxyethylamino)-4,6-two { N-[1-(cyclohexyloxy)-2,2,6,6-tetramethyl piperidine-4-yl]-Ding amino-S-triazine, have 2, N-{[2-(N-2,2 of 4-two (dibutylamino)-S-triazine-6-base terminal, 6,6-tetramethyl piperidine-4-yl) fourth amino]-S-triazine-4-yl }-N, N '-two (2,2,6,6-tetramethyl piperidine-4-yl)-1, the oligopolymer of 6-hexanediamine, N, N ', N "-three { 2,4-two [N-(1; 2; 2,6,6-pentamethyl-piperidin-4-yl)-Ding amino]-S-triazine-6-yl }-3; 3 '-ethylene imino-bis-propylamine; N; N ', { 2, [N-(1 for 4-two for N -three, 2,2,6,6-pentamethyl-piperidin-4-yl)-Ding amino]-S-triazine-6-yl }-3,3 '-ethylene imino-bis-propylamine and N, N ', N ", N -four { 2; 4-two [N-(1; 2,2,6; 6-pentamethyl-piperidin-4-yl)-Ding amino]-S-triazine-6-yl }-3,3 '-ethylene imino-bis-propylamine; N, N ', N "-three { 2; 4-two [N-(1-cyclohexyloxy-2,2,6; 6-tetramethyl piperidine-4-yl)-Ding amino]-S-triazine-6-yl }-3,3 '-ethylene imino-bis-propylamine; N, N '; N -three { 2,4-two [N-(1-cyclohexyloxy-2,2; 6,6-tetramethyl piperidine-4-yl)-Ding amino]-S-triazine-6-yl }-3,3 '-ethylene imino-bis-propylamine, N, N ', N ", N -four { 2; 4-two [N-(1-cyclohexyloxy-2,2,6; 6-tetramethyl piperidine-4-yl)-Ding amino]-S-triazine-6-yl }-3,3 '-ethylene imino-bis-propylamine; have 2, N-{[2-(1-propoxy--2; 2,6,6-tetramethyl piperidine-4-yl) the fourth amino of 4-two (dibutylamino)-S-triazine-6-base terminal]-S-triazine-4-yl }-N; N '-two (1-propoxy--2,2,6,6-tetramethyl piperidine-4-yl)-1, the oligopolymer of 6-hexanediamine or 2-morpholine-4,6-two chloro-S-triazine and N, N '-two (1,2,2,6,6-pentamethyl-piperidin-4-yl)-1, the polycondensate of 6-hexanediamine.
Most preferred hindered amine compound is two (2,2,6,6-tetramethyl piperidine-4-yl) sebate, two (1,2,2,6,6-pentamethyl-piperidin-4-yl) sebate, two (1,2,2,6,6-pentamethyl-piperidin-4-yl) (3,5-di-t-butyl-4-acrinyl) butyl malonic acid ester, 1-(2-hydroxyethyl)-2,2,6, the polycondensate of 6-tetramethyl--4-hydroxy piperidine and succsinic acid, 2, the hot amino of 4-two chloro-uncles 6--S-triazine and 4,4 '-hexylidene two (amino-2,2,6, the 6-tetramethyl piperidine) polycondensate, N, N, N ", N -four [(4; 6-two (butyl-1; 2,2,6; 6-pentamethyl-piperidin-4-yl)-amino-S-triazine-2-yl]-1; 10-diamino-4,7-phenodiazine nonane; two (1-octyloxies-2,2,6,6-tetramethyl piperidine-4-yl) sebate, two (1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate, 1-octyloxy-2,2,6,6-tetramethyl--4-hydroxy-piperdine, poly--{ [uncle's 6-octyl group amino-S-triazinyl-2,4-two bases] [2-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) imino--hexylidene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl] imino-or 2,4,6-three [N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) the n-butyl amine base]-the S-triazine.
The present invention can also contain the ultraviolet absorbers that is selected from S-triazine, oxalyl pentanoic, dihydroxy benaophenonel, benzoic ether and alpha-acrylic hydrocyanic ester in addition.
Specifically, this composition can also contain at least a 2-hydroxyphenyl-2H-benzotriazole of effective stable quantity, another kind of three-aryl S-triazine or hindered amine or its mixture.
Preferred 2-hydroxyphenyl-2H-benzotriazole is selected from: 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl)-2H-benzotriazole, 2-[2-hydroxyl-3,5-two (α, the alpha, alpha-dimethyl benzyl) phenyl]-the hot phenyl of 2H-benzotriazole, 2-[2-hydroxyl-3-(α, alpha, alpha-dimethyl benzyl)-uncle 5-]-2H-benzotriazole, the 2-{2-hydroxyl-3-tertiary butyl-5-[2-(ω-hydroxyl-eight (inferior ethoxyl) carbonyl) ethyl] phenyl }-the 2H-benzotriazole; And the 2-{2-hydroxyl-3-tertiary butyl-5-[2-(octyloxy) carbonyl) ethyl] phenyl }-the 2H-benzotriazole.
Preferably, 2-hydroxyphenyl-2H-benzotriazole also can be selected from:
(a) 5-trifluoromethyl-2-(the hot phenyl of 2-hydroxy-3-alpha-cumyl--uncle 5-)-2H-benzotriazole;
(b) 5-trifluoromethyl-2-(the hot phenyl of 2-hydroxyl-uncle 5-)-2H-benzotriazole;
(c) 5-trifluoromethyl-2-(2-hydroxyl-3, the hot phenyl of 5-two uncles)-2H-benzotriazole;
(d) 2,2 '-methylene radical-two [the hot phenol of 6-(5-trifluoromethyl-2H-benzotriazole-2-yl)-uncle 4-];
(e) methylene radical-uncle 2-[4-octyl group-6-(2H-benzotriazole-2-yl) phenol] 2 '-[uncle 4-octyl group-6-(5-trifluoromethyl-2H-benzotriazole-2-yl) phenol];
(f) 3-(5-trifluoromethyl-2H-benzotriazole-2-yl)-5-tertiary butyl-4-hydroxy benzylacetic acid;
(g) 3-(5-trifluoromethyl-2H-benzotriazole-2-yl)-uncle's 5-octyl group-4-hydroxyl hydrogenation methyl cinnamate;
(h) 3-(5-trifluoromethyl-2H-benzotriazole-2-yl)-different monooctyl ester of 5-tertiary butyl-4-hydroxy phenylpropionic acid;
(i) 5-trifluoromethyl-2-[2-hydroxyl-5-(3-hydroxypropyl) phenyl]-the 2H-benzotriazole;
(j) 5-trifluoromethyl-2-[2-hydroxyl-5-(3-acryloxy propyl group) phenyl]-the 2H-benzotriazole;
(k) 5-trifluoromethyl-2-[2-hydroxyl-5-(3-methacryloxypropyl) phenyl]-the 2H-benzotriazole;
(l) 5-trifluoromethyl-2-[2-hydroxyl-5-(3-acrylamido propyl group) phenyl]-the 2H-benzotriazole;
(m) 5-trifluoromethyl-2-[2-hydroxyl-5-(3-methacrylamido propyl group) phenyl]-the 2H-benzotriazole;
(n) 5-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl--5-trimethylphenylmethane base)-2H-benzotriazole;
(o) 5-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl--5-nonyl phenyl)-2H-benzotriazole;
(p) 5-trifluoromethyl-2-[2-hydroxy-3-alpha-cumyl--5-(2-hydroxyethyl) phenyl]-the 2H-benzotriazole;
(q) 5-trifluoromethyl-2-[2-hydroxy-3-alpha-cumyl--5-(3-hydroxypropyl) phenyl]-the 2H-benzotriazole;
(r) 5-trifluoromethyl-2-(2-hydroxyl-3,5-two uncles penta phenyl)-2H-benzotriazole;
(s) 5-trifluoromethyl-2-(2-hydroxyl-3,5-two trimethylphenylmethane bases)-2H-benzotriazole;
(t) 5-trifluoromethyl-2-(2-hydroxyl-3-lauryl-5-tolyl)-2H-benzotriazole;
(u) 5-trifluoromethyl-2-(the 2-hydroxyl-3-tertiary butyl-5-(3-hydroxypropyl) phenyl)-2H-benzotriazole;
(v) 5-trifluoromethyl-2-(the 2-hydroxyl-3-tertiary butyl-5-(2-hydroxyethyl) phenyl)-2H-benzotriazole;
(w) 5-trifluoromethyl-2-(2-hydroxyl-5-(2-hydroxyethyl) phenyl)-2H-benzotriazole;
(x) 5-trifluoromethyl-2-(2-hydroxyl-3,5-two-α-cumyl phenyl)-2H-benzotriazole;
(y) 5-fluoro-2-(2-hydroxyl-3,5-two-α-cumyl phenyl)-2H-benzotriazole;
(z) 5-fourth alkylsulfonyl-2-(2-hydroxyl-3,5-two-α-cumyl phenyl)-2H-benzotriazole;
(aa) 5-fourth alkylsulfonyl-2-(2-hydroxyl-3,5-two-tert-butyl-phenyl)-2H-benzotriazole;
(bb) 5-fourth alkylsulfonyl-2-(2-hydroxyl-3,5-two-uncle octyl phenyl)-2H-benzotriazole;
(cc) 5-benzenesulfonyl-2-(2-hydroxyl-3,5-two-tert-butyl-phenyl)-2H-benzotriazole.
Preferably, another triaryl S-triazine is selected from:
2,4-two (2, the 4-3,5-dimethylphenyl)-6-(2-hydroxyl-4-octyloxyphenyl)-S-triazine;
2,4-phenylbenzene-6-(2-hydroxyl-4-hexyloxy phenyl)-S-triazine;
2,4-two (2, the 4-3,5-dimethylphenyl)-6-[2-hydroxyl-4-(3-12/tridecane oxygen base-2-propoxyl)-phenyl]-the S-triazine; And
2-(2-hydroxyethylamino)-4,6-two [N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-are sent pyridine-4-yl) amino]-S-triazine.
The present invention treats that stable other materials is recording materials.These materials for example are Research Disclosure1990, and 31429 (474-480 pages or leaves) are described those that are used for photographic reproduction and other reprography technology.
Novel recording materials comprise those that for example are used for pressure-sensitive copy system, microcapsule photoprinter system, thermal copying machine system, photographic material and spray ink Printing.
Novel photographic material can be black and white or color photographic materials; Preferred color photographic materials.The detailed description of the structure of color photographic materials and the component that can be used for this type material can find in the publication that United States Patent (USP) 5538840A the 27th hurdle the 25th row-Di 106 hurdles the 16th row and this paper quote as proof; These sections among the US5538840A are incorporated herein by reference.In the document, the purposes of this novel cpd is mainly described as ultraviolet absorbers or hindered amine stabilizer.Most important component, particularly coupler are described in the United States Patent (USP) 5578437.
Can stablize with acrylic resin paint fast light, wet and oxygen according to the present invention is acrylic resin baking finish or the thermosetting resin that comprises the acrylic/melamine system traditionally, they are at for example H.Kittel ' s " Lehrbuch andBeschichtungen " Vol.1, Part 2 on pages, 735 and 742 (Berlin 1972), " Lackkunstharze " (1977) by H.Wagner and H.F.Sarx on pages 229-238, and is at S Paul ' s " Surface Coatings:Science and Technology ", and (1985) have description.
Can be stabilized with fast light and wet polyester lacquer is traditionally baking finish, as H.Wagner and H.F.Sarx, and op.cit., on pages 86-99 is described.
It is traditionally baking finish that the present invention can stablize with fast light and wet alkyd varnish, it is used in particular for applying automobile (automobile final lacquer), it for example is the lacquer (referring to H.Wagner and H.F.Sarx, " Lackkunstharze " (1977) pages 99-123) of base-material with alkyd/melamine resin and alkyd/acrylic/melamine resin.Other linking agents comprise glycoluril resin, block or the not isocyanic ester or the Resins, epoxy of block.Other enamel-covers that can be stable draw together have the crosslinkable official can be as those of carbamate and siloxanes.
Suitable to metal extreme trace coating and solid shading final lacquer according to the present invention through stable lacquer, particularly as retouching final lacquer (retouching finishes) and different coil coating purposes.According to the present invention through the preferably coating in a conventional manner of stable lacquer, perhaps with a step coating process or a coating process neither.In one method of back, at first coating contains the priming paint of pigment, then with the Clear paint coating in the above.
Although main in this application being stressed that through acid catalyzed not road baking vanish, but it should be noted that also compound of the present invention can be used for non-acid catalyzed thermosetting resin such as epoxy, epoxy-polyester, ethene, alkyd, vinylformic acid and vibrin, optionally uses silicon, isocyanic ester or tricarbimide ester modified.This epoxy and epoxy polyester resin are crosslinked as acid, acid anhydrides, amine etc. with traditional linking agent.Therefore, this epoxide can be used for different vinylformic acid or polyester resin systems as linking agent, in the presence of reactive group on backbone structure through modification.
Based on solvent-free tackiness agent, the consumption of stabilizer compounds of the present invention is 0.1-5wt%, preferred 0.5-2wt%.Can or be dispersed in the common organic solvent or water the tackiness agent dissolving, also can be solvent-free.
When using for two steps applied the road lacquer, compound of the present invention can be added Clear paint or at Clear paint with contain in the priming paint of pigment and all add.
In order to obtain maximum light stability, it is best using simultaneously with other photostabilizers of tradition.The example of ultraviolet absorbers has benzophenone, benzotriazole, acrylic acid derivative, phenylbenzene oxalamide, aromatic base S-triazine or containing metal class (for example organic nickel compound).In two step application systems, can add these additional photostabilizers to Clear paint and/or contain in the pigment priming paint.
If use the stablizer of combination like this, based on film-forming resin, the amount of all photostabilizers is 0.2-20wt%, preferred 0.5-5wt%.
When but hope obtains water-soluble, water mixing or the dispersible coating of water, can on the acidic-group of resin, form ammonium salt.Can be with glycidyl methacrylate and selected alkoxide component prepared in reaction powder paint compositions.
Can expect equally, when compound of the present invention uses together with water-soluble China ink and relevant polarity position application, when wherein hydroxyl provides the better compatibleness performance relevant with this water pendular ring border, can find that compound of the present invention is valuable especially.
The compounds of this invention also can be used for stablizing disclosed acid catalyzed thermosetting resin in the United States Patent (USP) 5112890, and relevant portion is incorporated herein by reference.
These resins are used for baking vanish or baking finish.Known hindered amine as light stabilizer can be stablized the organic substrate main body that comprises the polymkeric substance that is subject to oxygen and photo damage effectively.These hindered amine as light stabilizer be used for stablizing the Synolac or the acrylic metallic baking paint (referring to United States Patent (USP) 4426472) of thermally cross-linkable and be used for stable with heat cross-linking acrylic polyester or Synolac be base-material through acid catalyzed baking vanish (referring to United States Patent (USP) 4344876 and 4426471).There is not a kind of hindered amine as light stabilizer to have the structure of O-substituted hydroxy direct substitution on the hindered amine nitrogen atom in these patents.The compounds of this invention has this replacement, and the alkalescence than the NOR compound of describing in the United States Patent (USP) 5112890 is lower in addition, referring to embodiments of the invention 114.
On its industrial application, having with cross-linked acrylic acid, polyester, urethane or Synolac is that the lacquer of the high solid content of base-material solidifies with additional acid catalyst.The photostabilizer that contains alkaline nitro seldom yields satisfaction in this uses.Salt form between acid catalyst and the photostabilizer makes this salt incompatible or insoluble, make that the sodified water pancake is low and anti-light effect is reduced and wet fastness poor.
Can accept for its function when finally using, this acid catalysis thermo-setting paint must be through stable.Used stablizer is a hindered amine, preferred those that on nitrogen-atoms, are replaced by the inertia blocking group, to prevent carrying out basic amine and acid catalyst precipitates along with solidified, optionally can with above-mentioned ultraviolet absorbers combination.Another section is solidified paint relatively, and this stablizer must be more durable (by gloss, image definition, crackle or the chalk rating under 20 °).(the normal baking of automobile final lacquer is at 121 ℃ in this not overslaugh of stablizer curing, lower baking is repaired at 82 ℃), this can pass through hardness, viscosity, solvent resistance and wet fastness and measure, lacquer is not answered flavescence in solidification process, the colored change should be minimum under the light being exposed to, stablizer should dissolve in the organic solvent commonly used in the application of paints, for example the just own ester of Methyl amyl ketone, dimethylbenzene, acetic acid, alcohol etc.
The hindered amine as light stabilizer of the present invention that is contained the O-replacement of free hydroxyl on nitrogen-atoms satisfies each above-mentioned needs, can provide separately or provide with having good light ultraviolet absorbers stable and protection curing acid catalysis thermo-setting paint.
The present invention also provides can abundant at ambient temperature solidified resin system.For example, the available resin comprises as S.Paul ' s " Surface Coatings:Science and Technology " (1985), the described alkyd of pages70-310, vinylformic acid, polyester and Resins, epoxy.Various vinylformic acid and the acrylic resin modified H.Kittel ' s " Lehrbuch der Lacke unde Beschichtungen " that is described in, Vol.1, Part 2, on pages 735 and 742 (Berl in 1972), and " Lackkunstharze " (1977) by H.Wagnerand H.F.Sarx, op.cit is among the on pages 229-238.Can stablize with typical crosslinked polyester resin fast light, moisture and be described in for example H.Wagner and H.F.Sarx, op.c it. is among the on pages 86-89.Non-modified that can be stable and be the common resins of commercially available use, maintenance and automobile smoothing coating through the Synolac of modification.For example these coating are base-material with Synolac, alkyd/acrylic resin and alkyd/silicone resin (referring to H.Wagner and H.F.Sarx, op.cit., on pages99-123), optionally by isocyanic ester or cross linking of epoxy resin.
Other various acrylic paint coating compositions are disclosed in United States Patent (USP) 4162249.In United States Patent (USP) 4471083, disclose other vinylformic acid/Synolac, in United States Patent (USP) 4525521, described the acrylic resin that contains side group urethano or glycidyl with polyisocyanate ester additive.
The self-vulcanizing coating stable by The compounds of this invention both had been suitable for the metal final lacquer, also was suitable for solid shading lacquer, particularly retouched final lacquer.The lacquer stable by The compounds of this invention preferably applies with 2 kinds of traditional ways, perhaps a step coating process or two step coating processs.In one method of back, at first coating contains the priming paint of pigment, then varnish is applied on it.When using two to go on foot coating process, hindered amine compound of the present invention can be added in the varnish, also can all add in varnish and pigment base-material priming paint.
The present invention also provides the suitable coating composition that is coated in the wear-resisting wiping on the polycarbonate.These coating of describing at United States Patent (USP) 5214085 comprise acrylic silane ester, water-based colloid silica, photoinitiator and optionally multifunctional acrylic ester and ultraviolet absorbers.These coating be exposed to when outdoor can long-term anti-sunlight, moisture, the thermal cycling flavescence, the layering that cause, avoid forming tiny crack and the transparency reduces.
Described hindered amine stabilizer can use separately, also can use to improve the performance of indoor solidified vanish system with ultraviolet absorbers.Although passed through such improvement, still need further to prevent the photoxidation and the photodegradation of these self-vulcanizing systems, therefore the effect of increase is provided by the physical integrity that keeps coating.These effects can by prevent the coating embrittlement, split, burn into etch, loss of gloss, efflorescence and flavescence confirm.
Confirm that now aforesaid improvement can realize that use these derivatives in United States Patent (USP) 5124378 instruction to be arranged, it is incorporated herein by reference by replacing with-OR group in the self-vulcanizing vanish system on the nitrogen-atoms of hindered amine.The alkalescence of this compound low than in the United States Patent (USP) 5124378, and suitable especially this task.Specifically, the physical integrity of coating be can keep, and gloss forfeiture and flavescence greatly reduced.Therefore, the present invention relates to the purposes of this NOR compound, wherein the R group is further replaced by hydroxyl, optionally to be used from equalization chamber's temperature coating material solidified with other stablizers one, the base-material of these coating is a Synolac, the thermofixation acrylic resin, the vinylformic acid Synolac, optionally use silicon, isocyanic ester, chlorinated isocyanurates, the vinylformic acid Synolac or the vibrin of ketoimine or oxazolidine modification, and use carboxylic acid, acid anhydrides, the Resins, epoxy that polyamine or mercaptan are crosslinked, with with the reactive group modification on its main chain with epoxy crosslinked vinylformic acid and polyester resin systems, fast light, wet and oxygen is degraded.
The present invention also relates to be applied to the electrocoating paint on the metal matrix, wherein can apply various surface coating materials thereon.The inclusion of The compounds of this invention has prevented described electrocoating paint layering in electrocoating paint.Initial resin in described electrocoating paint is vinylformic acid or Resins, epoxy.These electrocoating paints have description in EP0576943A1.
The present invention also provides the ultraviolet-curing paint system that uses unsaturated acrylic resin, urethane acrylate, epoxy acrylate, polyester acrylate, unsaturated polyester/styrene resin and acrylic silane ester.
Powder coating
The present invention also provides the powder coating goods that need fast light degraded.The resin system of coating is comprised with the crosslinked glycidyl methacrylate of bisgallic acid or acid anhydrides or the vinylformic acid or the acrylic acid mixture of acrylate-functional, with the crosslinked acid of TGIC or the vinylformic acid or the vibrin of anhydride-functional, with the vinylformic acid or the vibrin of isocyanate-crosslinked hydroxyl-functional.One deck can be on substrate, applied through stable coating, perhaps one deck varnish can be on water-based or solvent priming paint, applied.
Also can contain the ultraviolet absorbers of forming by one of above-claimed cpd through stable coating.
The radiation curing system
The present invention also provides the radiation curable coating system.These systems composed as follows:
A. vinyl unsaturated polymerizable compound
B. at least a photoinitiator
C. one or more stable compounds of the present invention.
This coating composition also can comprise a kind of ultraviolet absorption stablizer as herein described.
This coating can comprise that also pigment or other tinting materials are to provide opaque or aesthetic characteristic.
Vinyl unsaturated polymerizable compound can contain the two keys of one or more alkenes.They can be molecular weight low (monomer) or molecular weight height (oligomeric) compound.
The monomeric exemplary that contains two keys is the acrylate or the methacrylic ester of alkyl or hydroxyalkyl, for example the methyl esters and the ethyl ester of methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethylmethacry,ate, vinylformic acid Isobornyl and methacrylic acid.These monomeric other examples be vinyl cyanide, acrylamide, Methacrylamide, N-replace (methyl) acrylamide, as the vinyl acetate of vinyl acetate, vinyl ether such as IVE, vinylbenzene, ring-alkylated styrenes, halogenated styrenes, N-vinyl pyrrolidone, vinylchlorid and vinylidene chloride.
The monomeric example that contains a plurality of pairs of keys is a glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, the cyclohexanediol diacrylate, bisphenol a diacrylate, 4,4 '-two (2-acryloyl-oxy base oxethyl) diphenyl propane, three methyl alcohol propyl group triacrylates, pentaerythritol triacrylate and tetraacrylate, tetramethylolmethane base divinyl ether, vinyl acrylate, Vinylstyrene, succsinic acid divinyl ester, Phthalic acid, diallyl ester, triallyl phosphate, triallyl isocyanurate or three (2-acryloyl ethyl) chlorinated isocyanurates.The example of the poly-unsaturated compound of high molecular (oligomeric) is acrylic Resins, epoxy, acrylic polyethers, acrylic urethane and acrylic polyester.Other examples of unsaturated oligomer are unsaturated polyester resins, and it is usually by toxilic acid, phthalic acid and the preparation of one or more dibasic alcohol, and its molecular weight is greater than about 500.This class unsaturated oligomer is also referred to as prepolymer.
The exemplary of unsaturated compound is the ester of vinyl unsaturated carboxylic acid and polyvalent alcohol or polyepoxide, with the polymkeric substance that on main chain or side chain, contains the vinyl unsaturated group, comprise unsaturated polyester, polymeric amide and urethane and its multipolymer, the multipolymer of the multipolymer of polyhutadiene and divinyl, polyisoprene and isoprene, the polymkeric substance and the multipolymer that contain (methyl) acrylic acid groups at side chain, and the compound of one or more these polymkeric substance.
The example of described unsaturated carboxylic acid is vinylformic acid, methacrylic acid, Ba Dousuan, methylene-succinic acid, styracin, as linolenic acid or oleic unsaturated fatty acids.Preferred vinylformic acid and methacrylic acid.
Suitable polyvalent alcohol is the also preferred aliphatic series and the cycloaliphatic polyol of fragrance.Aromatic polyol is quinhydrones, 4 typically, 4 '-dihydroxyl phenylbenzene, 2,2-two (4-hydroxy phenyl) propane and phenolic varnish and cresols.Polyepoxide comprises that the polyvalent alcohol that is cited is those of basis, preferably based on aromatic base polyvalent alcohol and epoxy chloropropane.Other suitable polyvalent alcohols are the polymkeric substance and the multipolymer of hydroxyl on main polymer chain or side chain, for example polyvinyl alcohol and its multipolymer or hydroxyalkyl polymethacrylate or its multipolymer.Other suitable polyvalent alcohols are the oligomer esters with the hydroxyl ending.
The example of described aliphatic series and cycloaliphatic polyol is the aklylene glycol that preferably contains the 2-12 carbon atom, comprise ethylene glycol, 1,2-or 1, ammediol, 1,2-, 1,3-or 1, the 4-butyleneglycol, pentanediol, hexylene glycol, ethohexadiol, 12 carbon glycol, glycol ether, triglycol, molecular weight is preferably the polyoxyethylene glycol of 200-1500,1,3-encircles pentanediol, 1,2-, 1,3-or 1, the 4-cyclohexanediol, 1, the 4-hydroxymethyl-cyclohexane, glycerine, three (beta-hydroxyethyl) amine, trimethoxy-ethane, trimethoxy propane, tetramethylolmethane, Dipentaerythritol and Sorbitol Powder.
These polyvalent alcohols can be through partially or completely esterification of unsaturated carboxylic acid a kind of or not of the same race, and wherein the free hydroxyl of part ester can be modified, for example etherificate or with other carboxylic esterifications.
The example of carboxylicesters is: Viscoat 295, the trimethylolethane trimethacrylate acrylate, trimethylolpropane trimethacrylate, the trimethylolethane trimethacrylate methacrylic ester, 1, the 4-butylene glycol dimethacrylate, the triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, the Dipentaerythritol diacrylate, the Dipentaerythritol triacrylate, the Dipentaerythritol tetraacrylate, Dipentaerythritol five acrylate, dipentaerythritol acrylate, tripentaerythritol eight acrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, the Dipentaerythritol dimethacrylate, Dipentaerythritol tetramethyl-acrylate, tripentaerythritol prestox acrylate, the tetramethylolmethane diitaconate, Dipentaerythritol three itaconic esters, Dipentaerythritol five itaconic esters, Dipentaerythritol six itaconic esters, glycol diacrylate, 1, the 3-butylene glycol diacrylate, 1, the 3-butylene glycol dimethacrylate, 1,4-butyleneglycol diitaconate, the Sorbitol Powder triacrylate, the Sorbitol Powder tetraacrylate, the triacrylate of tetramethylolmethane modification, Sorbitol Powder tetramethyl-acrylate, Sorbitol Powder five acrylate, Sorbitol Powder six acrylate, oligomer ester acrylate and methacrylic ester, glycerine two and triacrylate, 1,4-hexanaphthene diacrylate, having molecular weight is the double methacrylate and the double methyl methacrylate of the polyoxyethylene glycol of 200-1500, or its mixture.Polyfunctional monomer and oligopolymer for example can be from UCB Chemicals, Smyrna, and Georgia, and Sartomer, Exton, Pennsylvania obtains.
Suitable vinyl unsaturated polymerizable compound is the acid amides of the carboxylic acid of identical or different unsaturated fragrance, cyclic aliphatic and aliphatic poly-amine equally, and this polyamine preferably contains 2-6, particularly 2-4 amino.The example of these polyamine is quadrols, 1,2-or 1,3-propylene diamine, 1,2-, 1,3-or 1,4-butanediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine, octamethylenediamine, dodecane diamines, 1,4-diamino-cyclohexane, isophorone diamine, inferior phenylenediamine, benzidine, two (β-aminoethyl) ether, diethylenetriamine, Triethylenetetramine (TETA), two (β-ammonia oxyethyl group) ethane or two (β-ammonia propoxy-) ethane.Other suitable polyamine are to contain other amino polymkeric substance and multipolymer and to contain amino oligoamide endways at side chain.
The example of these unsaturated amides is: methylene diacrylamine, 1,6-cyclohexyl diacrylamine, diethylenetriamine trimethylammonium acrylamide, two (Methacrylamide propoxy-) ethane, Beta-methyl acrylamido ethyl-methyl acrylate, N-[(β-hydroxy ethoxy) ethyl] acrylamide.
Suitable unsaturated polyester and polymeric amide typically obtain from toxilic acid and dibasic alcohol or diamines.Toxilic acid can part be substituted by other dicarboxylic acid such as fumaric acid, methylene-succinic acid, citraconic acid, methylfumaric acid or chloromaleic acid.For the reactivity of controlling polyester and influence degree of crosslinking and product property, can use saturated dicarboxylic acid such as phthalic acid, m-phthalic acid, terephthalic acid, tetrahydrochysene phthalic acid, succsinic acid or the hexanodioic acid of the difference amount except that unsaturated dicarboxylic acid.Unsaturated polyester can use with vinyl unsaturated comonomer such as vinylbenzene.Polyester and polymeric amide also can obtain from dicarboxylic acid and the unsaturated dibasic alcohol of vinyl or diamine, and particularly those of long-chain that contain the 6-20 carbon atom from the typical case obtain.Urethane obtains from saturated or unsaturated vulcabond and unsaturated and saturated dibasic alcohol typically.
The polyester of suitable polyester acrylate or acrylic by oligopolymer with as the reaction acquisition of the acrylate of Hydroxyethyl acrylate or Propylene glycol monoacrylate, this oligopolymer is epoxy compounds, urethane, polyethers or polyester typically.
Polyhutadiene and polyisoprene and their multipolymer are known.Suitable comonomer comprises alkene such as ethene, propylene, butylene, hexene, (methyl) acrylate, vinyl cyanide, vinylbenzene or vinylchlorid.The polymkeric substance that contains (methyl) acrylate in side chain is also for known.Typically they can be to be the homopolymer of Resins, epoxy and (methyl) acrylic acid reaction product, polyvinyl alcohol of base-material or multipolymer or their with phenolic varnish with the hydroxyalkyl derivant of (methyl) acroleic acid esterification or with the homopolymer and the multipolymer of (methyl) acrylate of hydroxyalkyl (methyl) acrylate esterification.
Preferred monomer is alkyl or hydroxyalkyl acrylates or methacrylic ester normally, vinylbenzene, glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, cyclohexyl omega-diol diacrylate or bisphenol a diacrylate, 4,4 '-two (2-acryloyl-oxy base oxethyl) diphenyl propane, Viscoat 295, pentaerythritol triacrylate or tetraacrylate, preferred acrylate, vinylbenzene, cyclohexyl glycol or bisphenol a diacrylate, 4,4 '-two (2-acryloyl-oxy base oxethyl) diphenyl propane or Viscoat 295.
Particularly preferred (oligomeric) poly-unsaturated compound is polyester acrylate or the unsaturated polyester resin that is typically 500-3000 by the molecular weight of toxilic acid, fumaric acid, phthalic acid and the preparation of one or more dibasic alcohol.
Preferred unsaturated carboxylic acid is vinylformic acid and methacrylic acid.
The compound of photopolymerization itself just can use, and perhaps uses with required arbitrarily mixture.The preferred mixture that uses polyvalent alcohol (methyl) acrylate.
Tackiness agent can be added in the compound of unsaturated photopolymerization.If the compound of photopolymerization is liquid state or viscous substance, the interpolation of tackiness agent is particularly useful.In whole composition, adhesive consumption can be 5-95%, preferred 10-90%, most preferably 40-90wt%.The selection of tackiness agent relies on use field and its desired properties, as composition in water liquid and organic solvent system the unfolded ability, on substrate adhesive capacity and to the susceptibility of oxygen.
Usually, Shi Yi tackiness agent is that molecular weight is about 5000-2000000; The polymkeric substance of preferred 1000-1000000.Described example is: the homopolymer of acrylate and methacrylic ester and multipolymer, they comprise the multipolymer of methyl methacrylate/ethyl acrylate/methacrylic acid, poly-(alkylmethacrylate), poly-(alkyl acrylate), cellulose ester and for example cellulose acetate, Mierocrystalline cellulose acetyl butyl ester, methylcellulose gum, the ether of cellulose of ethyl cellulose, the polyethylene butyraldehyde, polyethylene formaldehyde, thermoprene, as polyethylene oxide, poly(propylene oxide), the polyethers of polytetrahydrofuran, polystyrene, polycarbonate, urethane, chlorinatedpolyolefins, polyvinyl chloride, the multipolymer of vinylchlorid/Ethylene Dichloride, the multipolymer of Ethylene Dichloride and vinyl cyanide, methyl methacrylate and vinyl acetate, polyvinyl acetate (PVA), copolymerization (ethylene/vinyl acetate), as the polymkeric substance of polycaprolactam and poly-(cyclohexyl hexanediamide), as the polyester of poly-(glycol terephthalate) and poly-(cyclohexanediol succinate).
Unsaturated compound also can use with the form of the mixture of non-photopolymerisable film-forming components.These components can be through polymkeric substance or its solution at organic solvent of physical dryness, for example nitrocellulose or Mierocrystalline cellulose acetyl butyl ester.The unsaturated monomer of photopolymerization can be free redical ion solidified blend, for example blend of free redical cationic curing.The system of it is also important that can stand light and heat and induce cure cycle, for example is used for powder coating, laminating material, some tackiness agent and conformal coating.
Then prepolymer and the mixture that contains the poly-unsaturated monomer of other unsaturated monomers are used for the lacquer system.Prepolymer in this example has determined the performance of paint film at first, and by changing it, those skilled in the art can influence the performance of cured film.Poly-unsaturated monomer plays a part to make the undissolved linking agent of paint film.The react effect of thinner of single unsaturated monomer reduces its viscosity, and needn't use solvent.And the performance of curing composition such as curing ratio, degree of crosslinking and surface property rely on monomeric selection.
Unsaturated polyester resin with two-component system and single unsaturated monomer, preferably uses with vinylbenzene usually.
Bifurcation is rich in electronics/contain the few monomer system of electronics in being usually used in stiff pigment coating.For example, Vinyl Ether/unsaturated polyester system is used for powder coating and vinylbenzene/unsaturated polyester system is used for gel coating.
Preferred method is that therein ethylene base unsaturated polymerizable compound is following mixture: (i) at least a oligomeric compound and (ii) at least a monomeric mixture.
Beneficial method is that therein ethylene base unsaturated polymerizable compound is following mixture: (i) unsaturated polyester, particularly the molecular weight that is made by toxilic acid, fumaric acid and/or phthalic acid and one or more dibasic alcohol is those and (ii) acrylate, methacrylic ester or vinylbenzene or its combination of 500-3000.
One important method is that therein ethylene base unsaturated polymerizable compound is following mixture: (i) unsaturated polyester and (ii) acrylate or methacrylic ester or its combination.
Another useful method is that therein ethylene base unsaturated polymerizable compound is following mixture: (i) unsaturated polyester acrylate and (ii) acrylate or methacrylic ester or its combination.
Synthetic compound
What compound of the present invention can be captured the reaction of tributyl one hydrogen tin and halohydrin by nitryl compound with preparation is the free radical at center with carbon.
Compound of the present invention also can be by preparing N-oxygen base hindered amine and the free radical coupling that with carbon is the center, and the free radical that should be the center with carbon is under the situation that alcohol is arranged peresters or dialkyl peroxide to be carried out photochemistry or thermolysis generation.When two nitroxyl radicals and the coupling of same solvent molecule, particularly when quantity of solvent reduces, can form above-mentioned endo compound.
The preferred method for preparing compound of the present invention be with N-oxygen base hindered amine be the free radical reaction at center with carbon, should be that the free radical at center is with metal ion such as Fe with carbon 2+, Fe 3+, Cu 2+Or Cu +The aqueous solution or alcoholic solution with under the situation of alcoholic solvent, mixes generation down as the superoxide of tetrabutylammonium hydrogen superoxide at 20-80 ℃.Iron protochloride, iron(ic) chloride or ferrous sulfate are the most effective, particularly iron protochloride or iron(ic) chloride and hydrogen peroxide.Can in alcohol, add water at first with the solubleness that improves metal-salt or to be dissolved under the temperature of reaction be solid-state alcohol in reaction.Can be with as 2,2 '-dipyridyl, 2,2 ': 6 ', 2 " part of-four pyridyl adds in the reaction mixture.Sometimes two nitroxyl radicals can with identical solvent molecule coupling to make the endo compound described in the more listed formulas in front.When the amount of solvent reduces, easier formation endo compound.
The N-alkoxy compound that hydroxyls more of the present invention replace also can with simple function or two sense esters, acid or sour muriate or isocyanate reaction formation polyester or urethane derivatives.
Therefore, another object of the present invention is the method for the hindered amine that replaces of the N-(hydroxyl alkoxyl group) of a kind of synthesis type IV:
Figure A0010651500741
Wherein
G 1And G 2The alkyl of 1-4 carbon atom, perhaps G respectively do for oneself 1And G 2It all is pentylidene;
T is a divalence oxygen base free radical, require to realize containing five or six-ring of hindered amine carbon atom and two by G 1And G 2The quaternary ammonium carbon atom that replaces;
E is the cycloalkylidene of cycloalkylidene, 5-12 carbon atom of alkylidene group, the 5-12 carbon atom of 2-18 carbon atom (b+1) valency alkylidene group, 3-19 carbon atom or the alkylidene group of the 2-4 carbon atom that phenyl replaced that replaced by phenyl or replaced by 1-2 1-4 carbon atom; And
B is 1,2 or 3; As long as b is no more than the quantity of saturated carbon atom among the E, and when b is 2 or 3, different carbon atoms are continuous among each hydroxyl and the E;
This method comprises
In the presence of metal-salt that superoxide or oxygen base hydrogen peroxide and catalytic amount are arranged or metal ligand complex compound, the N-oxygen base hindered amine of formula V and the alcohol of formula VI are reacted.
Figure A0010651500751
E-(OH) b????(VI)
The N-oxycompound of formula V can pass through with corresponding N-H hindered amine and as E.G.Rozantsev etal., in Synthesis, 1971,192; Described hydrogen peroxide and sodium wolframate reaction, perhaps tertiary butyl hydrogen peroxide and molybdenum (VI) reaction with United States Patent (USP) 4691015 instructions makes.
More particularly, present method relates to the N-oxycompound reaction with the formula V of the mixture of the metal-salt of the hydrogen peroxide of the alcohol of the formula VI of 5-100 mole, 1-15 mole or organic hydroperoxide and 0.001-0.5 mole or metal ligand complex compound and 1 mole.This reaction is preferably carried out under 20-100 ℃ temperature.
Alcohol can have dual-use function promptly be reactant be again the reaction solvent.If the alcohol that reacts in present method contains the c h bond of non-equivalence, then may produce product mixtures.For example, the trimethyl carbinol produces a kind of product only, yet tertiary amyl alcohol can produce three kinds of differential responses products.If when alcohol not too dissolves in alcohol for solid-state or metal-salt or metal ligand complex compound under temperature of reaction, can use solubility promoter.Typical solubility promoter is water, methyl alcohol and ethylene glycol.
In superoxide, present method has mainly been used transition metal salt or the metal ligand complex compound that is less than stoichiometric quantity, this metal is selected from IVA in the periodictable, VA, VIIA, VIIIA or IB family (transition metal, the metal that nucleidic mass is minimum in these families are Ti, V, Mn, Fe, Co, Ni, Cu).Iron (II), iron (III), copper (I) and copper (II) are the most effective catalyzer.Metal can be the form of simple salt such as the muriate or the vitriol of metal, as the metal salts of organic acids of acetic acid, also can contain the cationic metal oxide of periodictable IA or IIA, as sodium metavanadate.This metal also can with the part complexing, part for example has 2,2 '-dipiperidino, ethylenediamine tetraacetic acid (EDTA) or its disodium salt, triphenylphosphine oxidation thing, or methyl ethyl diketone negatively charged ion.The commercially available acquisition of these metal ligand complex compounds or can self mix formation with part by metal-salt.The amount of part can be less than in the required amount of the complete complexing metal of its state of oxidation.Metal-salt or metal ligand complex compound can be bonded on solid-state carrier such as the silica gel, so that it can reclaim and utilize.
Can add mineral acid or sulfonic acid in reaction mixture, its amount can be up to 1 mole in every mole of nitryl.
Present method can be carried out in air or rare gas element such as nitrogen or argon gas.
Present method has several changes.The aqueous solution that a kind of change relates to hydrogen peroxide or organic hydroperoxide adds N-oxygen base hindered amine, pure and mild solubility promoter (if you are using) and acid (if you are using) to, and temperature is reached in the mixture of temperature required metal-salt of reaction or metal ligand complex compound.Interpolation speed or/or use heat or cooling bath maintenance proper temperature by the control superoxide.After adding superoxide, stirred reaction mixture disappears or no longer changes the compound of accepted way of doing sth IV up to the N-oxycompound of the formula V of beginning.The most handy thin layer chromatograph of reaction, vapour phase chromatographic instrument or liquid chromatograph monitoring.When carrying out, reaction can add the metal-salt or the metal-ligand complex of remainder.After initial superoxide all adds in the reaction mixture, several superoxide can be added again so that reaction is carried out thoroughly.
Second change of present method is to add superoxide and nitryl compound solution separately simultaneously in the mixture of alcohol, solubility promoter (if you are using), acid (if you are using) and metal-salt or metal ligand complex compound.In the alcoholic solvent that can be with nitryl compound uses in the water-soluble or reaction.Before adding initial superoxide, a part of nitryl compound can be added in the compound of reaction, and before the interpolation superoxide is finished, all nitryl compounds should be added wherein.
Another change of present method is simultaneously interpolation separates in the mixture of nitryl compound, alcohol, solubility promoter (if with) and acid (if with) the peroxide solutions and the water or the alcoholic solution of metal-salt or metal-ligand complex.Before adding initial superoxide, can in reaction mixture, add a part of metal earlier.
Another change of present method is to add peroxide solutions, the water of nitryl compound or the water or the alcoholic solution of alcoholic solution and metal-salt or metal ligand complex compound separately simultaneously in the mixture of alcohol, solubility promoter (if you are using) and acid (if you are using).Before adding initial superoxide, can be with in a part of nitryl compound and/or metal-salt or the metal-ligand complex adding compound of reaction.Before the interpolation superoxide is finished, all nitryl compounds should be added wherein.
If in reaction, use acid, when the reaction beginning, this part acid can be added, perhaps when the reaction beginning, add a part, remainder when carrying out, is added in reaction; Perhaps add all acid when carrying out when reacting.If reaction when carrying out metal-salt be when adding with solution, part or all sourly can be mixed with metal-salt.
If prepare metal-ligand complex on the spot, the most effective with hybrid metal before nitryl compound contacts and part.
After reaction finished, care should be used to ground decomposed remaining superoxide before separating spawn.
Preferred method
Formula (IV) and (V) in G 1And G 2Be preferably methyl.T is preferably 2-hydroxyl-1,3-glyceryl or 2-oxo-1,3-glyceryl.
When b is 1,-E-(OH) is for preferably by 2-methyl-2-propyl alcohol (=trimethyl carbinol), 2-propyl alcohol, 2, what 2-dimethyl-1-propyl alcohol, 2-methyl-2-butanols, ethanol, 1-propyl alcohol, 1-butanols, 1-amylalcohol, 1-hexanol, 1 nonyl alcohol, 1-decanol, 1-lauryl alcohol, 1-Stearyl alcohol, 2-butanols, 2-amylalcohol, 2-ethyl-1-hexanol, sec-n-octyl alcohol, hexalin, ring octanol, vinyl carbinol, phenylethyl alcohol or 1-phenyl-1-ethanol formed is the free radical at center with carbon, and-E-(OH) is most preferably formed by 2-methyl-2-the propyl alcohol (=trimethyl carbinol) or hexalin.
When b is 2 ,-E-(OH) 2For preferably by 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,4-butyleneglycol, 2,2-dimethyl-1, ammediol, 2,5-dimethyl-2,5-hexylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1, what the 4-cyclohexanediol formed is the free radical at center with carbon, and ,-E-(OH) 2Most preferably by 1,4-butyleneglycol, 2,1,2-cyclohexanediol, 1,3-cyclohexanediol or 1, the 4-cyclohexanediol forms.
When b is 3 ,-E-(OH) 3For preferably by 1,1,1-three (methylol) ethane, 2-ethyl-2-(methylol)-1, ammediol, 1,2, what 4-trihydroxybutane or 1,2,6-hexanetriol formed is the free radical at center with carbon, and ,-E-(OH) 2Most preferably by 1,1,1-three (methylol) ethane or 2-ethyl-2-(methylol)-1, ammediol forms.
B is preferably 1 or 2; Most preferably be 1.
The preferred product of present method is the compound of above-mentioned formula (1)-(30).
Preferred superoxide is addition compound, tertiary butyl hydrogen peroxide, uncle's penta hydrogen peroxide and the cumene hydroperoxide of hydrogen peroxide, urea and hydrogen peroxide.Preferred superoxide is the addition compound of hydrogen peroxide and urea and hydrogen peroxide, most preferably is hydrogen peroxide.
Hydrogen peroxide can be 15-50wt%, the aqueous solution of preferred 30-50wt%.
Preferably, metal is selected from IVA, VA, VIIA, VIIIA and the IB family of periodictable.Be more preferably iron (II), iron (III), copper (I), copper (II), cobalt (II), cobalt (III), manganese (II), manganese (III), vanadium (II), vanadium (III), cerium (III) and titanium (III).Most preferably be iron (II), iron (III), copper (I) and copper (II).
Preferably, the counter ion of metal are muriate, vitriol, acetylacetonate (acac), acetate, Citrate trianion, oxalate, nitrate, perchlorate, prussiate, oxyhydroxide, phosphoric acid salt, hypophosphite and oxide compound above.
Above-mentioned metal ligands preferably 2,2 '-dipyridyl, 2,2 ': 6 '; 2 "-four pyridyl, 1,10-phenanthroline, ethylenediamine tetraacetic acid (EDTA), disodium EDTA, pyridine, pyridine formic acid, 2-pyrazine carboxylic acid, by aniline or the aniline that is substituted and 1, the 2-diketone is as 2, and the 3-dimethyl diketone reacts aromatic base diimine and the triphenylphosphine oxidation thing that generates.
Metal-salt is iron protochloride, iron(ic) chloride, ferric acetyl acetonade, tertiary iron phosphate, ferric hypophosphite, ferrous phosphate, ferrous sulfate, ferric sulfate, Iron diacetate, ironic citrate, Ferrox, ironic oxalate, iron nitrate, Iron triperchlorate, cuprous chloride, cupric chloride, cuprous sulfate, protochloride manganese, sodium metavanadate, titanous chloride, vanadous chloride (II) and vanadium trichloride (III) preferably.Most preferred metal-salt is iron protochloride, iron(ic) chloride, ferric acetyl acetonade, tertiary iron phosphate, ferric hypophosphite, ferrous phosphate, ferrous phosphate, ferrous sulfate, ferric sulfate and cuprous sulfate.
Metal-ligand complex is iron (II), iron (III), copper (I) or copper (II) salt and 2 preferably, 2 '-dipyridyl, triphenylphosphine oxidation thing, ethylenediamine tetraacetic acid (EDTA) or disodium EDTA.Metal-ligand complex most preferably is from iron protochloride or iron(ic) chloride and 2, those of 2 '-dipyridyl.
Acid is spirit of salt, sulfuric acid, methylsulfonic acid, oxalic acid, trifluoroacetic acid, Tripyrophosphoric acid and phosphoric acid preferably; Most preferred acid is methylsulfonic acid, Tripyrophosphoric acid or phosphoric acid.
The preferred amounts that is used for the alcoholic solvent of present method relies on the respective amount of the reactive hydrogen atom on alcohol reactant and the hindered amine nitryl compound to a certain extent.Usually, every mole of nitryl had solvent 5-100 mole when reaction was carried out, and preferred every mole of nitryl has solvent 10-50 mole, and most preferably every mole of nitryl has solvent 10-30 mole.Solubility promoter can be arranged, preferably be selected from water, methyl alcohol, ethylene glycol or its mixture.
In 1 mole of nitryl, the preferred amounts of hydrogen or organic hydroperoxide is the 1-20 mole, more preferably 1-5 mole, most preferably 1-3 mole.
In 1 mole of nitryl, the preferred amounts of metal-salt or metal-ligand complex is the 0.001-0.5 molar equivalent, most preferably is the 0.001-0.05 mole.
If use acid in the method, in 1 mole of nitryl, the preferred amounts of acid is the 0.01-1 molar equivalent, most preferably is the 0.01-0.5 molar equivalent.
Reaction is usually at 20-100 ℃, carries out under preferred 60-100 ℃.
Ensuing embodiment only is a method for example, is not limited to the present invention.Room temperature is that temperature is 20-25 ℃.Abbreviation: v parts by volume w weight part 1Hnmr 1The nucleus magnetic resonance of H (NMR) m/z mass spectroscopy (atomic unit) amu molecular weight is in g/mol (=atomic unit)
The novel method of embodiment P1-P explanation preparation The compounds of this invention.
The purposes of iron(ic) chloride in embodiment P1 explanation present method.
Embodiment P1
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
To in 4 hours, under 45-50 ℃, add 3.44g (20.0mmol) 4-hydroxyl-1-oxygen base-2 to 20mL trimethyl carbinol blended 9.4g (140mmol) 50% aqueous hydrogen peroxide solution, 2,6, in the mixture of 6-tetramethyl piperidine, 0.125g (0.77mmol) Anhydrous Ferric Chloride, the 30mL trimethyl carbinol and 10mL water.Then temperature is remained on 45-50 ℃ and continue 19 hours down.Show the initial nitryl compound that exists less than 1% by the vapor-phase chromatography analysis.
Embodiment P2 has shown at solid-state carrier cocycle use metal catalyst.
Embodiment P2
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Will be on silica gel 2,2 '-dipyridyl (0.16g, 1.0mmol) and 5% the iron(ic) chloride of 2.54g (0.80mmol) stir with the 30mL trimethyl carbinol that is heated to 45 ℃.In this mixture, add 3.44g (20.0mmol) 4-hydroxyl-1-oxygen base-2,2,6,6-tetramethyl piperidine and 10mL water.In four hours, in reaction mixture, adding and 20mL trimethyl carbinol blended 9.4g (138mmol) 50% aqueous hydrogen peroxide solution under 45-50 ℃.Then temperature is remained on 45-50 ℃ and continue 30 hours down.Show that by the vapor-phase chromatography analysis initial nitryl compound complete reaction and formation surpass 90% title compound.
By filtering separation silica gel, use the silica gel that reclaims to repeat above-mentioned test.After adding to nearly all superoxide in the reaction mixture in 4.5 hours, vapor-phase chromatography shows, still has 36% initial nitryl compound.Under 45-50 ℃,, only be left 5% initial nitryl compound with after other 19 hours of the lasting heating of reaction mixture.
Embodiment P3
4-hydroxyl-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and Virahol
With 2, (0.156g 1mmol) adds in the mixture of 30mL Virahol of 0.20g is arranged (1mmol) iron(ic) chloride 2 '-dipyridyl under 40 ℃.In this mixture, add 3.44g (20mmol) 4-hydroxyl-1-oxygen base-2,2,6,6-tetramethyl piperidine and 10mL water.Under 45-50 ℃, in 7 hours, be added on the aqueous solution of 50% hydrogen peroxide that 9.4g (138mmol) is arranged in the 20mL Virahol in upward the mixture.React with the crude reaction mixture cooling and with the 0.5g sodium borohydride.Vapour phase chromatogram/mass spectroscopy shows that the main ingredient of reaction mixture is 4-hydroxyl-1-(2-propoxyl)-2,2,6,6-tetramethyl piperidine (m/z=231).
Embodiment P4
1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine-4-ketone and tertiary amyl alcohol
With 2, (0.078g 0.5mmol) adds in the mixture of 150mL tertiary amyl alcohol of 0.99g is arranged (5.0mmol) four water iron protochlorides 2 '-dipyridyl under 25 ℃.In this mixture, add 0.2g chlorination four fourth ammonia and 17.2g (101mmol) 1-oxygen base-2,2,6,6-tetramethyl piperidine 4-ketone.Under 25-30 ℃, in 3 hours, add the aqueous solution of 50% hydrogen peroxide of 29.5g (434mmol) in upward the mixture.In the superoxide that decomposes, add sodium sulfite aqueous solution.Obtain the 23.4g orange oil with the abundant abstraction reaction mixture of vinyl acetic monomer.Vapour phase chromatogram/mass spectroscopy shows that this oil contains three kinds of principal reaction products, and its ratio was near 2: 2: 1 (area ratio).Along with initial nitryl compound and every kind of carrying out that the possible carbon radicals that is formed by tertiary amyl alcohol reacts, these three kinds of products are consistent.
Embodiment P5
1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine-4-ketone and 1-butanols
Repeat the step of embodiment P4, just the propyl carbinol with 150mL replaces tertiary amyl alcohol.Reaction mixture obtains the 19.2g orange oil.Vapour phase chromatogram/mass spectroscopy shows, three kinds of components in the product mixtures and initial nitryl compound are corresponding with reacting phase from the free radical of 1-butanols extracting hydrogen evolution.
Embodiment P6
1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine-4-ketone and neopentyl glycol
Repeat the step of embodiment P4, just 2 (=neopentyl glycol) and the 55mL water with 400mL replaces tertiary amyl alcohol.Reaction mixture obtains the 14.0g brown oil.
Embodiment P7
1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine 4-ketone and sec-n-octyl alcohol
Repeat the step of embodiment P4, just mixture replaces tertiary amyl alcohol with the sec-n-octyl alcohol of 150mL.In 6 hours, add superoxide under 25-30 ℃, and at room temperature reaction mixture is being stirred a whole night.Reaction mixture obtains the 19.4g orange oil.Vapour phase chromatogram/mass spectroscopy shows, five kinds of components in the product mixtures and initial nitryl compound are corresponding with reacting phase from the free radical of sec-n-octyl alcohol extracting hydrogen evolution
Embodiment P8-P12 illustrates the purposes of mineral acid and different molysite in the method.
Embodiment P8
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
With 17.2g (100mmol) 4-hydroxyl-1-oxygen base-2 that is dissolved in the 40mL water, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 3/4 25.0g (0.37mmol) added under 40 ℃ in 3 hours in the mixture of 98% sulfuric acid of 1.12g (4.0mmol) iron vitriol, 25mL water, 0.5mL and the 200mL trimethyl carbinol simultaneously.Add at the end at nitryl, in reaction mixture, add the iron vitriol of 0.145g (0.5mmol), 98% sulfuric acid of 0.1mL and the water of 1-2mL.In 1 hour, adding remaining 1/4 peroxide solutions under 40 ℃.After 1 hour, in reaction mixture, drip 50% aqueous hydrogen peroxide solution of 2.9g (40mmol), after other 1.3 hours, with whole iron vitriol, 98% sulfuric acid of 0.15mL and the solution of 1-2mL water that adds 0.14g (0.5mmol).Under 40 ℃, reaction mixture was stirred other 40 minutes.After the S-WAT decompose hydroperoxide, use sodium hydroxide and sodium borohydride reaction mixture and warp to concentrate.Resistates is dissolved in the vinyl acetic monomer, obtains the white solid state title compound of 20.5g (84% productive rate) by silica gel.
Embodiment P9
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
With 34.5g (200mmol) 4-hydroxyl-1-oxygen base-2 that is dissolved in the 75mL water, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 49.5g (0.73mmol) added under 40 ℃ in 7 hours in the mixture of 37% spirit of salt of 1.61g (8.1mmol) four water iron protochlorides, 50mL water, 1.6mL and the 390mL trimethyl carbinol simultaneously.When adding about 4 hours, in reaction mixture, add the four water iron protochlorides of 0.22g (1.1mmol), 37% spirit of salt of 0.2mL and the water of 1-2mL.Stirred reaction mixture whole night at room temperature.The solution of the water of four water iron protochlorides by adding 0.11g (0.55mmol), 37% spirit of salt of 0.1mL and 1-2mL and 50% aqueous hydrogen peroxide solution of 5.8g (85mmol) is simultaneously at 40 ℃ of following reacting by heating mixtures, to finish reaction.Filter reaction mixture, is handled also through concentrating with sodium hydroxide and sodium borohydride with the S-WAT cooling to remove solid.Resistates is dissolved in the vinyl acetic monomer, obtains the white solid state title compound of 42.6g (87% productive rate) by silica gel.
Embodiment P10
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
With 17.2g (100mmol) 4-hydroxyl-1-oxygen base-2 that is dissolved in the 50mL water, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 25.3g (0.37mmol) added under 40 ℃ in 3-3.5 hour in the mixture of 37% spirit of salt of 0.27g (1.0mmol) Iron trichloride hexahydrate, 25mL water, 1.1mL and the 200mL trimethyl carbinol simultaneously.When adding about 2 hours, in reaction mixture, add 37% spirit of salt of 0.5mL.Reaction mixture add finish after, add 37% spirit of salt of 1.2mL, and in 40-50 ℃ of following reacting by heating mixture 3.5 hours.Stirred reaction mixture whole night at room temperature.By adding 37% spirit of salt of two parts of 0.3mL, continue 5.5 hours at 45 ℃ of following reacting by heating mixtures simultaneously, to finish reaction.Handle and obtain the white solid state title compound of 21.5g (88% productive rate) as embodiment P9 process.Gas chromatographic analysis shows that product purity is greater than 96%.
Embodiment P11
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
With 17.2g (100mmol) 4-hydroxyl-1-oxygen base-2 that is dissolved in the 40mL water, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 3/4 25.0g (0.37mmol) added under 40 ℃ in 2.5 hours in the mixture of 98% sulfuric acid of 1.46g (4.1mmol) ferric acetyl acetonade, 25mL water, 0.5mL and the 200mL trimethyl carbinol simultaneously.Add at the end at nitryl, in reaction mixture, add the ferric acetyl acetonade of 0.18g (0.5mmol).In 1 hour, adding remaining 1/4 peroxide solutions under 40 ℃.Heat after 2 hours, the vapour phase chromatogram shows, remains the nitryl compound less than 10% in reaction mixture.In 40 ℃ of downhill reaction mixtures, drip 50% aqueous hydrogen peroxide solution of sulfuric acid (0.3mL) and 4.9g (72mmol), and stirred reaction mixture whole night at room temperature.Pass through as the processing among the embodiment P9 white solid state title compound of 18.1g (74% productive rate).
Embodiment P12
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Repeat the step of embodiment P11, just do not add sulfuric acid, after superoxide adds 1.5 hours that finish, initial nitryl compound residue 69%.Under the corresponding time, with the comparison among the embodiment P11, nitryl compound only remains 10%.
Embodiment P13
1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-ketone
In 7.5 hours, 50% aqueous hydrogen peroxide solution of 23.6g (347mmol) is added to the 1-oxygen base-2 of 17.0g (100mmol), 2,6, in the mixture of the four water iron protochlorides of 6-tetramethyl piperidine-4-ketone, 0.994g (5mmol), 37% spirit of salt, the 360mL trimethyl carbinol and the 120mL water of 1mL.Use the Repone K saturated reaction, and extract water layer with the trimethyl carbinol.Compound organic layer is condensed into orange oil.This oil is dissolved in the methylene dichloride, on silica gel with 4: 1 (v/v) hexanes: vinyl acetic monomer purifies by the flash chromatography method.With the crystallization of gained yellow oil, obtain the 8.3g fusing point at 57-60 ℃ white solid.Isolating product is injected the vapour phase chromatogram, identical with the residence time of the standard model of title compound.
The different ligands of embodiment P14, P15 and P16 formula (IV) is to the influence of the compound formation of embodiment P13.
Figure A0010651500821
Embodiment P14
1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-ketone
At the N that in the mixture of the four water iron protochlorides of 0.994g (5mmol) and the 150mL trimethyl carbinol, adds 1.18g (5.0mmol) under 35 ℃ continuously, N '-(1,2-dimethyl-1, the 2-ethanetetrayl) the 1-oxygen base-2 of two (aniline) and 17.0g (100mmol), 2,6,6-tetramethyl piperidine-4-ketone, in formula IV, X is a hydrogen atom.Under 35-40 ℃, in 8 hours, add 50% aqueous hydrogen peroxide solution in upward the mixture with 60mL trimethyl carbinol blended 47.5g (700mmol).Other 16 hours of 40 ℃ of following stirring reactions.Show by gas chromatographic analysis: the initial nitryl solids removed by filtration less than 4% is arranged, the superoxide of filtrate and S-WAT water liquid reaction with decomposing excessive.With the abundant abstraction reaction mixture of ethyl acetate, obtain 21.4g after concentrating and contain the raw product of title compound greater than 93% (based on the vapour phase chromatogram).
Embodiment P15
1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-ketone
Repeat embodiment P14, with the N of 1.48g (5.0mmol), N '-(1,2-dimethyl-1, the 2-ethanetetrayl) two (4-anisidines) (in formula IV, X is a methoxyl group) replace N, N '-(1,2-dimethyl-1, the 2-ethanetetrayl) two (aniline) (in formula IV, X is a hydrogen atom).When reaction finishes, show by gas chromatographic analysis: 3% initial nitryl compound is arranged.After the processing, reaction mixture provides 17.7g to contain the orange material of 97% title compound (based on the vapour phase chromatogram).
Embodiment P16
1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-ketone
Repeat embodiment P14, with the N of 5.0mmol, N '-(1,2-dimethyl-1,2-ethanetetrayl) two (4-chloroanilines) (in formula IV, X is the chlorine atom) replace N, N '-(1,2-dimethyl-1,2-ethanetetrayl) two (aniline) (in formula IV, X is a hydrogen atom).
Embodiment P17
4 benzoic acid base-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
In 2 hours, will add the 4 benzoic acid base-1-oxygen base-2 of the 24.9g (0.090mol) under 60 ℃ with 50% aqueous hydrogen peroxide solution of 50mL trimethyl carbinol blended 18.4g (0.27mol) to, 2,6, in the mixture of the four water iron protochlorides of 6-tetramethyl piperidine, 7.13g (0.036mol), the pyridine formic acid of 3.7g (0.030mol) and the 150mL trimethyl carbinol.After the superoxide interpolation finishes, temperature of reaction is remained on 60 ℃ continue 5 hours.Filter reaction mixture to be removing solid, and stirs 30 minutes superoxide with decomposing excessive of filtrate with 1 liter 10% sodium sulfite solution.To this extraction with aqueous solution three times, make up organic layer with methylene dichloride, finally be concentrated into orange oil with anhydrous magnesium sulfate drying.On silica gel with 4: 1 (v/v) hexanes: vinyl acetic monomer purifies by the flash chromatography method and obtains the 12.0g amber oil.By nmr and mass spectroscopy standard product is title compound.
Embodiment P18 has shown the influence of removing pyridine formic acid from embodiment P17.
Embodiment P18
4 benzoic acid base-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
In 3 hours, will add the 4 benzoic acid base-1-oxygen base-2 of the 27.6g (0.10mol) under 40 ℃ with 50% aqueous hydrogen peroxide solution of 25mL trimethyl carbinol blended 20.4g (0.30mol) to, 2,6, in the four water iron protochlorides of 6-tetramethyl piperidine, 7.13g (0.036mol) and the mixture of the 115mL trimethyl carbinol.After the superoxide interpolation finishes, temperature of reaction is remained on 40 ℃ continue 20 hours.Crude reaction mixture obtains the 16.2g title compound by the purification of flash chromatography method on silica gel.
Embodiment P19
The reaction of two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebates and neopentyl alcohol
According to the step of embodiment 18, in the mixture of two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebates in neopentyl alcohol and iron protochloride, add aqueous hydrogen peroxide solution.
Embodiment P20
4-hydroxyl-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and neopentyl glycol
According to the step of embodiment 18,, add aqueous hydrogen peroxide solution in the mixture of 6-tetramethyl piperidine and iron protochloride to the hydroxyl of the 4-in neopentyl glycol-1-oxygen base-2,2,6.
Embodiment P21
4-stearyl Oxy-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and tertiary amyl alcohol
According to the step of embodiment 18, the 4-stearyl Oxy-1-oxygen base-2,2,6 in tertiary amyl alcohol adds aqueous hydrogen peroxide solution in the mixture of 6-tetramethyl piperidine and iron protochloride.
Embodiment P22
4-stearyl Oxy-1-oxygen base-2,2,6, the reaction of the 6-tetramethyl piperidine and the trimethyl carbinol
According to the step of embodiment 18, the 4-stearyl Oxy-1-oxygen base-2,2,6 in the trimethyl carbinol adds aqueous hydrogen peroxide solution in the mixture of 6-tetramethyl piperidine and iron protochloride.
Embodiment P23
4-stearyl Oxy-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and propylene glycol
According to the step of embodiment 18, the 4-stearyl Oxy-1-oxygen base-2,2,6 in propylene glycol adds aqueous hydrogen peroxide solution in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.
Embodiment P24
1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine-4-ketone and trimethylene glycol
According to the step of embodiment 18, the 1-oxygen base-2,2,6 in trimethylene glycol adds aqueous hydrogen peroxide solution in the mixture of 6-tetramethyl piperidine 4-ketone and four water iron protochlorides.
Embodiment P25
The reaction of two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebates and 2-propyl alcohol
According to the step of embodiment 18, in the mixture of two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebates in the 2-propyl alcohol and four water iron protochlorides, add aqueous hydrogen peroxide solution.
Embodiment P26
4 benzoic acid base-1-oxygen base-2,2,6,6-tetramethyl piperidine and 1, the reaction of 4-butyleneglycol
According to the step of embodiment 18, to 1, the 4 benzoic acid base in the 4-butyleneglycol-1-oxygen base-2,2,6 adds aqueous hydrogen peroxide solution in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.
Embodiment P27
4-hydroxyl-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and tetramethyl ethylene ketone
According to the step of embodiment 18,, add aqueous hydrogen peroxide solution in the mixture of 6-tetramethyl piperidine and four water iron protochlorides to the hydroxyl of the 4-in tetramethyl ethylene ketone-1-oxygen base-2,2,6.
Embodiment P28
4-hydroxyl-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and 2-ethyl-1-hexanol
According to the step of embodiment 18, to the 4-hydroxyl in 2-ethyl-1-hexanol-1-oxygen base-, 2,6, add aqueous hydrogen peroxide solution in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.
Embodiment P38-P47 has shown the effect of different metal in present method.
Embodiment P38
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
With the speed of about 100mmol/hour with 50% aqueous hydrogen peroxide solution and 17.2g (100mmol) 4-hydroxyl-1-oxygen base-2 that will be dissolved in 40-45mL water with the speed of 35-50mmol/hour, 2,6,6-tetramethyl piperidine solution adds in the mixture of the metal-salt, acid (if any), 25mL water and the 200mL trimethyl carbinol that remain under 35-45 ℃ simultaneously.All reactants remain on 35-45 ℃ with reaction mixture after adding, and to a certain degree reaction mixture are at room temperature being stirred whole night.By vapour phase chromatogram monitoring reaction.The results are shown in following table.
Table 1
Use hydrogen peroxide and different metal to form 4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,, 6,6-
Tetramethyl piperidine
The mol% metal aMol% acid aMolesH 2O 2 bProductive rate c
4％CoCl 2??????10％HCl????2.9??????????3％
11％MnCl 3?????10％HCl????3.6??????????16％
4%NaVO 3Do not have 1.5＜1%
4%CeCl 3Do not have 1.5＜1%
4％TiCl 3??????60％HCl????3.5??????????2％
4％VCl 2???????10％HCl????2.2??????????1％
4％VCl 3???????10％HCl????3.6??????????6％
(a) mole number of every mole of nitryl initiation material;
(b) every mole of nitryl causes material and adds superoxide mole number in the reaction to; And
(c) corresponding to the total area of all hindered amine components that occur in the reaction mixture, based on the vapour phase stratographic productive rate of the whole area of title compound.
Embodiment P39
1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-ketone
In 30 minutes, will add the 1-oxygen base-2 of 0.5g (2.9mmol) under 60 ℃ at 50% aqueous hydrogen peroxide solution of the 1.0g in the 5mL trimethyl carbinol (15mmol), 2,6, the N of 6-tetramethyl pyridine-4-ketone, 0.1g (0.16mmol), N '-two (3,5-two-tertiary butyl salicylidene)-1, in the mixture of the trimethyl carbinol of 2-hexamethylene diamino manganese (II) muriate (Jacobsen ' s catalyzer) and 10mL.Reaction stirred whole night under 60 ℃.The vapour phase chromatogram is presented at 2.5% title compound in the reaction mixture.
Embodiment P40
1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-ketone
Repeat the step of embodiment P39, use 0.25g (1.05mmol) seven water cobalt chloride (II) to replace Jacobsen ' s catalyzer.The vapour phase chromatogram is presented at 9% title compound in the reaction mixture.
Embodiment P41
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
To add the 0.16g (1.0mmol) 2 of the 120mL trimethyl carbinol at the 0.25g in the 5mL water (1.0mmol) cupric sulfate pentahydrate (II) solution to, in 2 '-dipyridyl solution.In this solution, add 8.6g (50mmol) 4-hydroxyl-1-oxygen base-2,2,6, the 6-tetramethyl piperidine.Under 23-40 ℃, in 3 hours, will be added drop-wise in the reaction mixture with 50% aqueous hydrogen peroxide solution of 13mL trimethyl carbinol blended 13.6g (200mmol).At room temperature continue to stir the mixture 72 hours then.The vapour phase chromatogram is presented at 9% title compound in the reaction mixture.
Embodiment P42
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
With 34.5g (200mmol) 4-hydroxyl-1-oxygen base-2 that is dissolved in the 75mL water, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 48.1g (0.71mol) added under 35-45 ℃ in 6 hours in the mixture of 37% spirit of salt of 0.79g (8.0mmol) cuprous chloride (I), 50mL water, 1.6mL and the 400mL trimethyl carbinol simultaneously.Stirred reaction mixture whole night at room temperature.Reaction mixture is heated to 40-45 ℃, and the solution-treated of 50% aqueous hydrogen peroxide solution of the cuprous chloride (I) of usefulness 1.78g (1.78mmol), 37% spirit of salt of 4.4mL and 85g (1.25mol) is so that the reaction of residue nitryl compound is thorough.Step process through embodiment P9 obtains the solid-state title compound of 38.6g tawny, is 88% with its productive rate of gas chromatographic analysis.
Embodiment P43
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
To be dissolved in 17.2g (100mmol) 4-hydroxyl-1-oxygen base-2 in the 50mL water simultaneously, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 31.5g (0.46mol) added in 3 and 4.5 hours respectively in the mixture of 37% spirit of salt of 0.69g (4.0mmol) copper chloride dihydrate (II) under 35-50 ℃, 25mL water, 0.8mL and the 200mL trimethyl carbinol.Reaction mixture is remained on 45-50 ℃, and the solution-treated of 37% spirit of salt of usefulness 0.32g copper chloride dihydrate (II), 0.6mL and 50% aqueous hydrogen peroxide solution of 35.5g (0.52mol) is so that the reaction of residue nitryl compound is thorough.Step process through embodiment P9 obtains 17.1g white solid state title compound, is 90% with its productive rate of gas chromatographic analysis.
Embodiment P44
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
To be dissolved in 17.2g (100mmol) 4-hydroxyl-1-oxygen base-2 in the 50mL water simultaneously, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 29.3g (0.43mol) added in 3 and 4.25 hours respectively in the mixture of 98% sulfuric acid of 1.0g (4.0mmol) cupric sulfate pentahydrate (II) under 35-50 ℃, 25mL water, 0.6mL and the 200mL trimethyl carbinol.Reaction mixture is remained on 45-50 ℃, and the solution-treated of 98% sulfuric acid of usefulness 0.44g cupric sulfate pentahydrate (II), 0.4mL and 50% aqueous hydrogen peroxide solution of 6.7g (98mmol) is so that the reaction of residue nitryl compound is thorough.Step process through embodiment P9 obtains 19.1g white solid state title compound, is 95% with its productive rate of gas chromatographic analysis.
Embodiment P45
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Under 43-60 ℃, in 5 hours, will be added drop-wise to by 5.4g (31.4nmol) 4-hydroxyl-1-oxygen base-2 that adds in order in 5mL water, 0.5mL Glacial acetic acid, the 60mL trimethyl carbinol and the 5mL water at 50% aqueous hydrogen peroxide solution of the 7.4g in the 10mL water (109mmol), 2,6, in the mixture that 6-tetramethyl piperidine solution prepares in 0.166g (0.95mmol) Iron diacetate.In 60 ℃ of downhill reaction mixtures, add the solution of the firm preparation of 50% hydrogen peroxide of 4.4g (65mmol) and 4mL water then.At room temperature stir the mixture whole night.
Show that by gas chromatographic analysis based on initial nitryl content, reaction mixture contains 52% title compound and 4 1% unreacted starting materials.
Embodiment P46
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Repeat the step of embodiment P9, only be to use the mixture of iron protochloride and iron(ic) chloride.
Embodiment P47
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Repeat the step of embodiment P9, only be to use the mixture of iron(ic) chloride and iron powder to replace iron protochloride.
Embodiment P48 and P49 have shown the reaction of using tertiary butyl hydrogenation hydrogen peroxide to replace hydrogen peroxide.
Embodiment P48
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
With 5.2g (30mmol) 4-hydroxyl-1-oxygen base-2 that is dissolved in the 20mL water, 2,6,70% tertiary butyl hydrogen peroxide aqueous solution of 6-tetramethyl piperidine solution and 7.8g (61mmol) added under 35-50 ℃ in 1 hour in the mixture of 37% spirit of salt of 0.33g (1.2mmol) Iron trichloride hexahydrate, 8mL water, 0.2mL and the 60mL trimethyl carbinol simultaneously.After adding, reaction mixture remained on 45 ℃ following 1 hour, at room temperature stirred lasting three days then.The vapour phase chromatogram shows that 3% title compound is arranged in the reaction mixture.
Embodiment P49
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Repeat the step of embodiment P48, only be to use iron protochloride to replace iron(ic) chloride.
Embodiment P50
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
This embodiment uses the addition compound that is formed by urethane and hydrogen peroxide to replace 50% aqueous hydrogen peroxide solution.
Preparation is dissolved in 52.2g (555mmol) urethane-hydrogen peroxide addition compound solution and the 3mL concentrated sulfuric acid solution that is dissolved in the 29mL water in the 75mL water.In 2 hours, under 40 ℃, add the part of two kinds of solution to 0.17g (61mmol) green vitriol, 34.75g (202mmol) 4-hydroxyl-1-oxygen base-2,2,6 simultaneously, in the mixture of 6-tetramethyl piperidine, the 410mL trimethyl carbinol and 70mL water.Add the 0.485g iron vitriol, stirred reaction mixture continues 16 hours whole night under 45 ℃.Residue superoxide and acid solution were added in the reaction mixture in 7 hours under 45 ℃ simultaneously.Add the vitriol oil (1.8mL), at room temperature stirring the mixture continues 64 hours.After 45-50 ℃ of following reacting by heating mixture continues 6.5 hours, add the 1.8mL vitriol oil and 0.101g iron vitriol.Continue 16 hours so that nitryl concentration is lower than 1% of initial value at 45 ℃ of following reacting by heating mixtures then.Then with embodiment 20 in identical step process obtain 38.1g (77% productive rate) white solid state product.
Show that with gas chromatographic analysis reaction product contains about 94% title compound.
Embodiment P51
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Embodiment 51-54 has shown the influence of different acid to present method.
To be dissolved in 17.2g (100mmol) 4-hydroxyl-1-oxygen base-2 in the 35mL water simultaneously, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 23.3g (342mmol) added in 2.5 hours and 6.5 hours respectively in the mixture of 0.527g (3.0mmol) ferrous acetate, 20mL water, 2.3g trifluoroacetic acid and the 200mL trimethyl carbinol that remain under 43 ℃.When superoxide adds near end, the trifluoroacetic solution of 1.25g in mixture interpolation 0.347g (2.0mmol) ferrous acetate and 5mL water.In 90 minutes, add fresh 50% aqueous hydrogen peroxide solution of 5.1g (75mmol) then, continue 15 hours at 42-45 ℃ of following stirred reaction mixture.Adopt and the described identical step process reaction mixture of embodiment P9, obtain 17.5g (71% productive rate) white solid state product.Show that with gas chromatographic analysis reaction product contains about 92% title compound.
Embodiment P52
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
To be dissolved in 17.2g (100mmol) 4-hydroxyl-1-oxygen base-2 in the 35mL water simultaneously, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 31.6g (464mmol) adds in 2.5 hours and 15 hours respectively that 0.561g (3.1mmol) oxalic acid dihydrate that remains under 43-65 ℃ is ferrous to, in the mixture of 20mL water, 1.26g oxalic acid dihydrate and the 200mL trimethyl carbinol.Superoxide adds after the end, continues 7 hours at 50-60 ℃ of following stirred reaction mixture.Ferrous to mixture interpolation oxalic acid dihydrate (1.26g) and 0.380g (2.2mmol) oxalic acid dihydrate, continue 7 hours at 65-80 ℃ of following continuously stirring reaction mixture then.
Show with gas chromatographic analysis, contain about 86% title compound and less than 4% initial thing in hindered amine content reaction product.
Embodiment P53
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
To be dissolved in 17.2g (100mmol) 4-hydroxyl-1-oxygen base-2 in the 35mL water simultaneously, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 23.46g (344mmol) added in 2.5 hours and 6 hours respectively in the mixture of 0.563g (2.0mmol) iron vitriol, 10mL water, 1.3mL methylsulfonic acid and the 200mL trimethyl carbinol that remain under 45 ℃.After superoxide has added, continue 2 hours at 45 ℃ of following stirred reaction mixtures.
Show with gas chromatographic analysis, contain about 85% title compound and less than 2% initial thing in hindered amine content reaction product.
Embodiment P54
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
To be dissolved in 46.5g (270mmol) 4-hydroxyl-1-oxygen base-2 in the 120.5mL trimethyl carbinol and the 108mL water simultaneously, 2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 37.4g (550mmol) added in 3 hours and 11.5 hours respectively in the mixture of 85% phosphoric acid of 3.5g (12.9mmol) the seven water iron(ic) chloride that remain under 80 ℃, 32mL water, 1.3g and the 292mL trimethyl carbinol.After superoxide has added, under 80 ℃, reaction mixture was kept 30 minutes.
Show that with gas chromatographic analysis initial nitryl compound is remaining less than 1%.Excessive superoxide destroys with S-WAT, filters raw product, and handles in the 14 molar sodium hydroxide aqueous solution with sodium borohydride, obtains the productive rate 71% of title compound with gas chromatographic analysis.
Embodiment P55
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
This embodiment shows and can drip metal salt solution to reaction mixture in the whole process of reaction.
Simultaneously 50% aqueous hydrogen peroxide solution of the solution of 16.2g (8.1mmol) four water iron protochlorides, 2mL37% spirit of salt and 50ml water and 35.7g (525mmol) was added in 13 hours and 16 hours respectively and remain on the 34.5g in 100mL water (200mmol) 4-hydroxyl-1-oxygen base-2 under 38-45 ℃, 2,6, in the mixture of the 6-tetramethyl piperidine and the 400mL trimethyl carbinol.After superoxide has added, continue 8 hours at 42-45 ℃ of following reacting by heating mixture.
Show that with gas chromatographic analysis reaction mixture contains 86% title compound and initial nitryl compound less than 5%.
Embodiment P56
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Embodiment 56-57 has shown the effect that increases temperature of reaction.
Simultaneously 50% aqueous hydrogen peroxide solution of 2mL98% sulphuric acid soln in the 30mL water and 27.1g (398mmol) was added in 5.5 hours and remain on 43-45 ℃ of following 0.119g (0.43mmol) iron vitriol, 70mL water, 34.6g (201mmol) 4-hydroxyl-1-oxygen base-2,2,6, in the mixture of the 6-tetramethyl piperidine and the 410mL trimethyl carbinol.After superoxide has added, continue 20 hours at 45 ℃ of following reacting by heating mixtures.
Show that with gas chromatographic analysis it is 18% that reaction mixture contains 73% title compound and initial nitryl compound.
Embodiment P57
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Simultaneously 50% aqueous hydrogen peroxide solution of 27.7g (407mmol) and the 2.2mL98% sulphuric acid soln in the 30mL water were added in 5.25 hours and 6.5 hours respectively and remain on 63-68 ℃ of following 0.115g (0.41mmol) iron vitriol, 70mL water, 34.6g (201mmol) 4-hydroxyl-1-oxygen base-2,2,6, in the mixture of the 6-tetramethyl piperidine and the 410mL trimethyl carbinol.All superoxide have all consumed after 6.5 hours.
Show that with gas chromatographic analysis it is 12% that reaction mixture contains 76% title compound and initial nitryl compound.
Embodiment P58
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Simultaneously with the 10.0g in the 20mL water (58.1mmol) 4-hydroxyl-1-oxygen base-2,2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 15g (220mmol) added in 1.5 hours and 7 hours respectively in the mixture of 0.394g (1.77mmol) the four water tertiary iron phosphates, 13mL water and the 120mL trimethyl carbinol that remain under 63-81 ℃.Stirred reaction mixture whole night at room temperature.Add 50% aqueous hydrogen peroxide solution of the 1.0g (15mmol) that has just prepared, and continued 24 hours so that the amount of nitryl compound reduces to less than 1.5% of initial amount at 80 ℃ of following stirred reaction mixtures.Superoxide with the S-WAT decomposing excessive.
Show with gas chromatographic analysis, contain about 89% title compound in total hindered amine amount reaction mixture.
Embodiment P59
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Simultaneously with the 10.1g in the 30mL water (58.7mmol) 4-hydroxyl-1-oxygen base-2,2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 16.3g (240mmol) added in 2 hours and 6 hours respectively in the mixture of 1.31g (1.76mmol) ferric hypophosphite, 20mL water and the 120mL trimethyl carbinol that remain under 60-79 ℃.Stirred reaction mixture whole night at room temperature.In reaction mixture, add 50% aqueous hydrogen peroxide solution of the 15mL trimethyl carbinol, 0.34g (0.46mmol) ferric hypophosphite and 3.8g (56mmol).Continue 10 hours at 75-80 ℃ of following reacting by heating mixture then.Superoxide with the S-WAT decomposing excessive.According to the same steps as reaction mixture described in the embodiment P9,, obtain (71% productive rate) white solid product that 10.2g is made up of title compound according to gas chromatographic analysis.
Embodiment P60
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
This embodiment has shown two kinds of different metal salt effect in the method.
Simultaneously the solution of 0.13g (0.52mmol) cupric sulfate pentahydrate, 1mL98% sulfuric acid and 10mL water and 50% aqueous hydrogen peroxide solution of 13.6g (200mmol) were added in 3.5 hours and 4.25 hours respectively the 17.4g in the 50mL water (101mmol) 4-hydroxyl-1-oxygen base-2,2,6, the 6-tetramethyl piperidine makes an addition in the solution that the mixture of 0.14g (0.50mmol) five aqueous ferrous sulfates, 10mL water and the 200mL trimethyl carbinol makes.In the interpolation process, reaction mixture is remained on 40-45 ℃, at room temperature stir whole night then.
Show have 77% initial compounds to be transformed into title compound with gas chromatographic analysis.
Embodiment P61
Two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] adipic acid ester and two [1-
(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] mixture of glutarate
50% aqueous hydrogen peroxide solution of 159g (2.34mol) is added drop-wise to 168.4g under 40 ℃ by DBE-3  (dibasic ester, have about 9: 1 dimethyl adipates: two [the 1-oxygen bases of Methyl glutarate) making-2,2,6,6-tetramethyl piperidine-4-yl] adipic acid ester and two [1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] in the mixture of mixture, 2.03g (7.5mmol) Iron trichloride hexahydrate of glutarate, 37% spirit of salt, the 1.9mL trimethyl carbinol and the 262mL water of 1.5mL.After reaction 30 hours, temperature is increased to 70 ℃, in 6 hours, in mixture, add 50% aqueous hydrogen peroxide solution of 7 1g (1.04mol).Under 65 ℃,, in 6 hours, add 50% aqueous hydrogen peroxide solution of another 71g, under 65 ℃, stirred the mixture 17 hours after the mixture stirring 13 hours.With S-WAT decomposing excessive superoxide.Filtering mixt is removed solid, removes most of trimethyl carbinol and water with heptane by condistillation.Use the ethyl acetate extraction resistates,, use the saturated nacl aqueous solution rinse solution.Evaporating solvent by flash chromatography purification residue on silica gel, obtains the 84.1g fusing point and is 131.5-133 ℃ white solid with hexane/ethyl acetate.Also obtain for the second time the 16.3g fusing point and be 128-130 ℃ white solid.NMR analyzes demonstration, and the structure of white solid is made up of the adipic acid ester/glutarate reaction product of expection.
Embodiment P62
Two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] adipic acid ester and two [1-
(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] mixture of glutarate
Repeat the step described in the embodiment P61, use is by DBE-2  (dibasic ester, have about 3: 7 dimethyl adipates: two [the 1-oxygen bases of Methyl glutarate DuPont) making-2,2,6,6-tetramethyl piperidine-4-yl] adipic acid ester and two [1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] mixture of glutarate replaces two [the 1-oxygen bases of being made by DBE-3 -2 described in the embodiment P61,2,6,6-tetramethyl piperidine-4-yl] adipic acid ester and two [1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] glutarate.
Embodiment P63
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Simultaneously with the 34.6g in the 50mL water (201mmol) 4-hydroxyl-1-oxygen base-2,2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 25.2g (370mmol) added in 4 hours and 8 hours respectively in the mixture of 1.12g (4.0mmol) iron vitriol, 20mL water, 1mL methylsulfonic acid and the 400mL trimethyl carbinol that remain under 80-85 ℃.In adding the superoxide process, in reaction mixture, be added on the iron vitriol of the 0.506g (1.8mmol) in the 2mL water and the solution of 0.3mL methylsulfonic acid.After superoxide had added, stirring the mixture under 80-85 ℃ continued 30 minutes.The vapour phase chromatogram shows that initial nitryl residue is less than 1%.Step process reaction mixture according to identical among the embodiment P9 obtains the white solid that 40.8g contains 98% title compound by gas chromatographic analysis.
The following examples further specify this fresh compound.
Embodiment 1
1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine-4-ketone and hexalin
In 4.25 hours, 30% aqueous hydrogen peroxide solution of 55g (0.49mol) is added drop-wise to 23.5g (0.14mol) the 1-oxygen base-2 in 14g (0.14mol) hexalin and the 150g hexanaphthene, 2,6, in the mixture of 6-tetramethyl piperidine-4-ketone and 4.0g (0.020mol) four water iron protochlorides.In whole interpolation process, reaction mixture is maintained at about 40 ℃.After superoxide has added 40 ℃ of following stirred reaction mixtures 30 minutes.(10g 0.09mol), continues 7 hours at 40 ℃ of following reacting by heating mixtures to add second section 30% aqueous hydrogen peroxide solution.After with the reaction mixture cool to room temperature, add S-WAT (5g).In 10 hours, carefully temperature of reaction is raised to 60 ℃ of superoxide with decomposing excessive.Through overcooling, separate organic layer, dry on anhydrous magnesium sulfate, concentrate and obtain the 22.6g brown oil.This oil is dissolved in the hexalin, passes through silica gel, obtain the 16.5g yellow oil with hexanaphthene and 1: 2 (v/v) ethanol/cyclohexane.
Show that by vapour phase chromatogram and mass spectroscopy product is to contain at least four kinds of 1-(hydroxyl cyclohexyloxy)-2,2,6,6-tetramethyl piperidine-4-ketone isomer.
Embodiment 2
Two [1-(2-hydroxy-2-methyl propoxy--2,2,6,6-tetramethyl piperidine-4-yl)] sebate
In 3.5 hours, 30% aqueous hydrogen peroxide solution of 73g (0.64mol) is added drop-wise to 30.0g (0.059mol) two [the 1-oxygen base-2 in the 150g trimethyl carbinol and the 6g water, 2,6,6-tetramethyl piperidine-4-yl)] in the mixture of sebate and 4.7g (0.024mol) four water iron protochlorides.In whole superoxide interpolation process, temperature of reaction is maintained at about 40 ℃.After having added 40 ℃ of following stirred reaction mixtures 4 hours.With 150g ethyl acetate diluted reaction mixture.Add the sodium sulfite aqueous solution of 100g20%, continue 1.5 hours with the decomposing excessive superoxide at 45-60 ℃ of following stirred reaction mixture.With 100g ethyl acetate extraction water layer, with the sulfuric acid flushing combination organic layer of 200g5%.Evaporating solvent obtains the pale brown look liquid of 39.4g, on silica gel with the ethyl acetate of 4: 1: 5 (volume ratio): Virahol: the mixture of hexane purifies by flash chromatography, obtains the brown yellow oil of 19.1g (49% productive rate) title compound.
1Hnmr(CDCl 3)∶δ＝3.65ppm(4H，-NOCH 2-)
Embodiment 3
The reaction of two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebates and hexalin
In 2.75 hours, 30% aqueous hydrogen peroxide solution of 70g (0.62mol) is added drop-wise to 32.4g (0.063mol) two (the 1-oxygen base-2 in the 100g hexalin, 2,6,6-tetramethyl piperidine-4-yl) in the mixture of sebate and 5.0g (0.025mol) four water iron protochlorides.In the interpolation process, reaction mixture is remained on 40-45 ℃.40 ℃ of following stirred reaction mixtures 5 hours, in this time, in reaction mixture, add 50% aqueous hydrogen peroxide solution (5.0g, 0.074mol) portion of just having prepared in two five equilibriums then.In ensuing one day, reaction mixture is heated to 40 ℃, (2.5g 0.037mol), keeps reaction mixture other 5 hours under 40 ℃ to add another part 50% aqueous hydrogen peroxide solution.In mixture, add the sodium sulfite solution of 100g20%, temperature of reaction is remained on 70 ℃ continue 45 minutes hydrogen peroxide down with decomposing excessive.Compound organic layer is concentrated, obtain the 151g raw product.Add water, remove remaining hexalin by evaporation.By flash chromatography on silica gel with 10: 1: 10 ethyl acetate: ethanol: the mixture of hexane purifies residue 50g raw product, obtains 32.9g oil.
NMR analyzes demonstration, and oil contains two [1-(trans-2-hydroxyl cyclohexyloxy)-2,2,6,6-tetramethyl piperidine-4-yl] sebate, also has other isomer of described sebate compound.
Embodiment 4
4-hydroxyl-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and hexalin
In 1.75 hours, 50% aqueous hydrogen peroxide solution of 50g (0.74mol) is added drop-wise to 35.0g (0.20mol) 4-hydroxyl-1-oxygen base-2,2,6 in the 100g hexalin, in the mixture of 6-tetramethyl piperidine and 10.0g (0.050mol) four water iron protochlorides.In whole interpolation process, temperature of reaction is maintained at about 40-45 ℃.After superoxide has added 40 ℃ of following stirred reaction mixtures 5 hours.With the mixture cool to room temperature, add the sodium sulfite aqueous solution of 100g20%.60 ℃ down careful reacting by heating mixtures 1 hour with the decomposing excessive superoxide.After organic layer adds acetone, filter crude product mixture and remove solid, concentrated filtrate.Add water and remove remaining hexalin by evaporation.By flash chromatography hexane with 2: 1 (v/v) on silica gel: ethyl acetate purifies raw product, obtains the 36.3g yellow oil.
Show that by mass spectroscopy oil is 1-(hydroxyl cyclohexyloxy)-4-hydroxyl-2,2,6,6-tetramethyl piperidine isomer and 1-(hydroxyl cyclohexyloxy)-4-hydroxyl-2,2,6, the mixture of 6-tetramethyl piperidine.
Embodiment 5
2,4-two [N-(1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino-6-chloro-S-triazine and hexamethylene
The reaction of alcohol
50% aqueous hydrogen peroxide solution with 30g (0.44mol) in 2 hours adds the 39.4g (0.070mol) 2 of temperature in 40-45 ℃ 150g hexalin to, 4-two [N-(1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) in the mixture of butyl amino-6-chloro-S-triazine and 7.0g (0.035mol) four water iron protochlorides.After having added, superoxide,, adds 50% aqueous hydrogen peroxide solution of another part 19g (0.28mol) in this stage 40 ℃ of following stirred reaction mixtures 10 hours.Add again a 50% aqueous hydrogen peroxide solution (25g, 0.37mol), simultaneously in 50-65 ℃ of following reacting by heating mixture 4 hours.60 ℃ down with 100g20% sodium sulfite aqueous solution reaction mixture 1 hour to decompose residual peroxide.Organic layer is condensed into brown oil, uses cyclohexane extract three times, use ethyl acetate extraction 1 time.Concentrate composite extract, obtain the 43.4g yellow oil.
Embodiment 5A
2,4-two N-[1-(trans-2-hydroxyl cyclohexyloxy)-2,2,6,6-tetramethyl piperidine-4-yl] butyl ammonia
Base }-6-(2-hydroxyethyl) amino-S-triazine
With product and thanomin and the sodium hydroxide solution reaction that obtains among the embodiment 5.With ethyl acetate dilution crude reaction mixture and water flushing.Use the ethyl acetate extraction water layer, concentrate compound organic layer.The ethyl acetate that is dissolved in resistates gathers and adds hexanaphthene.Remove brown oil.Concentrate surplus solution, obtain the 13.7g raw product.On silica gel, purify raw product by flash chromatography, obtain the 6.4g yellow oil with 2: 1 (v/v) ethyl acetate/hexane and 8: 1 (v/v) ethyl acetate/methanol.Dissolving oil in ethanol was handled 1 hour with decolorizing carbon under 60 ℃.Solids removed by filtration, evaporating solvent obtains the 6.5g white-yellowish solid, and fusing point is 67-80 ℃.
NMR analyzes demonstration, and solid contains title compound, goes back the mixture of hydroxyl-cyclohexyloxy and dihydroxyl cyclohexyloxy constitutional isomer.
Embodiment 6
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
In 2 hours, will add 4-hydroxyl-1-oxygen base-2 of 50 ℃ of following 25.8g (0.15mol) with 50% aqueous hydrogen peroxide solution of 25mL trimethyl carbinol blended 50.7g (0.75mol) to, 2,6, in the mixture of 6-tetramethyl piperidine, 8.95g (0.045mol) four water iron protochlorides and the 110mL trimethyl carbinol.Stirred reaction mixture remains on 50 ℃ and continues 6 hours then, and by the monitoring of vapour phase chromatogram.Add 50% hydrogen peroxide of another 17.7g (0.26mol),, initial nitryl compound reaction is roughly finished in 50 ℃ of following reacting by heating mixtures more than two hour.Filter reaction mixture is removed solid, the filtrate water dilution.With methylene dichloride tertiary butanol and water solution is extracted three times, water layer fully extracts with ethyl acetate, obtains the 7.4g title compound.With the aqueous solution in the saturated chlorination once with compound organic layer flushing, dry and concentrated on anhydrous magnesium sulfate, obtain the 21.7g orange oil.Orange oil by flash chromatography on silica gel with 3: 2 hexanes: vinyl acetic monomer purifies, obtaining another 12.4g title compound and 4.2g has and 1-(2-hydroxy-2-methyl propoxy-)-2 by the vapour phase chromatogram, 2,6, the compound of 6-tetramethyl piperidine-4-ketone identical residence time of standard model.
The effect of part is added in embodiment 6A-6D explanation in embodiment 6 described steps.
Embodiment 6A
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
(0.99g 5.0mmol) adds in the 400mL trimethyl carbinol that is heated to 40 ℃ with four water iron protochlorides.Stirred the mixture 15 minutes, with 0.78g (5.0mmol) 2,2 '-dipyridyl adds in the t-butanol solution.Stirred solution is 5 minutes then, adds 17.2g (100mmol) 4-hydroxyl-1-oxygen base-2,2,6, the 6-tetramethyl piperidine.In 10 hours, in 40-45 ℃ of downhill reaction mixture, add 50% aqueous hydrogen peroxide solution with 100mL trimethyl carbinol blended 49g (0.72mol).50% aqueous hydrogen peroxide solution that adds another 6g (0.088mol) then is simultaneously in 45 ℃ of following reacting by heating mixtures 4 hours, up to initial nitryl compound reaction.Gas chromatographic analysis shows that reaction mixture contains 6 area %1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-ketone, and contain 22 area % among the embodiment 6.Solids removed by filtration after adding the 1.5g sodium borohydride, was filtered filtrate 1 hour.The filtrate water dilution is fully extracted mixture with ethyl acetate.Concentrated extract obtains the slight tawny crystalline solid of 24.2g, and it has the vapour phase chromatogram residence time identical with the title compound standard model.In similar test, final product obtains the title compound of 16.9g (69% productive rate) through the hexane crystallization several times, and fusing point is at 127-131 ℃.
Embodiment 6B
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
In 6 hours, will add to 50% aqueous hydrogen peroxide solution of 35mL trimethyl carbinol blended 32.3g (475mmol) by the 4-hydroxyl that adds 0.362g (1.2mmol) ethylenediamine tetraacetic acid (EDTA), the 55mL trimethyl carbinol and 17.2g (100mmol) successively-1-oxygen base-2 down at 45-50 ℃, 2,6, in the mixture that the 6-tetramethyl piperidine makes to 0.80g (4mmol) solution of ferrous chloride that is dissolved in the 5mL water.Gas chromatographic analysis shows, adds remaining 15% initial nitryl compound when finishing at superoxide.45-50 ℃ of following stirred reaction mixture 1 hour, then 25 ℃ following 72 hours, finish reaction.Gas chromatographic analysis shows that reaction mixture contains title compound and 1-(2-hydroxy-2-methyl propoxy-)-2,2,6, and the ratio of 6-tetramethyl piperidine-4-ketone is 7: 1.
Embodiment 6C
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Repeat the step of embodiment 6B, use triphenylphosphine oxidation thing to replace ethylenediamine tetraacetic acid (EDTA).
Embodiment 6D
4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Repeat the step of embodiment 6B, use disodium EDTA to replace ethylenediamine tetraacetic acid (EDTA).
Embodiment 7
Two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] adipic acid ester
Aqueous hydrogen peroxide solution is added in the mixture of two [1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] adipic acid esters in the trimethyl carbinol and four water iron protochlorides under 30-50 ℃.With sodium sulfite aqueous solution decomposing excessive superoxide.Concentrate organic layer, on silica gel, purify raw product, obtain title compound by flash chromatography.
Embodiment 8
Two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] glutarate
Aqueous hydrogen peroxide solution is added in the mixture of two [1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] glutarates in the trimethyl carbinol and four water iron protochlorides under 30-50 ℃.With sodium sulfite aqueous solution decomposing excessive superoxide.Concentrate organic layer, on silica gel, purify raw product, obtain title compound by flash chromatography.
Embodiment 9
Two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] succinate
Aqueous hydrogen peroxide solution is added in the mixture of two [1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] succinates in the trimethyl carbinol and four water iron protochlorides under 30-50 ℃.With S-WAT decomposing excessive superoxide.Concentrate organic layer, on silica gel, purify raw product, obtain title compound by flash chromatography.
Embodiment 10
Two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] sebate
Aqueous hydrogen peroxide solution is added in the mixture of two [1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] sebates in the trimethyl carbinol and four water iron protochlorides under 30-50 ℃.With S-WAT decomposing excessive superoxide.Concentrate organic layer, on silica gel, purify raw product, obtain title compound by flash chromatography.
Embodiment 11
2,4-two N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] butyl ammonia
Base }-6-chloro-S-triazine
50% aqueous hydrogen peroxide solution that will add up to 40g (0.5 9mol) in 5 hours divides two parts of 43.2g (0.076mol) 2 that are incorporated in the 150g trimethyl carbinol and the 15g water, 4-two { N-[1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] butyl amino-mixture of 6-chloro-S-triazine and 7.0g (0.035mol) four water iron protochlorides in.To reaction mixture add another part 50% aqueous hydrogen peroxide solution (3g, 0.044mol), simultaneously in 2.25 hours with temperature Bao Te at 40-45 ℃.With 100g ethyl acetate diluted reaction mixture.Add 20% sodium sulfite aqueous solution of 100g, reaction mixture is heated 1 hour down to decompose residual peroxide at 60 ℃.The water layer ethyl acetate extraction concentrates compound organic layer.On silica gel, purify raw product by flash chromatography, obtain the 54.1g title compound with 1: 1 (v/v) hexane/ethyl acetate.
Embodiment 12
2,4-two N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] butyl ammonia
Base }-6-(2-hydroxyethyl) amino-S-triazine
Pass through this title compound of prepared in reaction of preparation intermediate among the embodiment 11 with thanomin and sodium hydroxide.Remove water layer, use the cyclohexane extract rest layers.The vapourisation under reduced pressure solvent purifies raw product with 1: 2 (v/v) hexane/ethyl acetate by flash chromatography on silica gel, obtain the 4.1g title compound, is white solid, and fusing point is at 110-120 ℃.
1Hnmr(CDCl 3)∶δ＝3.54?ppm(q，2H，NCH 2)；3.59?ppm(s，4H，NOCH 2)
Embodiment 13
The product of embodiment 11 and N, the reaction of N '-two (3-aminopropyl) quadrol
With the product and the N of preparation among the embodiment 11, N '-two (3-aminopropyl) quadrol was with 3: 1 molar ratio reactions.Product mixtures comprises N, N ', N "-3 2; 4-two [N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6; 6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine and N, N '; N -3 2; 4-two [N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6; 6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine.
Embodiment 14
2,4-two N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] butyl ammonia
Base }-6-octyl group amino-S-triazine
Use excessive octylame to produce title compound by the reaction of embodiment 11 preparation compounds, as yellow-white glass, fusing point is at 68-86 ℃.
Embodiment 15
N, N '-2 4,6-two N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]
Butyl amino]-S-triazine-2-yl }-1
Use the prepared in reaction title compound of cyclohexyl diamino by embodiment 11 preparation compounds.
Embodiment 16A
4-hydroxyl-1-oxygen base-2,2,6, the reaction of the 6-tetramethyl piperidine and the trimethyl carbinol
Add 50% aqueous hydrogen peroxide solution to the 30-60 ℃ of 4-hydroxyl-1-oxygen base-2,2,6 in the following trimethyl carbinol, in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.With sodium sulfite aqueous solution decomposing excessive superoxide.Concentrate organic layer, on silica gel, purify raw product, obtain sample 4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine by flash chromatography.
Embodiment 16B
1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-ylmethyl acrylate
Use methyl methacrylate to prepare the prepared in reaction title compound of compound by embodiment 16A.
Embodiment 17
4-allyloxy-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
60% sodium hydride suspension with the 8.4g in the mineral oil (0.21mol) under 50 ℃ divides in the compound solution that obtains among several parts of 49.1g (0.20mol) the embodiment 16A that add in the anhydrous diglyme of 500ml.(20.8ml, 29.1g 0.24mol), and stirred the mixture 7 hours under 50 ℃ to add allyl bromide 98 then in several hours in reaction mixture.Reaction mixture, and with 2N hydrochloric acid solution quenching.Add saturated sodium bicarbonate solution with in and after the excess acid, concentrate organic layer, obtain the title compound of 47.5g (83% productive rate), be yellow oil.
Embodiment 18
4-(2,3-glycidoxy-1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine
Use epoxy chloropropane to prepare the prepared in reaction title compound of compound by embodiment 16A.
Embodiment 19
1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-base 3-{[[[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-oxygen base] carbonyl]-amino] methyl }-3,5, the 5-3-methyl cyclohexanol
Base hydrogen carbamate
Use 5-isocyanide acyl-1-(isocyanide acyl group methyl)-1,3, (=isophorone diisocyanate prepares the prepared in reaction title compound of compound to the 3-trimethyl-cyclohexane by embodiment 16A.
Embodiment 20
Two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidines-4-yl] 1, the own diamino acid of 6-
Ester
Use cyclohexyl diisocyanate to prepare the prepared in reaction title compound of compound by embodiment 16A.
Embodiment 20A
Two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] Toluene-2,4-diisocyanate, the 4-diamino
Manthanoate
Use Toluene-2,4-diisocyanate, the 4-vulcabond prepares the prepared in reaction title compound of compound by embodiment 16A.
Embodiment 20B
1,3,5-three { [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-oxygen base] carbonyl ammonia
The base hexyl }-2,4,6-trioxa-S-triazine
Use 1,3,5-three [6-isocyanide acyl hexyl]-2,4,6-trioxa-S-triazine (DESMODUR  N-3390) prepares the prepared in reaction title compound of compound by embodiment 16A.
Embodiment 21
1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-base acrylate
Use methyl acrylate to prepare the prepared in reaction title compound of compound by embodiment 16A.
Embodiment 22
2,4,6-three N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] butyl ammonia
Base }-the S-triazine
In 1.25 hours, 30% aqueous hydrogen peroxide solution of 40g (0.35mol) added to the 11.7g (0.011mol) 2 in the 100g trimethyl carbinol and 9g water, 4,6-three [N-(1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] butyl amino-mixture of S-triazine and 3.0g (0.015mol) four water iron protochlorides in.In adding the superoxide process, temperature of reaction remains on 60-65 ℃.In reaction mixture, add two five equilibriums (2g, 50% aqueous hydrogen peroxide solution 0.29mol), simultaneously temperature is remained on 60 ℃ following 9.5 hours.After reaction mixture was with the ethyl acetate dilution, cool to room temperature added 20% sodium sulfite aqueous solution of 100g.In 60 ℃ of following reacting by heating mixtures 1 hour with the decomposing excessive superoxide.Use the ethyl acetate extraction water layer, concentrate compound organic layer.Purify raw product with 2: 1 (v/v) cyclohexane/ethyl acetate by flash chromatography on silica gel, grind with 1: 1 (v/v) cyclohexane/acetone, obtain the white solid of 4.0g title compound, fusing point is at 172-176 ℃.
Embodiment 23A
1-oxygen base-2,2,6, the reaction of the 6-tetramethyl piperidine-4-ketone and the trimethyl carbinol
Add aqueous hydrogen peroxide solution to the 30-60 ℃ of 1-oxygen base-2,2,6 in the following trimethyl carbinol, in the mixture of 6-tetramethyl piperidine-4-ketone and iron protochloride.With sodium sulfite aqueous solution decomposing excessive superoxide.Concentrate organic layer, by the flash chromatography purification residue, the 1-that obtains wanting (2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-ketone.
Embodiment 23B
4-fourth amino-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Use the mixture of Parr device platinum of 5% catalytic amount on the compound of hydrogenation butylamine, embodiment 23A preparation under 3 normal atmosphere and carbon.Remove by filter catalyzer, evaporating solvent obtains this title compound.
Embodiment 24
4-trimethylsiloxy-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
(6.4ml 0.050mol) adds in the mixture of the compound, 8.5ml triethylamine and the 125ml anhydrous tetrahydro furan that obtain among 12.25g (0.050mol) the embodiment 16A with chlorotrimethylsilane under 60 ℃ in 15 minutes.60 ℃ of following stirred reaction mixtures 2 hours, at room temperature stirred then 1 hour.Evaporating solvent separates resistates between water and methylene dichloride.Dry organic layer on sal epsom concentrates the yellow oil that obtains 14.6g (92% productive rate) title compound.
Embodiment 25
4 benzoic acid base-1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine
Slowly add 50% aqueous hydrogen peroxide solution to the 30-60 ℃ of 4 benzoic acid base-1-oxygen base-2,2,6 in the following trimethyl carbinol, in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.With sodium sulfite aqueous solution decomposing excessive superoxide.Concentrate organic layer,, obtain this title compound by the flash chromatography purification residue.
Embodiment 26
1-(2-hydroxy-2-methyl propoxy-)-4-[3-(trimethyl silyl) propoxy-]-2,2,6, the 6-tetramethyl-
Piperidines
Use (IV) this title compound of prepared in reaction by embodiment 17 preparation compounds of trimethyl silyl in the Virahol and chlordeneization one hydrogen platinum (Platinate).
Embodiment 26A
1-(2-hydroxy-2-methyl propoxy-)-4-[3-(diethyl monomethyl silyl) propoxy-]-2,2,6,6-
Tetramethyl piperidine
The mixture reflux of 2% chlordeneization, one hydrogen platinum (IV) solution of compound, 14.5ml (0.10mol) diethyl monomethyl silicomethane and the 1ml that obtains in will 28.5g (0.10mol) embodiment 17 in Virahol 4 hours.The vacuum distilling reaction mixture is to obtain viscosity, light yellow oil.Mass spectrum shows that the molion of reaction product is 387, with form by this title compound consistent.
Embodiment 27
Four 3-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-oxygen base] propyl group }-
1,3,5, the 7-tetramethyl-ring tetrasiloxane
By compound, the 6.3ml (0.026mol) 1 that obtains in will 30.3g (0.106mol) embodiment 17 in Virahol, 3,5, the mixture of 2% chlordeneization, one hydrogen platinum (IV) solution of 7-tetramethyl-ring tetrasiloxane and 1ml prepared this title compound in 4 hours 100 ℃ of heating.Reaction mixture, and layering between methylene dichloride and water.Filter organic layer and concentrating under reduced pressure, obtain the title compound of 31.7g (98% productive rate), be viscosity, orange oil.
Embodiment 28
Poly-{ [3-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-oxygen base] propyl group } methyl]
Silane
Use poly-(methyl-monosilane) and chlordeneization one hydrogen platinum (IV) and this title compound of prepared in reaction that passes through preparation compound among the embodiment 17 in the Virahol.
Embodiment 29
Poly-[3-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-oxygen base] propyl group] methyl }
Siloxanes, end is a trimethylsiloxy
Be 1700 and heat at 100 ℃ with the mixture of 1% chlordeneization, one hydrogen platinum (IV) solution of poly-(the first hydride siloxane) of trimethylsiloxy ending and 1ml and to prepare this title compound in 1 hour by compound, 6.8g (0.004mol) molecular-weight average that obtains in will 29.6g (0.104mol) embodiment 17 in Virahol.The resulting polymers piece is partly dissolved in the hot methylene dichloride, uses hot water extraction suspension.Concentrate organic layer, obtain the title compound of 34.7g, be white rubber shape solid.
Anal.Calcd.for C 439.5H 910N 25.5O 103Si 27.5(n=25.5 in initial substance): C, 58.82; H, 10.21; N, 3.97 Found C, 59.62; H 10.11, and N 3.08
Embodiment 30
Two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] glutarate and two [1-
(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] mixture of adipic acid ester
Mixture reflux in dimethylbenzene with the compound, DBE-2 dimethyl ester mixture (DuPont) and the lithium amide that make among the embodiment 16A.Distillating carbinol from reaction mixture.With diluted mineral acid quenching reaction mixture, water flushing organic layer, dry on anhydrous magnesium sulfate.The reduction vaporization xylene solution obtains the mixture of this title compound.
Embodiment 30A
Two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] adipic acid ester and two [1-
(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] mixture of glutarate
50% aqueous hydrogen peroxide solution is added drop-wise to iron(ic) chloride, spirit of salt water liquid, water, the trimethyl carbinol and by two (1-oxygen bases-2 of DBE-3 dibasic ester (DuPont ) preparation, 2,6,6-tetramethyl piperidine-4-yl) adipic acid ester and two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) in the mixture of glutarate.Superoxide with the sodium sulfite aqueous solution decomposing excessive.Filter reaction mixture, evaporating solvent.Resistates purifies with hexane/ethyl acetate on silica gel by flash chromatography, obtains this title compound, is white solid, and fusing point is 131.5-131 ℃.
Embodiment 30B
Two [1-(2-hydroxy-2-methyl-propoxy-)-2,2,6,6-four-methyl-piperidin-4-yl]
Glutarate and two [1-(2-hydroxy-2-methyl-propoxy-)-2,2,6,6-four-
Methyl-piperidin-4-yl] mixture of succinate
When repeating the step of embodiment 30, promptly prepare this title mixture with DBE-9=methyl ester mixture (DuPont).
Embodiment 31
The reaction of two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebates and neopentyl alcohol
According to the step of embodiment 25, aqueous hydrogen peroxide solution is added in the mixture of two [1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] sebates in neopentyl alcohol and iron protochloride.
Embodiment 32
1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine-4-ketone and neopentyl glycol
According to the step of embodiment 25, add aqueous hydrogen peroxide solution in neopentyl glycol 1-oxygen base-2,2,6, in the mixture of 6-tetramethyl piperidine-4-ketone and iron protochloride.
Embodiment 33
4-stearoyl Oxy-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and tertiary amyl alcohol
According to the step of embodiment 25, add aqueous hydrogen peroxide solution in tertiary amyl alcohol 4-stearoyl Oxy-1-oxygen base-2,2,6, in the mixture of 6-tetramethyl piperidine and iron protochloride.
Embodiment 33A
4-hydroxyl-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and 2-methyl-2-butanols
Under 90-95 ℃ with the 34.5g in the 50ml water (0.20mol) 4-hydroxyl-1-oxygen base-2,2,6,50% aqueous hydrogen peroxide solution of 6-tetramethyl piperidine solution and 22.5g adds in the mixture that contains 1.88g iron vitriol, 2.05g methylsulfonic acid, 20ml water and 450mL2-methyl-2-butanols (tertiary amyl alcohol).In 6 hours, finish reaction.Filter reaction mixture then stirs filtrate with alkaline sodium borohydride to remove solid with S-WAT.Remove water layer, concentrate organic layer, on silica gel, purify, obtain the yellow oil of 46.3g with hexane/ethyl acetate by flash chromatography.The analysis of vapour phase chromatography-mass spectroscopy shows that product is the mixture of 3 main ingredients, and all molecular weight are 259, is consistent with tertiary amyl alcohol in adding initial nitryl compound to.
Embodiment 33B
The reaction product of embodiment 33A and the transesterification reaction of methyl stearate
44.8g (0.173mol) is refluxed in the mixture heating up of reaction product, 47.1g (0.158mol) methyl stearate, 0.223g lithium amide and the toluene of embodiment 33A acquisition.Follow some toluene, from the reaction mixture distillating carbinol.With dilute acetic acid quenching reaction mixture, water, dilute aqueous solution of sodium bicarbonate and saturated nacl aqueous solution flushing continuously.Dry toluene solution on sal epsom filters and concentrates, and obtains a solid.Use the hexane/ethyl acetate purifying by flash chromatography on silica gel, obtain 70.0g white-yellowish solid product, fusing point is 38-43 ℃.
Embodiment 34
4 benzoic acid base-1-(2-hydroxyl cyclohexyloxy)-2,2,6, the 6-tetramethyl piperidine
Tributyl one hydrogen tin is added drop-wise to 2-bromine hexalin and excessive 4 benzoic acid base-1-oxygen base-2,2,6 in the chlorobenzene, in the solution of 6-tetramethyl piperidine.Heated mixt promotes reaction.Crude reaction mixture by silica gel, with using heptane/ethyl acetate behind the heptane, is obtained the suitable/anti-ionomeric mixture of this title compound earlier.
Embodiment 35
4-hydroxyl-1-(2-hydroxyl cyclohexyloxy)-2,2,6, the 6-tetramethyl piperidine
Compound by preparation among the heating embodiment 34 in the potassium hydroxide solution in methyl alcohol prepares this title compound.
Embodiment 36
4 benzoic acid base-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and propylene glycol
According to the step of embodiment 25, add aqueous hydrogen peroxide solution in propylene glycol 4 benzoic acid base-1-oxygen base-2,2,6, in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.
Embodiment 37
4 benzoic acid base-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and trimethylene glycol
According to the step of embodiment 25, add aqueous hydrogen peroxide solution in trimethylene glycol 4 benzoic acid base-1-oxygen base-2,2,6, in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.
Embodiment 38
Two [1-(2-hydroxyl-oxethyl-2,2,6,6-tetramethyl piperidine-4-yl)] sebate
Tributyl one hydrogen tin is added drop-wise in the solution of ethylene iodohydrin in the chlorobenzene and excessive two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebate.Crude reaction mixture by silica gel, with using heptane/ethyl acetate behind the heptane, is obtained this title compound earlier.
Embodiment 39
The reaction of two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebates and isopropylcarbinol
According to the step of embodiment 25, aqueous hydrogen peroxide solution is added in the mixture of two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebates in isopropylcarbinol and four water iron protochlorides.
Embodiment 40
4 benzoic acid base-1-oxygen base-2,2,6,6-tetramethyl piperidine and 1, the reaction of 4-butyleneglycol
According to the step of embodiment 25, aqueous hydrogen peroxide solution is added in 1, the 4 benzoic acid base in the 4-butyleneglycol-1-oxygen base-2,2,6 is in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.
Embodiment 41
4-hexyloxy-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and tetramethyl ethylene ketone
According to the step of embodiment 25, add aqueous hydrogen peroxide solution in tetramethyl ethylene ketone 4-hexyloxy-1-oxygen base-2,2,6, in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.
Embodiment 42
1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine-4-ketone and glycerine
According to the step of embodiment 25, add aqueous hydrogen peroxide solution in glycerine 1-oxygen base-2,2,6, in the mixture of 6-tetramethyl piperidine-4-ketone and four water iron protochlorides.
Embodiment 43
4-hydroxyl-1-oxygen base-2,2,6, the reaction of 6-tetramethyl piperidine and 2-ethyl-1-hexanol
According to the step of embodiment 25, add aqueous hydrogen peroxide solution in 2-ethyl-1-hexanol 4-hydroxyl-1-oxygen base-2,2,6, in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.
Embodiment 44
1-(2-hydroxy-2-methyl propoxy-)-4-palmitoyl oxygen base-2,2,6, the 6-tetramethyl piperidine
The mixture heating up of the compound, 12.11g (44.84mmol) methyl palmitate (Uniphat A60), 0.76g lithium amide and the toluene that obtain among 12.11g (49.4mmol) the EXAMPLE l 6A is refluxed.Steam from reaction mixture with a part of toluene and to increase methyl alcohol.With dilute acetic acid quenching reaction mixture, continuously with methanol-water liquid, dilute aqueous solution of sodium bicarbonate and saturated nacl aqueous solution flushing.Dry toluene solution on sal epsom filters and concentrates, and obtains a solid.Purify with hexane/ethyl acetate on silica gel by flash chromatography, obtain the 18g solid.Recrystallize from methyl alcohol is produced this title compound of 10.7g white solid, and fusing point is 60-64 ℃.
Embodiment 44A
1-(2-hydroxy-2-methyl propoxy-)-4-20 acyloxy-2,2,6, the 6-tetramethyl piperidine
The mixture heating up of the compound, 10.17g (31.1mmol) arachic acid methyl esters, 0.35g lithium amide and the toluene that obtain among 8.40g (34.2mmol) the embodiment 16A is refluxed.With dilute acetic acid quenching reaction mixture, continuously with methanol-water liquid, dilute aqueous solution of sodium bicarbonate and saturated nacl aqueous solution flushing.Dry toluene solution on sal epsom filters and concentrates, and obtains a solid.Purify with hexane/ethyl acetate on silica gel by flash chromatography, obtain this title compound of 9.9g white solid, fusing point is 69-73 ℃.
Embodiment 44B
1-(2-hydroxy-2-methyl propoxy-)-4-(2-ethyl hexanoyl oxygen base)-2,2,6, the 6-tetramethyl piperidine
The mixture heating up of the compound, 30.6g (0.193mol) 2 ethyl hexanoic acid methyl esters, 1.26g lithium amide and the toluene that obtain among 51.6g (0.210mol) the embodiment 16A is refluxed.With a part of toluene from the reaction mixture distillating carbinol.With dilute acetic acid quenching reaction mixture, continuously with methanol-water liquid, dilute aqueous solution of sodium bicarbonate and saturated nacl aqueous solution flushing.Dry toluene solution on sal epsom filters and concentrates, and obtains a yellow solid.Purify with hexane/ethyl acetate on silica gel by flash chromatography, obtain this title compound of 51.0g, be light yellow oil.
Embodiment 44C
1-(2-hydroxy-2-methyl propoxy-)-4-lauroyl oxygen base-2,2,6, the 6-tetramethyl piperidine
The mixture heating up of the compound, 51.9g (0.242mol) methyl laurate (Laurate methyl), 0.43g lithium amide and the toluene that obtain among 72.7g (0.297mol) the embodiment 16A is refluxed.With a part of toluene from the reaction mixture distillating carbinol.With dilute acetic acid quenching reaction mixture, continuously with methanol-water liquid, dilute aqueous solution of sodium bicarbonate and saturated nacl aqueous solution flushing.Dry toluene solution on sal epsom filters and concentrates, and obtains a solid.Purify with hexane/ethyl acetate on silica gel by flash chromatography, obtain this title compound of 96.7g white solid, fusing point is 46-8 ℃.
Embodiment 45
N, N ', N ", N -4 2,4-two [N-(1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] butyl amino-
S-triazine-6-yl }-3, the reaction of 3 '-second diamino dipropyl amine and hexalin
According to the method for embodiment 4, N that will be in hexalin, N ', N "; N -4 2, and 4-two [N-(1-oxygen base-2,2; 6,6-tetramethyl piperidine-4-yl] butyl amino-S-triazine-6-yl }-3, the mixture of 3 '-second diamino dipropyl amine and aquae hydrogenii dioxidi liquid and the reaction of four water iron protochlorides.Obtaining the white solid fusing point is 133-175 ℃.
Embodiment 46
2,4, and 6-three [N-(1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] butyl amino-S-triazine and hexalin
Reaction
According to the step of embodiment 4, with in 2,4, the mixture of 6-three [N-(1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl] butyl amino-S-triazine and hexalin and aquae hydrogenii dioxidi liquid and the reaction of four water iron protochlorides.Obtain light brown oil.
Embodiment 47
Two [1-(3-hydroxyl propoxy--2,2,6,6-tetramethyl piperidine-4-yl)] sebate
Tributyl one hydrogen tin is added drop-wise in the solution of 3-bromo-1-propyl alcohol in the chlorobenzene and excessive two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebate.Heated mixt is to promote reaction.Crude reaction mixture by silica gel, with using heptane/ethyl acetate behind the heptane, is obtained this title compound earlier.
Embodiment 48
Two [1-(12-hydroxyl-1-dodecane acidic group-2,2,6,6-tetramethyl piperidine-4-yl)] sebate
Tributyl one hydrogen tin is added drop-wise in the solution of 12-bromo-1-dodecanol in the chlorobenzene and excessive two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebate.Heated mixt is to promote reaction.Crude reaction mixture by silica gel, with using heptane/ethyl acetate behind the heptane, is obtained this title compound earlier.
Embodiment 49
Two [1-(2-hydroxyl propoxy--2,2,6,6-tetramethyl piperidine-4-yl)] sebate
Tributyl one hydrogen tin is added drop-wise in the solution of 1-bromo-2-propyl alcohol in the chlorobenzene and excessive two (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebate.Heated mixt is to promote reaction.Crude reaction mixture by silica gel, with using heptane/ethyl acetate behind the heptane, is obtained this title compound earlier.
Embodiment 50
The product of embodiment 11 and N, the reaction of N '-two (3-aminopropyl) quadrol
With N, the product of preparation is with 1 among N '-two (3-aminopropyl) quadrol and the embodiment 11: 3.0-1: 3.5 molar ratio reactions.Product mixtures comprises N, N ', N "-3 2; 4-two [N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6; 6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine; N, N '; N -three { 2; 4-two [N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine and N, N ', N "; N -4 2; 4-two [N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6; 6-tetramethyl piperidine-4-yl] butyl oxygen base]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine.
Embodiment 51
N, N ', N ", N -4 2,4-two [N-[2-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl-piperazine
Pyridine-4-yl] butyl amino]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine
This title compound is the step according to embodiment 7, add aqueous hydrogen peroxide solution to N, N '; N ", N -4 2,4-two [N-(1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-S-triazine-6-yl }-3, make in the mixture of 3 '-second diimino dipropyl amine, iron protochloride and the trimethyl carbinol.
Embodiment 51A
N, N ', N -3 2,4-two [N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6, the 6-tetramethyl piperidine-
The 4-yl] butyl amino]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine
This title compound is the step according to embodiment 7, add aqueous hydrogen peroxide solution to N, N ', N -three { 2,4-two [N-(1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-S-triazine-6-yl }-3, make in the mixture of 3 '-second diimino dipropyl amine, iron protochloride and the trimethyl carbinol.
Embodiment 51B
N, N ', N "-3 2,4-two [N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-
Base] butyl amino]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine
This title compound is the step according to embodiment 7, add aqueous hydrogen peroxide solution to N, N '; N "-three { 2,4-two [N-(1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-S-triazine-6-yl }-3, make in the mixture of 3 '-second diimino dipropyl amine, iron protochloride and the trimethyl carbinol.
Embodiment 52
The product of embodiment 11 and N, the reaction of N '-two (3-aminopropyl) quadrol
With N, the product of preparation was with 1: 4.0 molar ratio reaction among N '-two (3-aminopropyl) quadrol and the embodiment 11.Product mixtures comprises N, N ', N "-3 2; 4-two [N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6; 6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine; N, N '; N -three { 2; 4-two [N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine and N, N ', N "; N -4 2; 4-two [N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6; 6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-6-yl }-3,3 '-second diimino dipropyl amine.
Embodiment 53A
2-{N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] butyl amino }-
4,6-two chloro-S-triazines
Under 0 ℃,, obtain this title compound with the compound for preparing among the embodiment 23B and the cyanuryl chloride and the reaction of sodium bicarbonate of equimolar amount.
Embodiment 53B
N, N '-two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-1,6-hexanediamine
By the compound, 1 that will obtain among the embodiment 23A, the hydrogenation under 50psi of the platinum of 5% catalytic amount prepares this title compound on 6-hexanediamine, methyl alcohol and the carbon.
Embodiment 53C
N, N '-two 2-[N-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] butyl amino]-4-chloro-S-triazine-6 base }-N, N '-two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine
-4-yl]-1, the 6-hexanediamine
Use sodium hydroxide as acid vectors, in 60-80 ℃ dimethylbenzene, two kinds of compounds that prepare among embodiment 53A and the 53B are prepared this title compound with 2: 1 molar ratio reactions.
Embodiment 53D
With 2, the N-{2-[N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6 of 4-two (dibutylamino)-S-triazine-6-base ending, 6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-4 base }-N, N '-two [1-(the 2-hydroxyl-
2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-1, the oligopolymer of 6-hexanediamine
Use sodium hydroxide as acid acceptor, in 100-160 ℃ dimethylbenzene with the compound for preparing among embodiment 53B and the 53C with 2: 1 mixed in molar ratio.Use 2 under the same conditions then, 4-two (dibutylamino)-6-chloro-S-triazine reaction mixture obtains with 2,4-two (dibutylamino)-S-triazine-6-base oligomer product ending, lower (2,4,6,8) repeating unit, and structure is as follows.
Embodiment 54
With 2, the N-{2-[N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6 of 4-two (dibutylamino)-S-triazine-6-base ending, 6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-4 base }-N, N '-two [1-(the 2-hydroxyl-
2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-1, the oligopolymer of 6-hexanediamine
Use sodium hydroxide as acid vectors, in 100-160 ℃ dimethylbenzene with N, N '-two (2,2,6,6-tetramethyl piperidine-4-yl)-1,6-hexanediamine and N, { 2-[N-(2,2 for N '-two, 6,6-tetramethyl piperidine-4-yl) butyl amino]-4-chloro-S-triazine-6}-N, N '-two (2,2,6,6-tetramethyl piperidine-4-yl)-1, the 6-hexanediamine is with 2: 1 mixed in molar ratio together.Use 2 under the same conditions then, 4-two (dibutylamino)-6-chloro-S-triazine reaction mixture.With the gained oligomer mixture with as 1, the tert-butyl hydroperoxide in the inert solvent of 2-ethylene dichloride and the molybdic oxide of catalytic amount heat together to form corresponding N-oxycompound.According to the step of embodiment 7, in N-oxycompound mixture, add four water iron protochlorides in the aquae hydrogenii dioxidi liquid and the trimethyl carbinol then.Final product is the mixture as oligopolymer among the embodiment 53D, although single component may with embodiment 53D in inequality.
Embodiment 55
With 2-butyl amino-4-{N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-the basic N-{2-[N-[1-(2-hydroxy-2-methyl propoxy-)-2 that ends up of butyl amino-S-triazine-6-, 2,6,6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-4 base }-N, N '-two [1-(2-hydroxy-2-methyl propoxy-)-
2,2,6,6-tetramethyl piperidine-4-yl]-1, the oligopolymer of 6-hexanediamine
Use sodium hydroxide as acid vectors, in 100-160 ℃ dimethylbenzene, the compound for preparing among embodiment 53A and the 53B heated with 1.33: 1.0 mol ratios and prepare this title compound.In reaction mixture, add dibutylamine then under the same conditions to finish this reaction.Product is the mixture of the oligopolymer of the repeating unit of the 1-4 shown in the following structure.
Figure A0010651501101
Embodiment 56
With 2-butyl amino-4-{N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-the basic N-{2-[N-[1-(2-hydroxy-2-methyl propoxy-)-2 that ends up of butyl amino-S-triazine-6-, 2,6,6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-4 base }-N, N '-two [1-(2-hydroxy-2-methyl propoxy-)-
2,2,6,6-tetramethyl piperidine-4-yl]-1, the oligopolymer of 6-hexanediamine
Use sodium hydroxide as acid vectors, in 100-160 ℃ dimethylbenzene, the compound for preparing among embodiment 53B and the 53C heated with 0.5: 1 mol ratio and prepare this title compound.In reaction mixture, add dibutylamine then under the same conditions to finish this reaction.Product is the mixture of the oligopolymer of 1,3,5 and 7 repeating unit shown in the following structure.
Figure A0010651501111
Embodiment 57
With 2-butyl amino-4-{N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl]-the amino S-triazine of butyl-basic N-{2-[N-[1-(2-hydroxy-2-methyl third oxygen)-2 that ends up of 6-, 2,6,6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-4 base }-N, N '-two [1-(2-hydroxy-2-methyl propoxy-)-
2,2,6,6-tetramethyl piperidine-4-yl]-1, the oligopolymer of 6-hexanediamine
Use sodium hydroxide as acid vectors, in 100-160 ℃ dimethylbenzene with N, N '-two (2,2,6,6-tetramethyl piperidine-4-yl)-1,6-hexanediamine and N, { 2-[N-(2,2 for N '-two, 6,6-tetramethyl piperidine-4-yl) butyl amino]-4-chloro-S-triazine-6}-N, N '-two (2,2,6,6-tetramethyl piperidine-4-yl)-1, the 6-hexanediamine is with 0.5: 1 mixed in molar ratio together.Use the dibutylamine reaction mixture then under the same conditions.The gained oligomer mixture is used as 1, and the tert-butyl hydroperoxide in the inert solvent of 2-ethylene dichloride and the molybdic oxide of catalytic amount are handled to form corresponding N-oxycompound.According to the step of embodiment 7, in the mixture of N-oxycompound, add four water iron protochlorides in the aquae hydrogenii dioxidi liquid and the trimethyl carbinol then.Final product be as among the embodiment 56 preparation oligomer mixture, although single component may with embodiment 56 in inequality.
Embodiment 58
With the N-{2-[N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6 of ethanoyl ending, 6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-4 base }-N, N '-two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl
Phenylpiperidines-4-yl]-1, the oligopolymer of 6-hexanediamine
Use sodium hydroxide as acid vectors, in 100-160 ℃ dimethylbenzene, the compound for preparing among embodiment 53B and the 53C is in the same place with 2: 1 mixed in molar ratio.After reaction finishes, the concentrating under reduced pressure reaction mixture.At room temperature add diacetyl oxide, then at 130 ℃ of following heated mixt to reaction mixture.Crude mixture is cooled off, and neutralized with salt of wormwood.The concentrating under reduced pressure reaction mixture.Product is the mixture of the oligopolymer of 2,4 and 6 repeating units shown in the following structure.
Embodiment 59
With the N-{2-[N-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6 of ethanoyl ending, 6-tetramethyl piperidine-4-yl] butyl amino]-S-triazine-4 base }-N, N '-two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl
Phenylpiperidines-4-yl]-1, the oligopolymer of 6-hexanediamine
Repeat embodiment 54, only be to use the displaced step of diacetyl oxide according to embodiment 58,2,4-two (dibutylamino)-6-chloro-S-triazine.Final product is the oligomer mixture described in embodiment 58, although component ratio may with preparing product among the embodiment 58 in different.
Embodiment 60
Poly-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-ylmethyl acrylate
Prepare this title compound by the compound that obtains among the embodiment 16B through radical polymerization.The molecular-weight average of polymkeric substance is 1500-3000amu.
Embodiment 61
Poly-[1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-base acrylate
Prepare this title compound by the compound that obtains among the embodiment 21 through radical polymerization.The molecular-weight average of polymkeric substance is 1500-3000amu.
Embodiment 62
1,2-two (4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base)-2-butanols
Tributyl one hydrogen tin is added drop-wise to 1 in the chlorobenzene, and 4-two bromo-2-propyl alcohol and excessive 4-hydroxyl-1-oxygen base-2,2,6 is in the solution of 6-tetramethyl piperidine.Heated mixt promotes reaction.Crude reaction mixture by silica gel, with using heptane/ethyl acetate behind the heptane, is obtained this title compound earlier.
Embodiment 63
1,3-two (4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base)-2-propyl alcohol
Tributyl one hydrogen tin is added drop-wise to 1 in the chlorobenzene, and 3-two bromo-2-propyl alcohol and excessive 4-hydroxyl-1-oxygen base-2,2,6 is in the solution of 6-tetramethyl piperidine.Heated mixt promotes reaction.Crude reaction mixture by silica gel, with using heptane/ethyl acetate behind the heptane, is obtained this title compound earlier.
Embodiment 64
2-hydroxy-2-methyl propane-1,3-two is two { [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyls very
Phenylpiperidines-4-yl] (1-oxygen base-2,2,6,6-tetramethyl piperidine-4-yl) sebate
The rough reaction product that obtains among the embodiment 2 is made this title compound by the high pressure liquid chromatography separation.
Embodiment 65
1,3-two (4-stearoyl oxygen base-2,2,6,6-tetramethyl piperidine-1-oxygen base)-2-methyl-2-propyl alcohol
Add aqueous hydrogen peroxide solution under the 30-50 ℃ 4-stearoyl Oxy-1-oxygen base-2,2,6 in the trimethyl carbinol, in the mixture of 6-tetramethyl piperidine and four water iron protochlorides.With sodium sulfite aqueous solution decomposing excessive superoxide.Concentrate organic layer, obtain to comprise 1-(2-hydroxy-2-methyl propoxy-)-4-stearoyl oxygen base-2,2,6, the mixture of 6-tetramethyl piperidine and this title compound.By high pressure liquid chromatography this mixture separation is obtained this title compound.
Embodiment 66
1,3-two (4-hydroxyl-2,2,6,6-tetramethyl piperidine-1-oxygen base)-2-methyl-2-propyl alcohol
The rough reaction product that obtains among the embodiment 16A is made this title compound by the high pressure liquid chromatography separation.
Embodiment 67
1,3-two (4-oxo-2,2,6,6-tetramethyl piperidine-1-oxygen base)-2-methyl-2-propyl alcohol
The rough reaction product that obtains among the embodiment 23A is made this title compound by the high pressure liquid chromatography separation.
Embodiment 68
1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-base capronate
By the mixture of the compound, lithium amide and the dimethylbenzene that make among reflux methyl caproate, the embodiment 16A, distillation for removing methanol makes this title compound simultaneously.
Embodiment 69
4 benzoic acid base-1-(2-hydroxyl-oxethyl)-2,2,6, the 6-tetramethyl piperidine
Tributyl one hydrogen tin is added drop-wise to ethylene iodohydrin and 4 benzoic acid base-1-oxygen base-2,2,6 in the chlorobenzene, in the solution of 6-tetramethyl piperidine.Crude reaction mixture by silica gel, with using heptane/ethyl acetate behind the heptane, is obtained this title compound earlier.
Embodiment 70
4-hydroxyl-1-(2-hydroxyl-oxethyl)-2,2,6, the 6-tetramethyl piperidine
Methanolizing solution by with the compound that obtains among the potassium hydroxide heating embodiment 69 makes this title compound.
Embodiment 71
Poly-[4-hydroxyl-1-(2-hydroxyl-oxethyl)-2,2,6,6-tetramethyl piperidine-4-base succinate]
The reaction of the compound of preparation makes this title compound among Succinic acid dimethylester by equimolar amount roughly and the embodiment 70.
Embodiment 72
Poly-[4-hydroxyl-1-(2-hydroxyl cyclohexyloxy)-2,2,6,6-tetramethyl piperidine-4-base succinate]
The reaction of the compound of preparation makes this title compound among Succinic acid dimethylester by equimolar amount roughly and the embodiment 35.
Embodiment 73
1-(2-hydroxy-2-methyl propoxy-)--4--stearoyl oxygen base-2,2,6,6-tetramethyl piperidine
Mixture reflux in dimethylbenzene with the lithium amide of the compound that makes among methyl stearate, the embodiment 16A and catalytic amount.From the reaction mixture distillating carbinol.With diluted acid quenching reaction, concentrate organic layer, raw product is purified on silica gel by flash chromatography, obtain this title compound white solid, fusing point is 51-56 ℃.
Embodiment 73A
1-(4-octadecane acidic group-2,2,6,6-tetramethyl piperidine-1-oxygen base)-2-octadecyl oxygen base-2-methyl-prop
Alkane
The lithium amide reaction of catalytic amount in the compound for preparing among the embodiment 16A and excessive methyl stearate and the dimethylbenzene is made this title compound.
Embodiment 74
4-hydroxyl-1-(2-hydroxyl-1-phenyl ethoxy)-2,2,6, the 6-tetramethyl piperidine
With potassium hydroxide the methanolizing solution heating of the compound that obtains among the embodiment 10 is made this title compound.
Embodiment 75
Poly-[4-hydroxyl-1-(2-hydroxyl-1-phenyl ethoxy)-2,2,6,6-tetramethyl piperidine-4-base succinate]
The reaction of the compound that obtains among Succinic acid dimethylester by equimolar amount roughly and the embodiment 74 makes this title compound.
Embodiment 76
The stabilization of thermoplastic olefin
Thermoplastic olefin (TPO) particle that contains the mixture of pigment, phosphite, phenolic antioxidant or azanol, Metallic stearates, ultraviolet absorbers or hindered amine stabilizer or ultraviolet absorbers and hindered amine stabilizer by injection moulding makes moulded specimen.
With the TPO of pure color element or pigment enriched material, auxiliary and commercially available acquisition at Superior/MPM 1 with Universal screw rod (24: 1 L/D) " mix down at 400 °F (200 ℃) in the single-screw extrusion machine, cooling and granulation make painted TPO particle in water-bath.The gained particle is to be molded into 60mil (0.006 inch), 2 on the BOY 30M injection moulding machine under about 375 °F (190 ℃) " * 2 " plate.
The painted TPO that is made up of the polypropylene of rubber modifier blending is stable with alkaline stable system, wherein rubber modifier is the multipolymer of id reaction or contains propylene and the blend of ethylene copolymer, the ternary component that also can not contain as ethylidene norbornene can be arranged, the alkalescence stable system is by N, N-dialkyl group azanol or hindered phenol antioxidant are formed, and can contain also and can not contain organic phosphorus compound.
All additives in the end article and the concentration of pigment are the weight percents based on resin.
The prescription that contains thermoplastic olefin particle and one or more following components:
The 0.0-2.0% pigment,
The 0.0-50.0% talcum,
The 0.0-0.1% phosphite,
The 0.0-1.25% phenolic antioxidant,
The 0.0-0.1% azanol,
The 0.05-0.10% calcium stearate,
The 0.0-1.25% ultraviolet absorbers,
The 0.0-1.25% hindered amine stabilizer.
Before extruding and injection moulding, component is mixed through doing in roller dryer.
Test panel is placed in the metal frame, and be exposed to have alternately light/secretly circulation and blackboard temperature are 70 ℃, are 0.55W/m under 340 nm 2With relative humidity be among 50% the Atlas Ci65 Xenon Arc Weather-Ometer, and water spray (Society of Automotive Engineers-SAE J 1960 Test Procedure).Under about 625 kilojoules in interval (Kilojoule),, come test sample by on an Applied Color Systems spectrophotometer, carrying out color measurenent by the reflection mode according to ASTM D 2244-79.The data of collecting comprise Δ E, L*, a* and b* value.According to ASTM D 523, on BYK-GardnerHaze/Gloss Meter, carrying out gloss mensuration under 60 ℃.
UV-light exposes test
When with comprise 2-(2-hydroxyl-3,5-two-tert-pentyl phenyl)-2H-benzotriazole (TINUVIN  328, Ciba), compound and the N of embodiment 73, N ', N ", N -four [4; 6-two (butyl-(1,2,2; 6; 6-pentamethyl-piperidin-4-yl) amino)-S-triazine-2-yl]-1,10-diamino-4,7-phenodiazine decane (CHIMASSORB  119; during the photostabilizer system stability sample of combination Ciba), the sample that is exposed to ultraviolet radiation presents fast light especially degraded.Control sample is by forming at industrial stablizer commonly used with ultraviolet light stability.All samples all contains pigment, Pigment Red 177 and talcum.
Foregoing test panel contains following component (all concentration all are the weight percents based on resin):
Polymeric substrates is the polyolefin blend POLYTROPE  TPP 518-01 (by A.Schulman Inc.Akron, Ohio supplies with) of commercially available acquisition.
Colored packing is 0.025%Red 3B-Pigmen t Red 177, C.I.#65300.
Each plate contains:
0.2％TINUVIN328；
0.1% calcium stearate; With
15% talcum.
Control board contains in addition:
0.1%IRGANOX  B225 (50: 50 IRGANOX  1010, Ciba (new penta 4 bases four (4-hydroxyl-3,5-two-tertiary butyl hydrogenated cinnamate) and IRGAFOS  168, the blend of Ciba[three-(2,4-two-tert-butyl-phenyl) phosphorous acid ester;
0.2%TINUVIN  770, Ciba[two (2,2,6,6-tetramethyl piperidine-4-yl) sebate];
0.2%CHIMSSORB 944, Ciba[4,4 '-cyclohexyl-two (amino-2,2,6,6-tetramethyl piperidine) and 2, the polycondensate of 4-two chloro-uncle 6-octyl group amino-S-triazines].
Two test panels (NOR-1 and NOR-2) S-contains 0.05%N, N-dialkyl group azanol;
NOR-1 also contains:
0.2% CHIMSSORB  119 and
0.2% TINUVIN  123, Ciba, [two (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate].
NOR-2 also contains:
0.2% CHIMSSORB  119 and
The compound of 0.2% embodiment 73.
The UV-light test result is shown in following table.
DE* gloss number % gloss number
0?????3000?????0?????3000?????0?????3000
Sample Kj/m 2Kj/m 2Kj/m 2Kj/m 2Kj/m 2Kj/m 2
Contrast 0.0 4.7 66.6 5.4 100 8.1
NOR-1????0.0????4.0????65.5????16.9????100????25.8
NOR-2????0.0????3.8????64.9????45.3????100????69.8
The compound of the embodiment 73 that occurs in test panel NOR-2 demonstrates especially and very largely improves the gloss retention, and the effect of contradistinction system is relatively poor.In fact also effective than the corresponding hindered amine compound among the test panel NOR-1 (TINUVIN  123).Anti-color change is also strengthened under UV-light.
The polymer blend such as the EPDM blend that contain unsaturated ternary component, above-mentioned photostabilizer of the present invention system is more effective with making.
In all cases, this light stabilized formulations has shown that ratio is without the bigger fast light degraded of stable sample, without the very fast degraded under above-mentioned UV-light exposure condition of stable sample.
Embodiment 77
Paintable TPO
Thermoplastic olefin (TPO) particle that contains other auxiliarys described in The compounds of this invention, pigment and the embodiment 76 by injection moulding prepares the mold pressing sample.
Pack lacquer system japanning light stable article with one, and the TPO/ lacquer interacted test.Before japanning, wash sample according to GM998-4801, and descended dry 15 minutes at 200 °F (94 ℃).Short stick to the desciccator diaphragm thickness of coating is 0.2-0.4mils.With sample drying 5 minutes, be coated with 1K priming paint then to thickness 1.2-1.4mils.With dry 3 minutes of lacquered board, varnish then, then expansion drying is 10 minutes, and bakes 30 minutes with the stove of 250 (121 ℃), to desciccator diaphragm thickness 1.2-1.5mils.
By Aggressive Adhesion Test ing (Technical Finishing, the proprietary test procedure of Inc.) and Taber Scuff test lacquer viscosity.The final lacquer that lacquered board keeps more than 80% is considered to acceptable.After Aggressive Adhesion Testing, the lacquer that sample is lost is considered to acceptable less than 5%.Sample interacts as follows to estimate the TP0/ lacquer: goods * Taber Scuff Test Aggressive Adhesion Test HALS pKa
A 100% removes 6% and loses (failure) 9.1
B 0% removes 4% and loses (success) 4.6
C 0% removes 3% and loses (success) 4.0
Goods A is for containing 0.2%CHIMSSORB  944,0.2%TINUVIN  328,500ppm calcium stearate and 750ppm N, N-dialkyl group azanol in reactor grade TPO.
A also contains 0.2% 2 (2,2,6,6-tetramethyl piperidine-4-yl) sebates (TINUVIN  770, pKa are 9.1).
Goods B and C are for containing 0.2%CHIMSSORB  119,0.2%TINUVIN  328,500ppm calcium stearate and 750ppm N, N-dialkyl group azanol in reactor grade TPO.
B also contains 0.2% 2 (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate (TINUVIN  123, pKa are 4.6).
C also contains 0.2%1-(2-hydroxy-2-methyl propoxy-)-4-stearoyl oxygen base-2,2,6,6-tetramethyl piperidine (compound of embodiment 73, pKa are 4.0).
Data presentation in the table, although goods A has failed in Taber Scuff and Aggressive Adhesion test, goods B and C have passed through two lacquer concentration determinations.And the pKa value proved the pKa value low more (low alkalinity) of test hindered amine compound, coat with lacquer in this Aggressive Adhesion Test ing lose few more.Compound with embodiment 73 of hydroxyl has minimum pKa value, and lacquer is lost minimum, and is all better than the compound that does not have hydroxyl in the prior art.
Embodiment 78
The stabilization of polypropylene pressing
The polypropylene GRANULES that contains the mixture of pigment, phosphite, phenolic antioxidant or azanol, Metallic stearates, ultraviolet absorbers or hindered amine stabilizer or ultraviolet absorbers and hindered amine stabilizer by injection moulding makes moulded specimen.
With the polypropylene of pure color element or pigment enriched material, stablizer, auxiliary and commercially available acquisition at Superior/MPM 1 with Universal screw rod (24: 1 L/D) " mix down at 475 °F (250 ℃) in the single-screw extrusion machine, cooling and granulation make the coloured polypropylene particle in water-bath.The gained particle is to be molded into 60mil (0.06 inch is thick), 2 on the BOY 30M injection moulding machine under about 475 °F (250 ℃) " * 2 " plate.
Stable with alkaline stable system by the coloured polypropylene goods that homopolymer polypropylene or polypropylene copolymer are formed, alkaline stable system is by N, and N-dialkyl group azanol or hindered phenol antioxidant are formed, and can contain also and can not contain organic phosphorus compound.
All additives in the end article and the concentration of pigment are the weight percents based on resin.
The prescription that contains polypropylene GRANULES and one or more following components:
The 0.0-2.0% pigment,
The 0.0-50.0% talcum,
0.0-50.0% lime carbonate,
The 0.0-0.1% phosphite,
The 0.0-1.25% phenolic antioxidant,
The 0.0-0.1% azanol,
The 0.05-0.10% calcium stearate,
The 0.0-1.25% ultraviolet absorbers,
The 0.0-1.25% hindered amine stabilizer.
Before extruding and injection moulding, component is mixed through doing in roller dryer
Test panel is placed in the metal frame, and be exposed to have alternately light/secretly circulation and blackboard temperature are 70 ℃, are 0.55W/m at 340 nm 2With relative humidity be among 50% the Atlas Ci65 Xenon Arc Weather-o-meter, and water spray (Society of Automotive Engineers-SAE J 1960 Test Procedure).Under about 625 kilojoules in interval,, come test sample by on an Applied ColorSystems spectrophotometer, carrying out color measurenent by the reflection mode according to ASTM D 2244-79.The data of collecting comprise Δ E, L*, a* and b* value.According to ASTM D 523, on BYK-GARDNER Haze/Gloss Meter, carrying out gloss mensuration under 60 ℃.
UV-light exposes test
When with the photostabilizer system stability sample of the combination that comprises the compound of TINUVIN328, embodiment 73 and CGL 2020, the sample that is exposed to ultraviolet radiation presents fast light especially degraded.CGL 2020 is with 2, N-{[2-(N-2,2,6 of 4-two (dibutylamino)-S-triazine-6-base ending, 6-tetramethyl piperidine-4-yl) butyl amino]-S-triazine-4-yl }-N, N '-two (2,2,6,6-tetramethyl piperidine-4-yl)-1, the oligopolymer of 6-hexanediamine.Control sample is by forming at industrial stablizer commonly used with ultraviolet light stability.All samples all contains PigmentRed 177.
????DE* Gloss number % gloss keeps
Red 3B goods 0Kj/m 2 ??3000Kj/ ????m 2 ?0Kj/m 2 ??3000Kj/ ????m 2 ??0Kj/m 2 ??3000Kj/ ????m 2
Component 1 Component 2 Component 3
Contrast ?0.14％T ??123 ??0.20％ ??CGL ??2020 ??0.2％ ??Tin. ??328 ????0 ????6.5 ????88％ ????24％ ????100％ ????28％
Embodiment 73 0.10% embodiment 73 ??0.10％ ??OGL ??2020 ??0.1％ ??Tin. ??328 ????0 ????0.6 ????88％ ????77％ ????100％ ????88％
??NOR2 ?0.10％ ?NOR?2 ??0.10％ ??CGL ??2020 ??0.1％ ??Tin. ??328 ????0 ????8.2 ????87％ ????13％ ????100％ ????14％
It is stable that all goods are that the dialkyl group azanol with 0.05% in the final resin carries out alkalescence.
Polymeric substrates is the homopolymer polypropylene-Profax 6501 (supplier MontellPolyolefins) of commercially available acquisition.
Colored packing is 0.25% Red 3B-Pigment Red 177 in final resin, C.I.#65300.
Each goods contains hydroxy-phenyl benzotriazole ultraviolet absorbers-Tinuvin 328,2-(hydroxyl-3,5-two-tert-pentyl phenyl)-2H-benzotriazole.
NOR 2 is two (1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) succinates.
Each goods contains 0.1% calcium stearate.
Sample is 60mil thick 2 " * 2 " injection molding plates.
Carrying out UV-light under SAE J 1960-Exterior Automotive condition exposes.
The concentration of all additives and pigment all is the weight percent based on resin in the end article.
Even under low total concn, the goods that contain the purpose compound of embodiment 73 demonstrate the very large gloss retention of improving especially, and the effect of contrast stabiliser system is relatively poor.Anti-color change is also strengthened greatly under UV-light.Compare with other solids of similar molecule N-O-R HALS (NOR 2) under the isoconcentration, the purpose compound of embodiment 73 is also more effective aspect the maintenance outward appearance.
In all cases, this light stabilized formulations has shown ratio without the bigger fast light degraded of stable sample, and without the very fast degraded under above-mentioned UV-light exposure condition of stable sample.
Embodiment 79
Polypropylene fibre
By fibrous polypropylene and The compounds of this invention, auxiliary and pigment extruding are prepared fiber sample.Typical products and its contains the The compounds of this invention of 0.05-2.0%, the Metallic stearates as calcium stearate of 0.05-0.5%, the pigment of 0-5%, the ultraviolet absorbers of 0.05-2.0%, the phosphite of 0-0.1%, the phenolic antioxidant of 0-1.25%, the N of 0-0.1%, and other of N-dialkyl group azanol and 0-2.0% are hindered amine optionally.The concentration of all additives and pigment is the weight percent based on resin in the end article.
The pigment enriched material is preparation like this: plain and polypropylene (the PROFAX  with pure color, Hercules) in high-shear mixer with these two kinds of components of mixed of the resin of 25% pigment and 75%, upward gained resin/colorant mixture is pressed into thin slice at WabashCompression molder (Model#30-1515-4T3), this thin slice is divided into fine debris, is dispersed in the polypropylene with the concentration that reduces.Perhaps, the pigment enriched material is that pigment is dispersed in the appropriate carrier resin, then is blended in the concentration that reduces to obtain in the fiber.
Containing the ultraviolet absorbers of polypropylene, 0.05-0.1% phosphite, 0-1.25% phenolic antioxidant, 0-0.1% dialkyl group azanol, 0.05-0.1% calcium stearate, 0-1.25% and the goods of 0-1.25% hindered amine mixes through doing in rotating drum dryer, at Superior/MPM 1 with Universal screw rod (24: 1 L/D) " in the single-screw extrusion machine in 475 (246 ℃) extruding down, cooling and granulation in water-bath.Under about 475 °F (246 ℃), upward the gained particle is spun into fiber at the HILLS Research Fiber Extruder (Model#REM-3P-24) that 41 holes, Δ structure spinning nozzle are installed.The tow that spins stretches with 3.2: 1 stretch ratios, makes final and Neil (denier) is 615/41.
On Lawson-HemphillFiber Analysis Knitter fiber sample is woven into socks, cutting into suitable length and being exposed to blackboard temperature is that 89 ℃, 340 nm are 0.55W/m 2With relative humidity be among 50% the AtlasCi65 Xenon Arc Weather-O-meter (Society of Automotive Engineers-SAE J 1885Test Procedure).
According to ASTM D 2244-79, test fiber samples by on an Applied Color Systemsspectrophotometer, carrying out color measurenent by the reflection mode.Equally, but dividually, the sudden change destruction and the record required time of destructive of test fiber sample.
The sample that contains The compounds of this invention presents the satisfactory stability performance to the destroying infection of UV-light.
Embodiment 80
To be exposed to as other tacryl socks of preparation among the embodiment 79 in the Blue M forced air draft oven (draft oven) under 120 ℃.Determine to destroy by the standard of design among the embodiment 79.The time that the destruction of undergoing mutation spends is long more, and stable system is effective more.
The socks that contain The compounds of this invention have good thermostable effect.
Embodiment 81
Compound with about 10wt% test additive such as embodiment 51 is done mixed film-grade polyethylene, fuses into " master batch " particle then under 200 ℃." master batch " particle of full formula is mixed with polyvinyl resin is dried, obtain required final stablizer enriched material.Typical products and its contains the Metallic stearates, 0-0.1% phosphite, the phenolic antioxidant of 0%-1.25%, the N of 0%-0.1% of 0.05-2.0% The compounds of this invention, 0.05-0.5% such as calcium stearate, N-dialkyl group azanol and the hindered amine of 0-2.0% optionally.To on the DOLCI thin film wire, blow out the film of 150 micron thickness through stablizing this resin of all filling a prescription then 200 ℃ of leewards.
To be exposed to through the film of blowing and not be with 0.35W/m under water spray round-robin 63 ℃ of bpt, 340nm according to ASTM G26 2Atlas Xenon Arc Weather-O-meter in.Use the Instron 112 any variations of tension tester results of regular determination film aspect elongation.Measure the destruction of this test by the loss of % elongation in the viewing film.The time of this loss occurrence cost is long more, and this stabiliser system is effective more so.
The film that contains the The compounds of this invention mixture has shown good light stabilising effect.
Embodiment 82
Compound with the embodiment 51 described in 10wt% test additive such as the embodiment 81 is done mixed film-grade polyethylene, fuses into the master batch particle of full formula then under 200 ℃.This master batch particle is mixed with polyvinyl resin is dried, obtain required final stablizer enriched material.Then the resin of this full formula is blown out the film of 150 micron thickness 200 ℃ of leewards on the DOLCI thin film wire.
The gained film is exposed on the galvanized iron liner in greenhouse.Processing is included in the regular substrate (that is: sodium N methyl dithiocarbamate, per six months VAPAM ' and the SESMETRIN ' of every month) and coats sterilant.Carry out performance measurement by the residual elongation of monitoring per-cent.With 50% timing definition that loses of initial elongation is time to rupture.
The film that contains The compounds of this invention has shown good anti-sterilant.
Embodiment 83
A master batch dried polyvinyl resin that blendes together that will prepare described in embodiment 81 is to obtain final stablizer enriched material.Then the resin of this full formula is blown out the film of 150 micron thickness 200 ℃ of leewards with the DOLCI thin film wire.
The gained film is exposed on the soil identical with the agriculture film condition of growing seedlings.Processing comprises and being exposed to 60g/m 3The monobromethane fumigant in three days.Carry out performance measurement by the monitors physical embrittlement.
The film that contains The compounds of this invention has shown good anti-fumigant.
Embodiment 84
Preparation greenhouse film sample described in embodiment 81, but except that The compounds of this invention, also contain Metallic stearates or metal oxide.Typical products and its contains the Metallic stearates of 0.05-2.0% hindered amine of the present invention, 0.05-0.5% such as calcium stearate and for example zinc oxide or the magnesian metal oxide of 0.05-0.5%.
Monitoring effect described in embodiment 82.The film that contains The compounds of this invention has shown good light stability.
Embodiment 85
Described in embodiment 79, prepare polypropylene fibre, except that The compounds of this invention, in goods, also comprise halogenated fire-retardants through selecting.This fire retardant is three (3-bromo-2,2-two (brooethyl) propyl group) phosphoric acid ester, decabromodiphynly oxide, ethylene-(tetrabromo phthalimide) or ethylene-(two bromo-norborneol-dicarboxyl imide).
Use the light stabilized reference described in the embodiment 79, the socks that woven by the polypropylene fibre that contains The compounds of this invention have shown good light stability.
Embodiment 86
With test additives dry blended injection grade polypropylene, fuse into particle then.Except that The compounds of this invention, also comprise fire retardant through selecting.This fire retardant is three (3-bromo-2,2-two (brooethyl) propyl group) phosphoric acid ester, decabromodiphynly oxide, ethylene-(tetrabromo phthalimide) or ethylene-(dibromo norborneol-dicarboxyl imide).Use Boy 50M Laboratary type injection molder to be injection molded into sample then through the resin of the full formula of granulation.
Be placed on test panel in the metal frame and be exposed among the Atlas Ci65 Xenon Arc Weather-Ometer according to the tape alternation light/dark cycle of ASTM G26 test procedure and water spray.The results of regular determination sample is in the elongation changes of properties.Destruction by this test of tensile property loss decision in the viewing film.The time that spends during this loss occurrence is long more, and this stabiliser system is effective more so.
The sample that contains The compounds of this invention has shown good light stability.
Embodiment 87
Thermoplastic olefin (TP0) particle described in injection moulding such as the embodiment 76 is with the preparation moulded specimen.Except that The compounds of this invention, in sample, also comprise halogenated fire-retardants through selecting.This fire retardant is three (3-bromo-2,2-two (brooethyl) propyl group) phosphoric acid ester, decabromodiphynly oxide, ethylene-(tetrabromo phthalimide) or ethylene-(two bromo-norborneol-dicarboxyl imide).
The sample that comprises hindered amine of the present invention has shown good light stabilizing active.
Embodiment 88
Laminated film level polyethylene uses the DOLCI thin film wire to be blow molded into film described in embodiment 82 under 200 ℃.Except that The compounds of this invention, in goods, also comprise fire retardant through selecting.This fire retardant is three (3-bromo-2,2-two (brooethyl) propyl group) phosphoric acid ester, decabromodiphynly oxide, ethylene-(tetrabromo phthalimide) or ethylene-(two bromo-norborneol-dicarboxyl imide).
When measuring the light stabilizing active described in embodiment 82, the film that contains The compounds of this invention has shown satisfactory stability.
Embodiment 89
Thermoplastic olefin (TP0) particle that contains other auxiliarys described in The compounds of this invention, pigment and the embodiment 77 by injection moulding prepares the mold pressing sample.
Pack lacquer system japanning sample with one, and the TPO/ lacquer interacted test.Before japanning, at first remove dust with Virahol flushing sample and with air blast.At 5 minutes burrs (flash) afterwards, with short stick coating, be priming paint with these samples then, be varnish optionally then.The typical membrane thickness degree of these different coating is 0.1-0.3mils for the short stick of coating, priming paint 0.6-0.8mils and varnish 1.2-1.5mils.After the japanning, solidified sample is 30 minutes in 120 ℃ stove.
Press following specimen to estimate the interaction of TP0/ lacquer: in the adhesive test of beginning, use a clean transparent paper adhesive tape on the lacquer surface of the wide design of 3mm, to draw; Perhaps, in humid test, the painted plate exposed with relative humidity be 98%, temperature is in 38 ℃ the environment 240 hours.According to the ratio of ASTM D 714 by the visual inspection blister.
By as top evaluating and measuring, the sample that contains The compounds of this invention has good TPO/ lacquer interaction performance.
Embodiment 90
Thermoplastic elastomer
The resin material of the known thermoplastic elastomer of general purpose grade is mixed and fuse into particle with The compounds of this invention through doing, and elastomeric example wherein comprises the multipolymer of vinylbenzene and divinyl or different propylene and/or ethene-common butylene such as SBS, SEBS and SIS.Typical products and its contains Metallic stearates, 0-5% pigment, 0.05-2.0% ultraviolet absorbers, 0.0-0.1% phosphite, 0.0-1.25% phenolic antioxidant, the 0.0-0.1%N of 0.05-2.0% The compounds of this invention, 0.05-0.5% such as calcium stearate, N-dialkyl group azanol and other hindered amine stabilizer of 0.0-2.0% optionally.
To become useful goods through the resin treatment of this full formula of granulation then, for example blowing or casting extruding film forming is injection molded into moulded product, is thermoformed into moulded product; Be squeezed into line or and cable house; Rotational moulding becomes hollow piece.
The material that contains The compounds of this invention has shown good ultraviolet resistance and heat collapse performance.
Embodiment 91
The goods that make according to embodiment 90 also contain the organic pigment through selecting, and the goods that contain The compounds of this invention have equally shown good fast lightization light and heat destructive characteristics.
Embodiment 92
The goods that make according to embodiment 90 also contain hindered phenol antioxidant; this antioxidant is selected from neopentane four bases four (3; 5-di-t-butyl-4-hydroxyl hydrogenated cinnamate); 3; 5-di-t-butyl-4-hydroxyl phenylpropionic acid octadecane ester; 1; 3; 5-trimethylammonium-2; 4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; 1; 2-two (3; 5-di-t-butyl-4-hydroxyl hydrocinnamoyl) hydrazine; [two (ethyl 3,5-di-tert-butyl-4-hydroxyl benzyl)-phosphoric acid] calcium; 1,3; 5-three (3; 5-di-t-butyl-4-acrinyl) chlorinated isocyanurates and 1,3, the 5-three (3-hydroxyl-4-tertiary butyl-2; the 6-dixylyl) chlorinated isocyanurates, the goods that contain The compounds of this invention have equally shown good fast lightization light and heat destructive characteristics.
Embodiment 93
The goods that make according to embodiment 90 also contain the organophosphorus stablizer, this organophosphorus stablizer is selected from three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, two (2,4-di-t-butyl-6-aminomethyl phenyl) phosphorous acid ethyl ester, 2,2 '; 2 "-inferior amino [triethyl-three-(3,3 ', 5,5 '-tetra-tert-1,1 '-biphenyl-2,2 '-two bases) phosphorous acid ester], four (2, the 4-di-tert-butyl-phenyl) 4,4 '-diphenylene diphosphites, three (nonyl phenyl) phosphorous acid ester, two (2, the 4-di-tert-butyl-phenyl)-Ji five erythrityls (pentaerythrityl) diphosphites, 2,2 '-ethylene (2, the 4-di-tert-butyl-phenyl)-fluorophosphites and 2-butyl-2-ethyl propane-1,3-two bases-2,4,6-tri-tert phenyl phosphorous acid ester, the goods that contain The compounds of this invention have equally shown good fast lightization light and heat destructive characteristics.
Embodiment 94
The goods that make according to embodiment 90 also contain 5, the benzofuranone stabilization agent of 7-two-tertiary butyl-3-(3, the 4-3,5-dimethylphenyl)-2H-benzofuran-2-ones, and same, the goods that contain The compounds of this invention have also shown the performance of ultraviolet resistance and heat collapse.
Embodiment 95
The goods that make according to embodiment 90 also contain by N, the N that N-two (h-tallow fat) amine direct oxidation makes, and the dialkyl group azanol stablizer of N-dialkyl group oxyamine, same, the goods that contain The compounds of this invention have also shown fast lightization light and heat destructive performance.
Embodiment 96
The goods that make according to embodiment 90 also contain other hindered amine stabilizer, and this stablizer is selected from two (2,2; 6,6-tetramethyl-piperazine-4-yl) sebate; 1-(2-hydroxyethyl)-2,2; 6; the polycondensate of 6-tetramethyl--4-hydroxy piperidine and succsinic acid; N, N, N "; N -four [(4; 6-two (butyl-1,2,2; 6; 6-pentamethyl-piperidin-4-yl)-amino-S-triazine-2-yl]-1,10-diamino-4,7-phenodiazine nonane; 4; 4 '-cyclohexyl two (amino-2; 2,6, the 6-tetramethyl piperidine) and 2; the polycondensate of the hot amino of 4-two chloro-uncles 6--S-triazine; 4; 4 '-cyclohexyl two (amino-2,2,6; the 6-tetramethyl piperidine) and 2; the polycondensate of 4-two chloro-6-morpholinyl-S-triazines; 2,2,6; 6-tetramethyl piperidine-4-yl) octadecane acid esters; 3-lauryl-1-(1-ethanoyl-2; 2,6,6-tetramethyl piperidine-4-yl)-pyridine-2; the 5-diketone; 1; 3,5-three { [N-cyclohexyl-N[2-(2,2; 6; 6-tetramethyl piperidine-3-ketone-4-yl) ethyl] amino }-the S-triazine; it is poly-that [methyl 3-(2,2,6; 6-tetramethyl piperidine-4-oxygen base) propyl group] siloxanes; 2; 4-two chloro-6-(2,2,6; 6-tetramethyl piperidine-4-yl) butyl amino)-S-triazine and 2; { [2,4-(2,2 for 2 '-ethylidene-two; 6; 6-tetramethyl piperidine-4-yl) butyl amino-S-triazine-6-yl] amino-trimethylene amino polycondensate, same, the goods that contain The compounds of this invention have also shown fast lightization light and heat destructive performance.
Embodiment 97
The goods that make according to embodiment 90 also contain the hindered amine that other is replaced by the N--oxyl, these hindered amines are selected from two (1-octyloxies-2,2,6,6-tetramethyl piperidine-4-yl) sebate, two (1-octyloxies-2,2,6,6-tetramethyl piperidine-4-yl) adipic acid ester, two (1-cyclohexyloxies-2,2,6,6-tetramethyl piperidine-4-yl) adipic acid ester, two (1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate and 1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-base octadecane acid esters, equally, the goods that contain The compounds of this invention have also shown fast lightization light and heat destructive performance.
Embodiment 98
The goods that make according to embodiment 90 also contain salicyl-2H-benzotriazole, hydroxyphenyl benzophenone or salicyl-S-triazine ultraviolet light absorbers, it is selected from 2-(2-hydroxyl-3,5-two-α-cumyl phenyl)-the 2H-benzotriazole, 2-(2-hydroxy-5-methyl base phenyl)-2H-benzotriazole, 5-chloro-2-(2-hydroxyl-3,5-two trimethylphenylmethane bases)-the 2H-benzotriazole, 2-(2-hydroxyl-3,5-two uncles penta phenyl)-the 2H-benzotriazole, 2-(the hot phenyl of 2-hydroxy-3-alpha-cumyl--uncle 5-)-2H-benzotriazole, 2,4-di-tert-butyl-phenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid ester, 2-hydroxyl-4-n-octyloxy benzophenone and 2,4-two (2, the 4-3,5-dimethylphenyl)-6-(2-hydroxyl-4-octyloxy-phenyl)-S-triazine, equally, the goods that contain The compounds of this invention have also shown the performance of ultraviolet resistance and heat collapse.
Embodiment 99
Hindered amine is tested stablizer add bi-component polyester urethane coating based on the chlorinated isocyanurates (DESMODUR  N-3390) of the polyester polyol (DESMOPHEN  670-80) of commercially available acquisition and commercially available acquisition with 2% of total resin solid weight.Vanish system is with 0.015% dibutyl tin dilaurate catalysis of total resin solid.
With each coating being coated on the transparent glass sheet by draw down in triplicate, size about 4 " * 6 ", the about 2mils of thickness (0.002 ").
These three parts of sheet glass are through following processing:
Plate 1-baked 30 minutes down at 180 °F (82 ℃); At room temperature aging; And observe every day.
Plate 2-dry air (self-vulcanizing); At room temperature aging; And observe every day.
Plate 3-dry air 1 day; Aging in the stove of 120 (49 ℃); Observe every day also aging down at 120 °F (49 ℃) continuously.
Time opening is 0, with the naked eye estimates the outward appearance of all plates, notes development muddy arbitrarily in the coating and any exudate of coating surface.Four days observations is as follows.
Plate 1
Sample * 01 days 2 days 3 days 4 days 18 months
A is transparent transparent
B is transparent fuzzy fuzzy
C is transparent transparent
Plate 2
Sample * 01 days 2 days 3 days 4 days 18 months
A is transparent transparent
B is transparent fuzzy fuzzy
C is transparent transparent
Plate 3
Sample * 01 days 2 days 3 days 4 days 18 months
A is transparent transparent
B is transparent fuzzy fuzzy
C is transparent transparent
* A is without stable.
B contains two (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate (TINUVIN  123) of 2wt%.
C contains compound two [1-(2-hydroxy-2-methyl propoxy--2,2,6,6-tetramethyl piperidine-4-the yl)] sebate of the embodiment 2 of 2wt%.
These data presentation, the group that on the 1-position of hindered amine, connects be the good solvability of the The compounds of this invention of hydroxyl and with the compatibleness of polyester urethane coating, yet this is that to lack the compound institute of described hydroxyl in the prior art irrealizable.
Experiment shows, if compound of the present invention is soluble and compatible in specific varnish, they should also be compatible and soluble in other resin system so.
Embodiment 100
Make stable two-pack Clear paint in 4 ounce jars of sealing the gelling identical of about 50mL with preparation described in the embodiment 99.Being observed visually curing back coating is still transparent.Muddy or fuzzy appearance explanation hindered amine stabilizer and coatings formulated are incompatible.
Coating material solidified in jar
Sample * 01 days 2 days 18 months
A is transparent
B is transparent muddy muddy
C is transparent
* A is without stable.
B contains two (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate (TINUVIN  123) of 2wt%.
C contains compound two [1-(2-hydroxy-2-methyl propoxy--2,2,6,6-tetramethyl piperidine-4-the yl)] sebate of the embodiment 2 of 2wt%.
These data presentation, the group that on the 1-position of hindered amine, connects be the The compounds of this invention of hydroxyl have good solvability and with the compatibleness of polyester urethane coating, yet this is that to lack the compound institute of described hydroxyl in the prior art irrealizable.
Embodiment 101
1-(2-hydroxy-2-methyl propoxy-)-4-[9-(methoxycarbonyl) acyloxy in the ninth of the ten Heavenly Stems]-2,2,6, the 6-tetramethyl piperidine
With the compound that makes among the embodiment 16A and lithium amide this title compound of prepared in reaction in dimethylbenzene of 1 equivalent or several normal dimethyl sebacate and catalytic amount.
Embodiment 102
1-(2-hydroxy-2-methyl propoxy-)-4-[5-(methoxycarbonyl) valeric acid base]-2,2,6, the 6-tetramethyl piperidine
Step by embodiment 101 prepares this title compound, and just the dimethyl adipate with equivalent replaces dimethyl sebacate.
Embodiment 103
1-(2-hydroxy-2-methyl propoxy-)-4-[3-(methoxycarbonyl) propionyloxy]-2,2,6, the 6-tetramethyl piperidine
Step by embodiment 101 prepares this title compound, and just the Succinic acid dimethylester with equivalent replaces dimethyl sebacate.
Embodiment 104
1-(2-hydroxy-2-methyl propoxy-)-4-[4-(methoxycarbonyl) butyric acid base]-2,2,6, the 6-tetramethyl piperidine
Step by embodiment 101 prepares this title compound, and just the Methyl glutarate with equivalent replaces dimethyl sebacate.
Embodiment 104A
1-(2-hydroxy-2-methyl propoxy-)-4-[5-(methoxycarbonyl) valeric acid base]-2,2,6,6-tetramethyl piperidine and 1-(2-hydroxy-2-methyl propoxy-)-4-[4-(methoxycarbonyl) butyric acid base]-2,2,6, the mixture of 6-tetramethyl piperidine
DBE-2 dibasic ester (DuPont ) with equivalent replaces dimethyl sebacate, repeats embodiment 101.
Embodiment 104B
1-(2-hydroxy-2-methyl propoxy-)-4-[5-(methoxycarbonyl) valeric acid base]-2,2,6,6-tetramethyl piperidine and 1-(2-hydroxy-2-methyl propoxy-)-4-[4-(methoxycarbonyl) butyric acid base]-2,2,6, the mixture of 6-tetramethyl piperidine
DBE-3 dibasic ester (DuPont ) with equivalent replaces dimethyl sebacate, repeats embodiment 101.
Embodiment 105
With the 4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6 of methoxyl group ending, the 6-tetramethyl piperidine with
The polycondensate of hexamethylene diisocyanate
Compound that makes among the embodiment 16A with equimolar amount roughly and hexamethylene diisocyanate reaction, then and this title compound of excessive methanol prepared in reaction.
Embodiment 106
With the 4-hydroxyl-1-(2-hydroxyl-oxethyl)-2,2,6 of methoxyl group ending, 6-tetramethyl piperidine and hexa-methylene
The polycondensate of vulcabond
Compound that makes among the embodiment 70 with equimolar amount roughly and hexamethylene diisocyanate reaction, then and this title compound of excessive methanol prepared in reaction.
Embodiment 107
With the 4-hydroxyl-1-(2-hydroxyl-1-benzene oxyethyl group)-2,2,6 of methoxyl group ending, 6-tetramethyl piperidine and six
The polycondensate of methylene diisocyanate
Compound that makes among the embodiment 74 with equimolar amount roughly and hexamethylene diisocyanate reaction, then and this title compound of excessive methanol prepared in reaction.
Embodiment 108
The stabilization of bi-component acrylic base urethane varnish
Hindered amine is tested stablizer to add in the bi-component acrylic base urethane coating described in the embodiment 99.This system is in order to the dibutyl tin dilaurate catalysis of total resin solid meter 0.02wt%.With sufficient quantity this stablizer is added in the acrylic acid or the like polyvalent alcohol of this two-component coating, mix with isocyanate component immediately before use then.
Be coated with smooth steel plate 3 with electrocoated primer " * 4 " then with light blue containing metal priming paint coating, use then through stable varnish coating.The priming paint coating thickness is 1.0mil (25 a microns) build, is 1.0mil (25 microns) build through stable varnish applied thickness.Coating is through dry air, and aging 2 weeks.These plates are exposed among the Xenon-Arc Weather-Ometer under the following conditions then:
Cam 180 circulation: light was only arranged in 40 minutes; 20 minutes light and preceding spray; Light was only arranged in 60 minutes; 60 minutes dark and back of the body spray enriched materials.
The lamp strainer is: the quartzy heart/borosilicate S outside.
Irradiance: 0.45w/m 2
Measured 20 ° of gloss before exposing and in the process-exposed every 500 hours.It is desirable to keep higher gloss.
20 ° of gloss percent retention
Sample * 4500 hours 8500 hours 12000 hours
A?????????????17??????????????-??????????????-
B?????????????60?????????????22??????????????-
C?????????????47?????????????17??????????????-
D?????????????34?????????????22??????????????-
E?????????????41?????????????23??????????????-
F?????????????75?????????????45?????????????28
G?????????????77?????????????45?????????????27
* A is without stable.
B contains two (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate (TINUVIN  123) of 1wt%.
C contains compound two [1-(2-hydroxy-2-methyl propoxy--2,2,6,6-tetramethyl piperidine-4-the yl)] sebate of the embodiment 2 of 0.9wt%.
D contains 2 of 1.04wt%, 4-two [N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl)-N-butyl amino]-6-(2-hydroxyethylamino)-S-triazine.
E contains the compound of the embodiment 12 of 1.01wt%.
F contains two (1-octyloxy-2,2,6,6-tetramethyl-the are sent pyridine-4-yl) sebates (TINUVIN  123) of 2wt%.
G contains compound two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-the yl)] sebate of the embodiment 2 of 1.8wt%.
These data presentation, the compound that hydroxyl of the present invention replaces obtain can with etc. 20 ° of gloss retention values comparing of the NOR compound of volumetric molar concentration.
Embodiment 109
The stabilization of bi-component acrylic base urethane varnish
The varnish of preparation among the embodiment 108 is coated in 1 by commentaries on classics " on the silicone disc, about 25 microns of the thickness of its dry film.Use the Zeiss interferometer to measure the initial optical thickness of each dish.These dishes are exposed among the Xenon-Arc Weather-Ometer under the following conditions then:
Cam 180 circulation: light was only arranged in 40 minutes; 20 minutes light and preceding spray; Light was only arranged in 60 minutes; 60 minutes dark and back of the body spray enriched materials.
The lamp strainer is: the quartzy heart/quartz outside.
Irradiance: 0.55w/m 2
Measured blooming every 250 hours, and the film of measuring each goods is lost.Because the film that causes of weathering is lost is listed in the table below, it is low more good more to wish that film is lost value after 3972 and 5561 hours.
Film is lost value (in micron)
Sample * 3972 hours 5561 hours
A 23.3 corrodes fully
B????????????????6.9?????????????????16.3
C????????????????6.7?????????????????17.8
D????????????????6.3?????????????????14.3
E????????????????5.9?????????????????12.4
F????????????????6.5?????????????????16.1
G????????????????6.6?????????????????16.7
* A is without stable.
B contains two (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate (TINUVIN  123) of 1wt%.
C contains compound two [1-(2-hydroxy-2-methyl propoxy--2,2,6,6-tetramethyl piperidine-4-the yl)] sebate of the embodiment 2 of 0.9wt%.
D contains 2 of 1.04wt%, 4-two [N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) N-butyl amino]-6-(2-hydroxyethylamino)-S-triazine.
E contains the compound of the embodiment 12 of 1.01wt%.
F contains the 1-octyloxy-2,2,6 of 0.78wt%, 6-tetramethyl--4-hydroxy piperidine.
G contains the compound 1-of the embodiment 16A of 0.56wt%, and (2-hydroxy-2-methyl propoxy--2,2,6,6-tetramethyl--4-hydroxyl is piperidines very.
These data presentation, the compound that hydroxyl of the present invention replaces obtain can with etc. 20 ° of gloss retention values comparing of the NOR compound of volumetric molar concentration.
Embodiment 110
Coating on plastic substrates
The main application of non-alkaline hindered amine is the finish paint that is used for protection automobile on the plastic substrates.But in dry and solidification process, many lower molecular weights, the photostabilizer of failing to react move in the plastic substrates.As a result, most of photostabilizer may enter substrate and loses from finish paint, does not therefore have the effect of the described finish paint of protection.
Concentration by hindered amine in the cured varnish that will apply on the plastic substrates with compare as the concentration of the identical varnish of coating on the impermeable substrate of glass or steel, be determined at that coating uses and solidification process in the degree that enters of hindered amine stabilizer.
Hindered amine stabilizer adding to be tested is suitable in the elasticity thermoset acrylics/melamine varnish of automobile plastic substrate.The add-on of hindered amine is 1.5% of total resin solid weight.
By automatic spray apparatus every kind of coating is coated on automotive grade RIM (through reaction injection molding) substrate and the TPO (TPO).Two kinds of substrates all are 4 " * 12 " plate.Be coated with every kind of coating and make the about 2.0mils of its dry film thickness (50 microns).Bake 20 minutes down with coating material solidified at 250 °F (121 ℃).
Three duplicate samples of solidified coating in every are taken off from every kind of substrate, and pulverize at low temperature becomes fine powder.In backflow toluene, extract every kind of sample of known quantity whole night.By the hindered amine that is diluted to known volume and exists by HPLC or SFC chromatographic quantitative analysis.Develop the calibration curve of every middle test stabilizer compounds.Measure every kind of hindered amine content that extracts coating by this method.
When will be on nitrogen-atoms the hindered amine compound of the present invention that replaces of usefulness-O-E-OH with do not have such hydroxyl corresponding-when the NOR compound is compared, the per-cent of the hindered amine compound of the present invention that reclaims the varnish of discovery on plastic substrates is higher, this explanation hindered amine of the present invention less enters plastic substrates, makes the stability of the clear finish on such plastic substrates better.
Embodiment 111
The stabilization of water transport woodwork varnish
Coating comprises the coating that is used for various uses in a large number in the water, comprise vehicle paint base, industrial coating and commercial coating, and proportion is increasing.These coating can be coloured can be transparent.And be tending towards containing more solids, this depends on the retention property of photostabilizer when exposing usually, and the amount of solubility promoter is fewer and feweri.This requires stablizer to have higher solubleness or in fact water-soluble in such solubility promoter (being water at first).
The test stablizer is added in the water be dissolved in the hydrotropy mixture in advance in the dispersion.Water gathers the vinylformic acid that dispersion is commercially available acquisition/urethane hydride resin.The solubility promoter blend be TEXANOL  (2,2,4-trimethylammonium-1, the 3-pentanediol, Texaco) and ARCOSOLVE  TPM (the tripropylene glycol methyl esters is AtlanticRichfield) with 1: 1 mixture.
0.45g is tested stablizer be dissolved in advance in the 10g solubility promoter blend, add following component then
PpwFLEXTHANE  (A ir Products) 100.0Foamaster VF 0.1 water 10.0TEKANOL/ARCOSOLVE/ hindered amine 10.5 ultraviolet absorbers (TINUVIN  1 130, Ciba) 1.2BYK 346 0.5MICHEMLUBE  162 2.0
It is 6 that every kind of paint brush is coated in the cross section " * 6 " cdear and deal board on.By the weight that the weight that claims coating and brush before use and is afterwards regulated coating, guarantee that the coating weight that each section be coated with is identical.
Make at room temperature dry two weeks of cross section of institute's coated plate, with the naked eye estimate gloss appearance and Hunter colourity L*, a* and b* then.These fragments are exposed on the frame of 45 of South Florida and continue 6 months, regain afterwards, and with the naked eye estimate outward appearance, gloss, colour-change and any degraded or stratified other sign.
Aspect outward appearance, gloss retention, anti-colour-change and the layering of naked eyes, with corresponding do not have this class hydroxyl-the NOR compound compares, the brush amine compound of the present invention that usefulness-O-E-OH replaces on nitrogen-atoms provides better stabilising effect.
Embodiment 112
The stabilization of coloured automotive OEM priming paint
Stable with the painted priming paint of Pigment Red 177 and micaceous mixture in order to 1% hindered amine stabilizer of total priming paint solid (pigment+resin) weight.With dried film thickness 1mil (25 microns) with priming paint spray to through finishing 4 " * 12 " on the steel plate, carry out face with the high automobile varnish of the solids content of commercially available acquisition then and be coated with.The plate that was coated with was solidified 30 minutes down at 250 ° (121 ℃).Under the following conditions these plates are exposed among the Xenon-ArcWeather-Ometer then:
Cam 180 circulation: light was only arranged in 40 minutes; 20 minutes light and preceding spray; Light was only arranged in 60 minutes; 60 minutes dark and back of the body spray enriched materials.
The lamp strainer is: the quartzy heart/borosilicate S outside.
Irradiance 0.55w/m 2
500 hours dams 4 fixed 20 before exposing and after exposing 3000 hours.Gloss, image definition, Hunter colourity blank value (L*, a*, b* and △ E).
Aspect image definition, gloss retention, anti-colour-change, with corresponding do not have this class hydroxyl-the NOR compound compares, the brush amine compound of the present invention that usefulness-O-E-OH replaces on nitrogen-atoms provides better stabilising effect.
Embodiment 113
The molded purposes of ABS
To comprise that styrene monomer and acrylonitrile compolymer reaction and styrene monomer mix with The compounds of this invention is dried with the thermoplastic (being commonly referred to ABS) of the copolymer mixture of butadiene copolymer reaction gained, and fuse into Metallic stearates, 0-5% pigment, 0.05-2.0% ultraviolet absorbers, 0.0-0.1% phosphite, 0.0-1.25% phenolic antioxidant, the 0.0-0.1%N that the particle representative formula contains 0.05-2.0% The compounds of this invention, 0.05-0.5% such as calcium stearate, N-dialkyl group azanol and other hindered amine stabilizer of 0.0-2.0% optionally.
To become useful goods through the resin treatment of this full formula of granulation then, for example extruding in flakes, film, profile and pipe; Mold becomes bottle; Be injection molded into moulded product; Be thermoformed into moulded product; Or rotational moulding becomes hollow piece.
The material that contains The compounds of this invention has shown good: the anti-purple sunset of looking up with eyes wide open is foretold the light and heat destructive characteristics.
Embodiment 114
The pKa value
In order to measure the pKa value of water-fast material, the titration of anhydrous ground has organic object of reference of known pKa value in the water.Draw this half-neutralization potential (HNP) figure of its known water liquid pKa value relatively with reference to material.The HNP of determination test material, thereby the corresponding pKa value of push out test material.These organic object of reference material packages draw together 2,2,6,6 one tetramethyl piperidines, 4-hydroxyl-2,2,6,6-tetramethyl piperidine, 1-hydroxyethyl-4-hydroxyl-2,2,6,6-tetramethyl piperidine, triacetonamine and methylphenylamine.
To test relevant slightly and the acetonitrile with reference to material and 1: 1 that can both be water-soluble of material with the present invention at least on the structure: chloroform is used to make anhydrous titration (1: 1 acetonitrile: chloroform solvent and 0.1N perchloric acid/two Alkane titrating solution) calibration chart of system.Claim about 0.5 millinormal test material to put into the titration beaker.Add the 30mL pyruvonitrile with sample dissolution.Before titration, add the 30mL chloroform.Carry out titration and measure HNP.The electrolytic solution of reference electrode is 2-(amino methyl) pyridine.Electrode was left standstill in solvent systems 2 hours, insert electrolytic solution then and reach balance.
All samples all repeats once.The pKa value sees the following form.
The pKa that sample * HPN (mv) calculates
I????????523??????????3.9
II???????426??????????4.9
III??????513??????????3.8
IV????????-???????????4.6
V?????????-???????????3.8
VI????????-???????????4.8
* I is the compound of embodiment 73.
II is 1-cyclohexyloxy-4-octadecane acidic group-2,2,6, the 6-tetramethyl piperidine.
III is the compound of embodiment 2.
Two (1-octyloxy-2,2,6,6-tetramethyl piperidine-4-yl) sebate that IV is.
V is the compound of embodiment 50.
VI is 2,4-two [N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) butyl amino]-6-chloro-S-triazine and N, the reaction product of N '-two (3-aminopropyl) quadrol.
Several being replaced by-O-R on the 1-position that their difference only is at piperidine ring still is to be replaced by-O-E-OH to related compound as can be seen from top, and the pKa value of of the present invention-O-E-OH compound is quite low.This meaning is that the distinctive points that described The compounds of this invention is compared with the N-OR compound of prior art is that basicity is relatively low.
Check gained result among the embodiment 77, shown that lower basicity and lower pKa value can be converted into premium properties, compare with the N-OR compound of maximally related prior art, prevent to coat with lacquer fall down from the TPO (TPO) that can be coated with aspect, The compounds of this invention is better.
Embodiment 115
Flame retardant resistance
With fibrous polypropylene and test additives dry blended, under 234 ℃ (450 °F), fuse into particle then.All goods also contain the stabiliser system of melt-processed.Use a Hills Laboratary type fiber extrusion machine will be spun into fiber through the full formula resin of granulation down then at 246 ℃ (475 °F).The ratio of 41 tow that spun of bundle with 1: 3.2 stretched, and obtaining final denier is 615/41.
On Lawson-Hemphill Analysis Knitter, fibrage is become socks then.Under NFPA701-1996 Vertical burn procedure with every kind of sample repeated test 10 times.In second down knit sock after removing the burning of infringement property to the time of extinguishing (being called " afterfire ").Effectiveness as fire retardant confirms, observes and compares with the relative blank sample that does not contain fire retardant, and combustion time is short thereafter.Also note from the drip combustion time and the weight of (drips) of material and lose.Data presentation NOR HALS of the present invention is more effective fire retardant.
Burning is dripped in additive afterfire (s), and (drip weight is lost (%)
burn)(s)
Blank, the compound of no fire retardant 32＞50 63 embodiment 73,1.0% 0.5 12.5 36
Embodiment 116
The flame retardant resistance in the thick cross section of polypropylene
With molded grade polypropylene and test additives dry blended, be fused into particle then.Except that The compounds of this invention, in goods, comprise halogenated fire-retardants.Representative formula contains The compounds of this invention and fire retardant as three (3-bromo-2,2 two (brooethyl) propyl group) phosphoric acid ester (FMC PB370); The dihydroxyphenyl propane (PE68) of two (2,3-dibromopropyl ether); Ten bromobenzene ethers (DBDPO); Ethylene-tetrabromo-phthalic imide (SATEX BT-93); Ethylene-dibromo norborneol two-carbonyl imide (SATEX BN-451).Except that brominated flame retardant, other goods can contain Sb 2O 3Other goods can contain the phosphorous-containigroups groups material flame-retardant as quadrol bisphosphate (EDAP).Use a WabashCompression Molder to be compression molded into sample then through the full formula resin of granulation.
Testing experiment plate under UL-94 Vertical burn condition.Every kind of minimum repeated test of sample 3 times.In second down sample after the property damaged burning is removed for the first time and for the second time to the mean time of extinguishing.Effectiveness as fire retardant confirms that it is short to observe combustion time.The compounds of this invention has been strengthened the halogenation of independent test or the flame retardant properties of phosphate flame retardant.
Embodiment 117
The thick segmental flame retardant properties of TPO
Thermoplastic olefin (TPO) particle that contains The compounds of this invention by injection moulding prepares moulded specimen.These TPO goods also can contain the mixture of pigment, phenolic antioxidant, phosphorous acid ester or azanol, Metallic stearates, ultraviolet absorbers (UVA) or hindered amine stabilizer (HALS) or ultraviolet absorbers and hindered amine stabilizer.
Except that The compounds of this invention, in these goods, comprise halogenated fire-retardants.Typical products and its contains The compounds of this invention and fire retardant as three (3-bromo-2,2 two (brooethyl) propyl group) phosphoric acid ester (FMC PB370); The dihydroxyphenyl propane (PE68) of two (2,3-dibromopropyl ether); Ten bromobenzene ethers (DBDPO); Ethylene-tetrabromo-phthalic imide (SATEXBT-93); Ethylene-dibromo norborneol two-carbonyl imide (SATEX BN-451).Except that halogenated fire-retardants, other goods can contain Sb 2O 3Other goods can contain the phosphorous-containigroups groups material flame-retardant as quadrol bisphosphate (EDAP).
Testing experiment plate under UL-94 Vertical burn condition.Every kind of minimum repeated test of sample 3 times.In second down sample after the property damaged burning is removed for the first time and for the second time to the time of extinguishing.The compounds of this invention has been strengthened the halogenation of independent test or the flame retardant properties of phosphate flame retardant.
Embodiment 118
Light stability in fire retardant ABS mold applications
With molded level ABS and test additives dry blended, be fused into particle then.Except that The compounds of this invention, in goods, also comprise fire retardant through selecting.Fire retardant is: three (3-bromo-2,2 two (brooethyl) propyl group) phosphoric acid ester; Ten bromobenzene ethers; Ethylene (tetrabromo-phthalic imide); Ethylene (dibromo norborneol two-carbonyl imide).Use a BOY 50M testing laboratory type injection moulding machine to be injection molded into sample then through the full formula resin of granulation.Except that halogenated fire-retardants, other goods can contain Sb 2O 3Other goods can contain the phosphorous-containigroups groups material flame-retardant as diamines bisphosphate (EDAP).
Test panel is installed in the metal frame, and is exposed to according to ASTM G26 test procedure and has among the Atlas Ci65 Xenon Arc Weather-O-meter of interval light/secretly circulate and spray water.The change of the elastic performance of periodic intervals specimen and the change of color.It is long more that performance is lost time of generation, and the color change of measuring by Δ E is few more, and then the effect of stable system is good more.
In the efflorescence of quickening, contain sample of the present invention and have good stretch-proof performance and minimum color change.
Embodiment 119
Light stability in fire retardant HIPS mold applications
Molded level is high anti-towards polystyrene and test additives dry blended, be fused into particle then.Except that The compounds of this invention, in goods, also comprise fire retardant through selecting.This fire retardant is: three (3-bromo-2,2 two (brooethyl) propyl group) phosphoric acid ester; Ten bromobenzene ethers; Ethylene (tetrabromo-phthalic imide) and ethylene (dibromo norborneol two-carbonyl imide).Use a BOY 50M testing laboratory type injection moulding machine to be injection molded into sample then through the full formula resin of granulation.Except that brominated flame retardant, other goods can contain Sb 2O 3Other goods can contain the phosphorous-containigroups groups material flame-retardant as quadrol bisphosphate (EDAP).
Test panel is installed in the metal frame, and is exposed to according to ASTM G26 test procedure and has among the Atlas Ci65 Xenon Arc Weather-O-meter of interval light/secretly circulate and spray water.The change of the tension force performance of periodic intervals specimen and the change of color.It is long more that performance is lost time of generation, and the color change of measuring by Δ E is few more, and then the effect of stable system is good more.
In the efflorescence of quickening, contain sample of the present invention and have good stretch-proof performance and minimum color change.
Embodiment 120
The stabilization of the acid catalyzed thermosetting acrylic resin enamel paint of high solid
Stablize by adding different The compounds of this invention for the catalytic high solid of lauryl Phenylsulfonic acid (50wt%) the thermosetting acrylic resin enamel paint of basis meter 0.8wt% in order to film forming resin.High solid thermosetting acrylic resin enamel paint goods (from the Acryloid AT400 of Rohm and Haas) are based on hydroxyethyl methylacrylate, methyl methacrylate, vinylbenzene, butyl acrylate and butyl methacrylate and melamine solidifying agent.
In order to polyester/Resins, epoxy is the steel thin slice 4 of the priming paint coating on basis " * 12 " (9.16cm * 30.48cm), be the painted priming paint coating of TiO2-of base-material then in order to tackiness agent and acid catalyst, this tackiness agent is 70% the monomer such as the melamine resin of Hydroxyethyl acrylate, vinylbenzene, vinyl cyanide, butyl acrylate and vinylformic acid and 30%, at last with transparent finished enamel coating.The thickness of priming paint with about 0.8mil (0.0203mm) is sprayed on the steel disc, and dry air 3 minutes.Then the thickness of transparent finished enamel with about 2.0mil is sprayed on the thin slice.After the dry air 15 minutes, under 121 ℃, should apply thin slice and bake in 30 minutes.
Before being coated in enamel paint on the priming paint, stablizer to be tested is added in the thermosetting acrylic resin finished enamel with 0.1wt%.
After in air-conditioning room (23 ℃/50% relative humidity), depositing for 3 weeks, according to SAE J1920 with the weathering 2000 hours in Xenon arc Weather-Ometer of institute's applying lame.In this device, make this sample recirculation carry out weathering in 180 minutes.Keep the stable effect of mensuration by 20 ° of glossy after the weathering.
Under extreme weathering condition, after the weathering, present 20 ° of good glossy retention through the stable thin slice of The compounds of this invention.
Embodiment 121
Equally, serve as the basis to through the sharpness (DOI) of the roasting and roasting sample that overdoes, image, at Hunter Associates Apparatus, 20 ° of gloss (ASTM D-523-80) and macroscopic embrittlement are estimated the sample for preparing among the embodiment 120 with Knoop Hardness (ASTM D-1474-68).
Present the pattern of bigger 20 ° of gloss retention and DOI through the stable sample of The compounds of this invention, and after exposing, do not have serious embrittlement for more time.
Embodiment 122
The thermoset acrylics enamel paint of embodiment 120 and 3wt% benzotriazole ultraviolet absorbers and 1.5wt% hindered amine test compounds of the present invention is formulated together.This enamel paint is coated on white primer or the silvery white containing metal priming paint.Baking is carried out under 121 ℃ of normal baking temperature or 82 ℃ automatically low bakings reparation temperature.
Coating plate is exposed in the Xenon arc exposing device.Measure 20 ° of gloss and clear picture (DOI) value.
Present the pattern of bigger 20 ° of gloss retention and DOI through the stable sample of The compounds of this invention.
Embodiment 123
Two kinds of thermoset acrylics enamel paint and 3wt% benzotriazole ultraviolet absorbers and the agent of 1wt% hindered amine stable testing of the present invention is formulated together.
This thermoset acrylics enamel paint is based on tackiness agent and acid catalyst, this tackiness agent is 70% the monomer such as the melamine resin of Hydroxyethyl acrylate, vinylbenzene, vinyl cyanide, butyl acrylate and vinylformic acid and 30%, acid catalyst such as tosic acid, dinonylnaphthalene disulfonic acid, lauryl Phenylsulfonic acid or phenyl-phosphate.
In order to polyester/Resins, epoxy is the steel thin slice 4 of the priming paint coating on basis " * 12 " (9.16cm * 30.48cm), then with the priming paint coating, at last with transparent finished enamel coating.The thickness of priming paint with about 0.8mil (0.0203mm) is sprayed on the steel disc, and dry air 3 minutes.Then the thickness of transparent finished enamel with about 2.0mil is sprayed on the thin slice.After the dry air 15 minutes, under 121 ℃, should apply thin slice roasting 30 minutes.
Coating plate is exposed in the Xenon arc exposing device.Measure 20 ° of gloss and clear picture (DOI) value.
Present the pattern of bigger 20 ° of gloss retention and DOI through the stable sample of The compounds of this invention.
Embodiment 124
To be that the nothing oil alkyl coil coating of base-material is used for this embodiment with white polyester/melamine.With the coil rod this full formula lacquer is coated onto the steel disc of process finishing to obtain the 0.6-0.8mil dry film.Under 220 ℃, this plate is baked about 90 seconds, remove stove and water quenching immediately.The plate of this coating is exposed in the Xenon Arc Weather-Ometer of South Florida with 45.Measure 20 ° of gloss numbers.
Present the pattern of bigger 20 ° of gloss retention through the stable sample of The compounds of this invention.
Embodiment 125
To comprise that the benzotriazole of the thermoset acrylics enamel paint of embodiment 124 of 0.8% lauryl Phenylsulfonic acid and different concns or S-triazine ultraviolet light absorbers and hindered amine test compounds of the present invention are formulated together.According to the step of embodiment 124, this enamel paint is coated on the silvery white containing metal priming paint.Baking is to carry out 30 minutes under 121 ℃ of normal baking temperature.
Coating plate is exposed among the Xenon arc Weather-Ometer.Measure 20 ° of gloss and lose time of 50%.
Present 20 ° of good gloss retention through The compounds of this invention and the stable sample of ultraviolet absorbers, and observe under 20 ° of gloss longer until 50% lost hours.
Embodiment 126
Preparation is the thermoset acrylics enamel paint of base-material with tackiness agent and acid catalyst, wherein tackiness agent is 70% the monomer such as the melamine resin of Hydroxyethyl acrylate, vinylbenzene, vinyl cyanide, butyl acrylate and vinylformic acid and 30%, and acid catalyst is as tosic acid, dinonylnaphthalene disulfonic acid or lauryl Phenylsulfonic acid.With the 9.16cm * 30.48cm of commercially available acquisition not lacquered board as substrate.This plate is applied with silvery white containing metal priming paint and transparent finished enamel.Priming paint is stable with 1% benzotriazole ultraviolet absorbers and 1% hindered amine test compound of the present invention (in solid resin), and is sprayed on this plate, and the about 0.6-0.8mil of thickness was through dry air 3 minutes.The varnish that will comprise aforementioned stable agent coating thickness then is 1.7-2.0mils, and dry air is 10 minutes afterwards, institute's coated plate 12 1 ℃ roasting 30 minutes down.The plate that will apply is exposed in the Xenon arc device then, and measures 20 ° of gloss numbers.
Present 20 ° of good gloss retention through The compounds of this invention and the stable sample of UV light stabilizing agent.
Embodiment 127: being formulated as follows of acrylic melamine enamel paint in the water:
(50% vinylformic acid in butyldiglycol is set 42 fat to resin solid umber Sythacryl VSW 6483 (from the acrylic acid dispersion of Hoechst) 30Sythacryl VSW 6484, Hoechst) Maprenal MF 915 (70% melamine resin in the isopropylcarbinol) 25Maprenal MF 927 3 (melamine resin) 100
Priming paint (from BASF) is sprayed on coiling and scribbles that to prepare with water on the aluminium sheet of epoxy primer be the priming paint/varnish enamel paint of base-material in the industrial silvery white containing metal water that 0.6-0.8mil is thick.This material 80 ℃ of 5 minutes following baking, is clearly applied enamel paint in the 1.6-1.8mil water then.With this system 80 ℃ 10 minutes down roasting, then 140 ℃ 30 minutes roasting down.Before coating varnish, sample of the present invention and photostabilizer are dissolved in the minimum acetate butyl glycol ester, add in the lacquer again.Coating plate is exposed in the Xenon arc device 975 hours.The clear picture of assay plate (DOI) retention.
Present bigger DOI value retention through the stable sample of The compounds of this invention.
Embodiment 128
The stabilization of tung oil phenol varnish
The western red cedar sheet of 1.27cm * 20.32cm * 30.48cm that will have thin radial notch is used to test the tung oil phenol varnish (being supplied with by McCloskey) of commercially available acquisition.Half of each plate applies without stable varnish with two kinds.The equivalent varnish that will contain the agent of 5wt% (in resin solid) stable testing is coated on second half of plate of two kinds of coating.After at room temperature depositing for two weeks, plank is placed on outdoor lasting 8 months with miter angle.According to ASTMD 523, at each 60 ° of gloss of half of top, middle part and bottom assay plate of plate.Because the timber substrate is inhomogeneous, the gloss retention of the identical varnish between plate and the plate has some difference.Therefore, because the existence of test compounds of the present invention makes the improved mensuration of gloss more meaningful to every plate coating without stable contrast varnish.
After long-term exposure, present good gloss retention through the stable plate of The compounds of this invention.
Embodiment 129
The stabilization of aromatic base urethane varnish
Test aromatic base urethane varnish (Flecto-Varathane#90) sample of commercially available acquisition by embodiment 128 described same procedure.Outdoor expose 5 months with miter angle after, in the assay plate without stable and through 60 ° of gloss retention values of steady component.
Present good gloss retention through the stable plate of The compounds of this invention.
Embodiment 130
The stabilization white polyester of bi-component polyester urethane gloss enamel paint is pressed following preparation:
Component I part Desmophen 670-90 (polyester glycol, Mobay) 132.4
Titanium dioxide 198.6
Methylcellulose gum acetic ester 98.9
Sand mill
Desmophen?670-90?????????????????94.98
Glidant 0.28
Tertiary amine 0.015
Methylcellulose gum acetic ester 332.6
Component I I Desmodur N-100 (polymeric polyisocyanate, Mobay) 93.9
Methylcellulose gum acetic ester 58.7
With the build of 1.5-2.0mil this material is sprayed on previously with industrial epoxy polyamide and keeps on the Bonderite40 cold-rolled steel sheet that priming paint (Sherwin-Williams Tile Clad II) applied.Before coating, in lacquer, add test compounds of the present invention.Room temperature was deposited after 2 weeks, and each three blocks of plate of every kind of goods are exposed to outdoor 9 months with miter angle.Measure 20 ° of gloss retention by ASTM D 523-80 in top, middle part and the bottom of every block of plate afterwards.Like this, obtain the mean value of 9 gloss reservation measured values of per three parts of plates.
Present good gloss retention through the stable plate of The compounds of this invention.
Embodiment 131
The stabilization of vinylformic acid Synolac smoothing enamel paint
The vinylformic acid Synolac priming paint that will have non-detachment aluminium pigment and dye nattier blue commercially available acquisition is stable with benzotriazole ultraviolet absorbers and hindered amine test compound of the present invention, is sprayed on then on the Bonderite40 plate that had applied with Synolac priming paint.After coating at room temperature solidified 14 days, these plates are exposed to outdoor 8 months with miter angle.Measure 20 ° of gloss of the plate that exposed.
Present good gloss retention through the stable plate of The compounds of this invention.
Embodiment 132
The stabilization of medium oil alkyd enamel paint
To use non-detachment aluminium coloring and dye nattier blue medium oil alkyd enamel paint stable, be sprayed on then on the cold-rolled steel sheet that applied with epoxy primer with benzotriazole ultraviolet absorbers and hindered amine test compound of the present invention.Coating was at room temperature solidified after 2 weeks, these plates were exposed among the Xenon arc Weather-Ometer accelerated weathering 840 hours.20 ° of gloss numbers of assay plate before exposure and after exposing.
Present good gloss retention through the stable plate of The compounds of this invention.
Embodiment 133
The electropaining composition
Add to dihydroxyphenyl propane, polyethylene oxide glycol, dihydroxyphenyl propane and the dimethylbenzene of diglycidylether in one beaker and be heated to 135 ℃ to prepare typical E-coating composition.Add the xylidene(s) catalyzer in the dimethylbenzene, temperature remain on 143 ℃ following 2 hours.Measure the weight (WPE) of each epoxy, add then prepare in advance by 2, the linking agent that 4-Xylene Diisocyanate, the three formyl radical propane of inlaying with alcohol are formed, temperature drops to 100 ℃.Then with two kinds of different secondary amine be two ketoimines of Diethylenetriamine and Mono Methyl Ethanol Amine at the phenyl cellosolve middle cover on the residual epoxide group.Under 110 ℃, temperature was kept 1 hour, add the linking agent hexamethylene diisocyanate of inlaying with alcohol.Near 100 ℃, temperature was kept 30 minutes, resin compound is added in deionized water, tensio-active agent and the lactic acid, obtain resin emulsion.
In this resin emulsion, add hindered amine compound of the present invention, other Resins, epoxy, carbon black, tributyltin oxide catalyst, titanium dioxide, lead silicate, water and ultraviolet absorbers.Use sand mill to disperse to reach after the suitable fineness, mixture is added in the electropaining pond that water is arranged be used for electropaining on metal substrates.
Steel coating thickness with top E-coating resin composition electropaining is 23-30 μ m, and solidifies 20 minutes under 176-201 ℃ temperature.Be used in the acrylic coating composition in organic solvent, pigment and the ultraviolet absorbers, apply the colored resin layer of 20-51 μ m thickness thereon.Then that institute's coated plate is roasting down to solidify pigmented layer at 121-129 ℃.
These plates are exposed to outdoor 4 months then.The plate that contains hindered amine compound of the present invention when particularly using with ultraviolet absorbers, has good opposing separates the E-coating from metal substrates performance.
Embodiment 134
Wear-resistant paint composite
With 1 of 50wt%; the solution for vacuum stripping of the Virahol in the 6-hexylene glycol, 10% 3-methylacrylic acid propyl trimethoxy silicane and 40% colloidal silica (with 34% water liquid dispersion form) with remove volatile matter and with hindered amine of the present invention, benzotriazole ultraviolet absorbers and 2; 4,6-trimethylbenzoyl diphenylphosphine light trigger mixes.These not gellings of component when storage.
Top composition is coated to by roller coating on the bisphenol-a polycarbonate film of 15mil, with the film of this coating with the linear velocity of 610cm/min by the mercury lamp under 43 ℃.On the polycarbonate substrate said composition is being solidified into transparent coating on the colourless and optics.
Measure abrasion property by Taber Abrasion Test (ASTM D 1044).
It is aging to use an Atlas Ci35A Xenon Arc Weather-Ometer also this sample to be carried out weathering.The result shows that the coating that contains hindered amine compound of the present invention has the yellow and muddy performance that forms of good resistance.
Embodiment 135
On polycarbonate, apply
Stablize bi-component polyester urethane coating by adding hindered amine compound of the present invention.With isocyanic ester be base-material resin (Desmodue N-3390, Bayer) crosslinked high-solid polyester polyvalent alcohol (Desmophen 670-80, Bayer).This coating of dibutyl tin dilaurate catalyst catalysis with 0.015wt%.
4 " * 6 " with the polycarbonate be of the Clear paint coating of plastic substrates (Xenoy) plate of base-material, the about 1.5mils of thickness with this preparation.Paint spay-coating on substrate, was baked 20 minutes down at 82 ℃ then.
At room temperature preserve after 1 week, every block of plate cut into 2 " * 3 " section, 5 parts of every kind of goods systems.Be placed in 8-oz jar and sealing with 2ml distilled water each sheet.In the stove of all samples side under 54 ℃.On at least two replicate samples, carry out weekly cross viscosity test, up to sample fails (viscosity loses 5%) or up to past 40 days.
The sample that contains hindered amine compound of the present invention has good anti-laminarity.
Embodiment 136
The gelatin emulsion hand that will contain Silver monobromide, yellow coupler and additive is coated in and scribbles the layer of making colour developing photography usefulness on the poly paper.
The component of this layer is listed in the table below, and amount is with mg/m 2Meter:
Amount in the component layers
Gelatin 5150
AgBr 520 yellow coupler 1.07mmol/m 2Coupler solvent solv1 33% coupler weight/m 2Additive (in the table 4) 30% coupler weight/m 2Stiffening agent ha1 300 tensio-active agent su1 340
In stink cupboard with this layer drying 7 days.
Progressively wedging by 0.3 logE exposing step is exposed to dry sample under the white light.They are developed at the egative film chromatics paper from the AgFa-Gevaert of manufacturer's recommended with the P94 method.
After exposing and handling, that measures yellow dyes in blue channel alleviates density (remissiondensity).Then this sample is exposed among the Atlas WeatherOmeter, the UV filters that had open in the back in a fen is so that receive 60kJ/cm 2Luminous energy.Form by emulsion on the polyester transparent carrier by being coated in for this UV filters, and this layer contains 1g/m like this 2Tinuvin B976 .Temperature is 43 ℃, and relative humidity is 50%.Density was lost and is decided to be 1 when blue density began.Wish that Δ D number is low.
Table 1
Coupler Additive -ΔD(60kJ/cm 2, from OD=1)
?CoupY1 Do not have ?63
?CoupY1 ?X ?50
?CoupY1 ?BX ?59
?CoupY2 Do not have ?40
?CoupY2 ?AX ?30
?CoupY3 Do not have ?24
?CoupY3 ?AX ?20
?CoupY3 ?BY ?22
?CoupY4 Do not have ?36
?CoupY4 ?AX ?23
These results show that additive of the present invention has improved the light stability of yellow development layer.
Embodiment 137
The gelatin emulsion hand that will contain Silver monobromide, yellow coupler and additive is coated in and scribbles the layer of making colour developing photography usefulness on the poly paper.
The component of this layer is listed in the table below, and amount is with mg/m 2Meter:
Component Amount in the layer
Gelatin ????5150
????AgBr ????520
Yellow coupler ????1.07mmol/m 2
Coupler solvent solv1 33% coupler weight/m 2
Additive (in the table 4) 30% coupler weight/m 2
Stiffening agent ha1 ????300
Tensio-active agent su1 ????340
In stink cupboard with this layer drying 7 days.
Progressively wedging by the 0.3logE exposing step is exposed to dry sample under the white light.They are developed at the egative film chromatics paper from the AgFa-Gevaert of manufacturer's recommended with the P94 method.
After exposing and handling, in blue channel, measure the density that alleviates of yellow dyes.Then this sample was preserved 28 days in a Weiss climatic cabinet.Density was lost and is decided to be 1 when blue density began.Wish that Δ D number is low.
Table 1
Coupler Additive -Δ D (28d under 80 ℃ and 70%RH is from OD=1) is in %
CoupY1 Do not have ?22
CoupY1 ?X ?16
CoupY1 ?Y ?20
CoupY2 Do not have ?18
CoupY2 ?X ?10
CoupY2 ?Y ?10
CoupY2 ?Z ?15
These top results have shown that additive of the present invention has also improved the dark stability of yellow development layer.The component of using among the embodiment 136 and 137:
CoupY1 ?CoupY2 ?CoupY3
X is the compound of embodiment 30.
Y is the compound of embodiment 73.
Z is the compound of embodiment 16A.
Embodiment 138
The stabilization of TPO
Prepare moulded specimen, and test, just use amine oxide, Genox according to the method for embodiment 76 TMEP replaces N, N-dialkyl group azanol alkaline stabiliser.The photostabilizer goods that comprise mixture, amine oxide and the The compounds of this invention of listed component among the embodiment 76 have good ultraviolet light destructive performance.
Embodiment 139
Paintable TPO
In embodiment 77, the preparation moulded specimen is just used amine oxide, Genox TMEP replaces the N among the sample NOR-2, N-dialkyl group azanol alkaline stabiliser.Comprise in goods and the prior art of mixture, amine oxide and The compounds of this invention of listed component among the embodiment 77 not having the goods of the hydroxyl of The compounds of this invention to compare, have better japanning viscosity.
Embodiment 140
The stabilization of polypropylene fibre
Prepare fiber sample, and test, just use amine oxide, Genox according to the method for embodiment 79 TMEP replaces the N among the sample NOR-2, N-dialkyl group azanol alkaline stabiliser.The photostabilizer goods that comprise mixture, amine oxide and the The compounds of this invention of listed component among the embodiment 79 have good ultraviolet light destructive performance.
Embodiment 141
The stabilization of glycidyl methacrylate powder clear coatings
One of main new coating technology that can be used to satisfy growing harsh VOC solvent launch requirements is to use powder coating.The application of the photostabilizer that need use comprises the varnish of smoothing automobile bottom varnish, smoothing garden furniture, with the varnish of protection autotyre casing.Add and the life-span optimum in order to make, the stablizer that is used for powder coating should be the solid of fusing point moderate (～100 ℃), no volatile matter and thermally-stabilised down in typical powder coating baking temperature (140-180 ℃).
Add in test before the hindered amine as light stabilizer, GMA based powders coating resin, ultraviolet absorbers and the glidant of commercially available acquisition carried out premix at 145 ℃ by extruding.1,12 dodecylic acid cross-linked resin of hindered amine as light stabilizer in the test and commercially available acquisition adds in this pre-composition of part then.Push final mixture down at 100 ℃, in ultra centrifugal mill and powder swirler, grind this extrudate then, and sieve.With this electrostatic powder spraying on priming paint, 60 microns of its thickness.This coating was solidified 30 minutes down at 160 ℃.
These plates in an Xenon WeatherOmeter at Florida with 5 ° of angle weathering.Measure gloss and color.
Shown good gloss retention with the stable plate of The compounds of this invention.
Embodiment 142
The stabilization of urethane Synolac that is used for the oily modification of wood usage
The hindered amine as light stabilizer of test is added among the solvent urethane Synolac McWhorter43-4355 of commercially available acquisition.Also in all goods, add 2-hydroxybenzotriazole UV absorption agent.The add-on of this hindered amine as light stabilizer equates with the piperidines amount.After the mixing, on white deal board, apply varnish by brushing.By 1 " dark groove is divided into 8 sections with every block of plate, and with the sealing of film forming transparent varnish, the back side and side are with the coating of white chlorinated chamber lacquer.Be coated in trisection on the cross section of plate through stable coating, to guarantee that contrasting goods is present on each piece plate so that relatively.With dry 1 week of wood sample, placement is exposed to Florida, Australia and New York then.
Shown good color retention with the stable plate of The compounds of this invention, anti-crisp and good gloss retention.
Embodiment 143
Be used for and the laminated formed film of parts of plastics
The invention still further relates to Manufactured protectiveness and decorative film, it is coated on the substrate by the dried lacquer transformation approach.These films are made up of the single ornament layer that is coated on the slide glass, are laminated to then on the spacer block of the thermoformable that self supports.Remove carrier-pellet from the reverse side of film then, expose ornament layer.This composite membrane/spacer block of thermoforming becomes 3D shape then.In addition, these films also can be made up of multilayer, and wherein, for example the varnish with thermoplasticity, thermoformable is coated on the slide glass, and sclerosis forms transparent film on the optics then.Then colo(u)r coating is coated to the exposure of varnish,, obtains Clear paint/colored paint film by carrier supported through sclerosis.Then as mentioned above, this composite layer is pressed onto on the spacer block of thermoformable.As above remove slide glass, then as above thermoforming composite transparent coating/colo(u)r coating/liner.
Polymer resin in using above must be thermoplastic, can be fluoropolymer/vinylformic acid blend.

Claims (21)

1. the hindered amine that replaces of a 1-alkoxyl group, wherein this alkoxyl group is replaced by 1-3 hydroxyl, shown in (1)-(28), the perhaps derivative of formula (29) or (30):
Figure A0010651500021
Figure A0010651500031
Figure A0010651500051
Figure A0010651500061
Figure A0010651500071
Figure A0010651500081
Wherein
G 1And G 2Be respectively the alkyl of 1-4 carbon atom, perhaps G 1And G 2Be pentamethylene together;
E is the ring alkylidene group, 5-18 carboatomic ring thiazolinyl of straight or branched alkylidene group, the 5-18 carbon atom of 1-18 carbon atom, by phenyl or the 1-4 carbon atom straight chain or the branched alkylidene that replace by the phenyl that the alkyl of 1 or 2 1-4 carbon atom replaces;
B is 1,2 or 3, as long as b is no more than the carbonatoms among E or the L, when b was 2 or 3, each hydroxyl was connected on the different carbon atoms of E or L; Two hindered amine groups are common, but not always, are connected on two different carbon atoms of L;
In formula (1)-(15):
M is 0 or 1;
R 1Be hydrogen atom, hydroxyl or methylol;
R 2Be the alkyl of hydrogen atom, 1-12 carbon atom or the thiazolinyl of 2-12 carbon atom;
N is 1-4;
When n is 1,
R 3Be the carbalkoxy of the alkyl of 1-18 carbon atom, 4-18 carbon atom or alkylene carbonyl, 2-18 carbon atom thiazolinyl, glycidyl, 2, the 3-12 carbon atom alkyl that 3-dihydroxypropyl, 2-hydroxyl or 2-(methylol) replace, wherein alkyl is interrupted by Sauerstoffatom, contains aliphatics or unsaturated aliphatic carboxylic acid or carbamic acyl group, the cycloaliphatic carboxylic acid that contains the 7-12 carbon atom or the carbamic acyl group of 2-18 carbon atom or contains the acyl group of 7-15 carbon atom fragrance carboxylic acid;
When n is 2,
R 3For the divalence acyl group of the divalence acyl group of the alkylidene group of 2-18 carbon atom, the aliphatics that contains the 2-18 carbon atom or unsaturated aliphatic dicarboxylic acid or diamino acid, the cycloaliphatic dicarboxylic acid that contains the 7-12 carbon atom or diamino acid or contain the divalence acyl group of 8-15 carbon atom fragrance dicarboxylic acid;
When n is 3,
R 3For containing the trivalent acyl group of 6-18 carbon atom aliphatic series, unsaturated aliphatic or cycloaliphatic tricarboxylic acid or triamino formic acid, perhaps contain the trivalent acyl group of 9-18 carbon atom fragrance tricarboxylic acid or triamino formic acid, perhaps R 3Trivalent acyl group for three (alkylamino formic acid) derivative of containing 12-24 carbon atom cyanuric acid;
N is 4 o'clock, R 3Be the tetravalence acyl group of aliphatics or unsaturated aliphatic tetracarboxylic acid, or R 3It is the tetravalence acyl group that contains the fragrant four carboxylic acid of 10-18 carbon atom;
P is 1-3,
R 4Be the alkyl of hydrogen atom, 1-18 carbon atom or the acyl group of 2-6 carbon atom;
When p is 1,
R 5For the alkyl of hydrogen atom, 1-18 carbon atom, the aliphatics that contains the 2-18 carbon atom or unsaturated aliphatic carboxylic acid or carbamic acyl group, the cycloaliphatic carboxylic acid that contains the 7-12 carbon atom or carbamic acyl group, contain the acyl group or the R of 7-15 carbon atom fragrance carboxylic acid 4And R 5All be-(CH 2) 5The divalence acyl group of CO-, phthaloyl or maleic acid;
When p is 2,
R 5For the divalence acyl group of the divalence acyl group of the alkylidene group of 2-12 carbon atom, the aliphatics that contains the 2-18 carbon atom or unsaturated aliphatic dihydroxy acid or diamino acid, the cycloaliphatic dicarboxylic acid that contains the 7-12 carbon atom or diamino acid or contain the divalence acyl group of 8-15 carbon atom fragrance dicarboxylic acid;
When p is 3,
R 5For the aliphatics or the tricarboxylic trivalent acyl group of unsaturated aliphatic that contain the 6-18 carbon atom or contain the tricarboxylic trivalent acyl group of 9-15 carbon atom fragrance;
When n is 1,
R 6For the alkenyloxy of the alkoxyl group of 1-18 carbon atom, 2-18 carbon atom, 1-18 carbon atom-NH alkyl or 2-36 carbon atom-N (alkyl) 2
When n is 2,
R 6For the alkene dioxy base of the alkylene dioxo base of 2-18 carbon atom, 2-18 carbon atom, 2-18 carbon atom-NH-alkylene-NH-, or the 2-18 carbon atom-N (alkyl)-alkylene-N (alkyl)-, perhaps R 6Be the 4-methyl isophthalic acid, the inferior phenyl diamino of 3-;
When n is 3,
R 6For containing the trivalent alkoxyl group of the saturated of 3-18 carbon atom or unsaturated aliphatic triol;
When n is 4,
R 6For containing the tetravalence alkoxyl group of the saturated of 4-18 carbon atom or unsaturated aliphatic tetrol;
R 7And R 8Be respectively chlorine, 1-18 carbon atom alkoxyl group ,-O-T 1, the amino, the 1-18 carbon atom that are replaced by the 2-hydroxyethyl-NH (alkyl), have the 1-18 carbon atom alkyl-N (alkyl) T 1, or the 2-36 carbon atom-N (alkyl) 2,
R 9Be bivalent oxygen atom or R 9For by the alkyl or the T of hydrogen atom, 1-12 carbon atom 1The divalence nitrogen-atoms that replaces;
Figure A0010651500121
R 10Be hydrogen or methyl,
Q is 2-8,
R 11And R 12Be respectively hydrogen atom or group T 2,
Figure A0010651500131
R 13The straight or branched hydroxyalkyl of the cycloalkenyl group of the straight or branched alkyl of the 1-4 carbon atom that replaces for the alkoxyl group of the straight or branched alkyl of hydrogen, phenyl, 1-12 carbon atom, 1-12 carbon atom, by phenyl, the cycloalkyl of 5-8 carbon atom, 5-8 carbon atom, the thiazolinyl of 2-12 carbon atom, glycidyl, allyloxy, 1-4 carbon atom or replaced three times silyl or siloxy-respectively by the alkoxyl group of the alkyl of hydrogen atom, phenyl, 1-4 carbon atom or 1-4 carbon atom;
R 14For hydrogen or replaced three times silyl respectively by the alkoxyl group of hydrogen atom, phenyl, 1-4 carbon atom alkyl or 1-4 carbon atom;
D is 0 or 1;
H is 0-4;
K is 0-5;
X is 3-6;
Y is 1-10;
Z is that to make the molecular weight of compound be the integer of 1000-4000amu;
R 15For the branched alkylamino of the alkylamino of morpholinyl, piperidino-(1-position only), 1-8 carbon atom, particularly 3-8 carbon atom for example uncle hot amino, by T 1Replace have the 1-8 carbon atom alkyl-N (alkyl) T 1, or the 2-16 carbon atom-N (alkyl) 2
R 16For the acyl group of hydrogen, 2-4 carbon atom, by the formamyl of the alkyl of 1-4 carbon atom replacement, by the chlorine atom with by R 15Replace once the S-triazinyl or by R 15Replace twice S-triazinyl, two R 15Can be different;
R 17For chlorine, by the alkyl of 1-8 carbon atom or T 1The amino that replaces, have the 1-8 carbon atom alkyl-N (alkyl) T 1, the 2-16 carbon atom-N (alkyl) 2Or group T 3:
Figure A0010651500141
R 18The formamyl that replaces for the acyl group of hydrogen, 2-4 carbon atom, by the alkyl of 1-4 carbon atom, by the 2-16 carbon atom-N (alkyl) 2Replace twice the S-triazinyl or with the alkyl with 1-8 carbon atom-N (alkyl) T 1Replace twice S-triazinyl;
L is the alkenyl of cycloalkenyl group, the 3-18 carbon atom of ring alkylidene group, the 5-8 carbon atom of straight or branched alkenyl, the 5-8 carbon atom of 1-18 carbon atom, the straight or branched alkylidene group of the 1-4 carbon atom that phenyl replaced that replaces by phenyl or by the alkyl of one or two 1-4 carbon atom;
In formula (16)-(28),, R 1, R 2, R 7, R 8, R 9, R 10, R 13, R 14, d, h, k, m, q and T 1Equivalent in meaning with in formula (1)-(15);
R 19Alkyl, the thiazolinyl of 2-18 carbon atom, glycidyl, 2 for hydrogen, 1-18 carbon atom, the alkyl of 3-dihydroxypropyl, the 3-12 carbon atom that replaces through 2-hydroxyl or 2-(methylol), wherein alkyl is interrupted by Sauerstoffatom, contains aliphatic series or unsaturated aliphatic carboxylic acid or carbamic acyl group, the cycloaliphatic carboxylic acid who contains the 7-12 carbon atom or the carbamic acyl group of 2-18 carbon atom or contains the sour acyl group of 7-15 carbon atom fragrance;
R 20For the divalence acyl group of the divalence acyl group of the alkylidene group of 2-18 carbon atom, the aliphatic series that contains the 2-18 carbon atom or unsaturated aliphatic dicarboxylic acid or diamino acid, the cycloaliphatic dicarboxylic acid who contains the 7-12 carbon atom or diamino acid or contain the divalence acyl group of the aromatic dicarboxilic acid of 8-15 carbon atom;
R 21Be the alkyl of hydrogen, 1-18 carbon atom or the acyl group of 2-6 carbon atom;
R 22For the alkyl of hydrogen, 1-18 carbon atom, the aliphatic series that contains the 2-18 carbon atom or unsaturated aliphatic carboxylic acid or carbamic acyl group, the cycloaliphatic carboxylic acid who contains the 7-12 carbon atom or carbamic acyl group, contain the acyl group or the R of the aromatic carboxylic acid of 7-15 carbon atom 4And R 5Be together-(CH 2) 5The divalence acyl group of CO-, phthaloyl or maleic acid;
R 23Be the alkyl of hydrogen, 1-4 carbon atom or the acyl group of 2-6 carbon atom;
R 24For the divalence acyl group of the divalence acyl group of the alkylidene group of 2-18 carbon atom, the aliphatic series that contains the 2-18 carbon atom or unsaturated aliphatic dicarboxylic acid or diamino acid, the cycloaliphatic dicarboxylic acid who contains the 7-12 carbon atom or diamino acid or contain the divalence acyl group of the aromatic dicarboxilic acid of 8-15 carbon atom;
R 25For the alkenyloxy of the alkoxyl group of 1-18 carbon atom, 2-18 carbon atom, 1-18 carbon atom-NH alkyl or 2-36 carbon atom-N (alkyl) 2
R 26For the NH-alkylene-NH-of the alkene dioxy base of the alkylene dioxo base of 2-18 carbon atom, 2-18 carbon atom, 2-18 carbon atom or 3-18 carbon atom-N (alkyl)-alkylene-N (alkyl)-,
In formula (29) and (30), G for from primary, the second month in a season or tertiary alcohol G-OH deutero-be the biradical at center with the carbon atom, wherein
Z is with defined above identical, and
G is the alkenyl of cycloalkenyl group, the 3-18 carbon atom of ring alkylidene group, the 5-8 carbon atom of straight or branched alkylidene group, the 5-8 carbon atom of 1-18 carbon atom, by phenyl or the straight or branched 1-4 carbon atom alkylidene group that phenyl replaced that replaced by the alkyl of one or two 1-4 carbon atom, in the solemnity (29) successive hindered amine molecule can be head to head or head to the mode orientation of tail;
T 4For hydrogen or
T 4Be
Figure A0010651500151
R 27For ring alkylidene group or cycloalkenyl group, the phenylene of the straight or branched alkylidene group of 1-18 carbon atom, 5-8 carbon atom or comprise 5-amino-1-aminomethyl-1,3, the 3-trimethyl-cyclohexane and-the 2-18 carbon atom of NH-xylylene-NH--NH-alkylidene group-NH-;
R 28For the alkyl of 1-4 carbon atom,
Figure A0010651500152
R 29For straight or branched alkyl or 1-18 carbon atom-NH-alkyl or 5-8 carbon atom-the NH-cycloalkyl; With
As long as in formula (1) and (2), when b was 1, E was not methyl, ethyl, 2-propyl group or 2-methyl-2-propyl group.
2. compound as claimed in claim 1, wherein in formula (1)-(30), G 1And G 2All be methyl, and in formula (1)-(28), b is 1 or 2,
When b is 1, it is the radical or the biradical at center that E-OH and L-OH are respectively with the carbon atom, preferably by 2-methyl-2-propyl alcohol, 2-propyl alcohol, 2,2-dimethyl-1-propyl alcohol, 2-methyl-2-butanols, ethanol, 1-propyl alcohol, 1-butanols, 1-amylalcohol, 1-hexanol, 1 nonyl alcohol, 1-decanol, 1-dodecanol, 1-Stearyl alcohol, 2-butanols, 2-amylalcohol, 2-ethyl-1-hexanol, hexalin, ring octanol, vinylcarbinol, phenylethyl alcohol or 1-phenyl-1-ethanol forms; Most preferably E-OH and L-OH are formed by 2-methyl-2-propyl alcohol or hexalin;
When b was 2, it was the radical or the biradical at center that E-OH and L-OH are respectively with the carbon atom, preferably by 1,2-ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,3-butyleneglycol, 1,4-butyleneglycol, 2,2-dimethyl-1, ammediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1, the 4-cyclohexanediol forms;
When b was 3, E-OH and L-OH were respectively by glycerine, 1,1, and 1-three (methylol) methane, 2-ethyl-2-(methylol-1, ammediol, 1,2,4-trihydroxybutane or 1,2, what the 6-hexanetriol formed is the radical or the biradical at center with carbon;
In formula (29) and (30) ,-G-O-is formed by ethanol, phenylethyl alcohol, hexalin or 2-methyl-2-propyl alcohol (=trimethyl carbinol);
In formula (3), m is 0, R 1Be hydrogen or methylol, R 2Be hydrogen; Perhaps m is 1, R 1Be hydroxyl or methylol, R 2Be hydrogen, methyl or ethyl;
R in formula (5) 2Be hydrogen or dodecyl;
In formula (6), n is 1-3, and when n is 1, R 3Be allyl group, glycidyl, acryl, methacryloyl, octadecanoyl, hexadecanoyl, tetradecanoyl, methoxyl group phosphinylidyne propionyl, methoxyl group phosphinylidyne butyryl radicals, methoxyl group phosphinylidyne pentanoyl or methoxyl group phosphinylidyne nonanoyl; Perhaps when n is 2, R 3Be succinyl, glutaryl-, adipyl, sebacoyl, 1, the own diamino formyl radical of 6-, anti-or suitable-5-formamyl-1-(carbamyl ylmethyl)-1,3,3-trimethyl-cyclohexane or Toluene-2,4-diisocyanate, 4-diamino formyl radical; Perhaps when n is 3, R 3Be 1,3,5-three (6-formamyl hexyl)-2,4,6-trioxy--S-triazine;
In formula (7), p is 1 or 2, when p is 1, and R 4Be hydrogen and R 5Be butyl; Perhaps R 4And R 5It all is the divalence free acyl radical of toxilic acid; Perhaps when p is 2, R 4Be hydrogen or ethanoyl and R 5Be 1, the 6-dihexyl;
In formula (8), n is 1 or 2, and when n is 1, R 6For oxyethyl group, 6-methyl isophthalic acid-heptan oxygen base, ethylamino, fourth is amino or hot amino; Perhaps when n is 2, R 6Be 1,2-ethylenedioxy, 1,4-fourth dioxy base, second diamino, cyclohexyl diamino or 4-methyl isophthalic acid, the inferior phenyl diamino of 3-;
In formula (9), R 7And R 8Be respectively chlorine, hot amino, the hot amino of uncle or by T 1Amino with ethyl, butyl or dodecyl replacement; And R 9Be the divalence nitrogen-atoms that is replaced by ethyl, butyl or dodecyl;
In formula (10), q is 2,4 or 6, R 7For chlorine, hot amino, octadecane is amino or by T 1Amino with ethyl, butyl or dodecyl replacement; And R 10Be hydrogen;
In formula (11), n is 3, and p is 2, R 2Be ethyl, butyl or dodecyl; And R 11And R 12One of be T 2, and another is a hydrogen;
In formula (12), k is 3, R 9For bivalent oxygen atom or by the divalence ammonia atom of ethyl, butyl or dodecyl replacement, R 13Be hydrogen or methyl, when d was 0, x was 5 or 6, and when d was 1, x was 3 or 4;
In formula (13), d is 0 or 1, and h is 0-2, and k is 0 or 3, and y is 1-8, R 9For bivalent oxygen atom or by the divalence nitrogen-atoms of ethyl, butyl or dodecyl replacement, R 13Be hydrogen, methyl, ethyl, methoxy or ethoxy, and R 14Be hydrogen or trimethyl silyl;
In formula (14), R 9Be bivalent oxygen atom, R 10Be hydrogen or methyl, m is 0, and z is that to make the molecular weight of compound be the integer of 1500-3000;
In formula (15), q is 6, and y is 1-7, R 15For the hot amino of uncle, morpholinyl, by T 1With the amino that butyl replaces, it also can be called T 1-butyl amino, R 16Be hydrogen, ethanoyl, ethylamino formyl radical, 2, two (the dibutylamino)-S-triazinyls, 2 of 4-, two (diethylin)-S-triazinyls of 4-, by T 1-butyl is amino to be replaced twice S-triazinyl or is replaced once and by T by diethylin or dibutylamino 1Amino S-triazinyl, the R that replaces once of-butyl 17Be dibutylamino, diethylin, T 1-butyl amino or R 17Be T 3, R wherein 18Be ethanoyl or ethylamino formyl radical;
In formula (17), m is 0, R 1Be hydrogen or methylol, R 2Be hydrogen, perhaps m is 1, R 1Be hydrogen or methylol, and R 2Be hydrogen or methyl;
In formula (19), R 2Be hydrogen or dodecyl;
In formula (20), R 19Be hydrogen, allyl group, acryl, methacryloyl, octadecanoyl or hexadecanoyl;
In formula (21), R 20Being succinyl, glutaryl-, adipyl, sebacoyl, 1, the own diamino formyl radical of 6-is anti-or suitable-5-formamyl-1-(carbamyl ylmethyl)-1,3, the 3-trimethyl-cyclohexane;
In formula (22), R 21Be hydrogen.R 22Be hydrogen or butyl; Perhaps R 21And R 22It all is the divalence acyl group of toxilic acid;
In formula (23), R 23Be hydrogen or ethanoyl, R 24Be ethylidene or cyclohexyl;
In formula (24), R 25For oxyethyl group, 6-methyl isophthalic acid-heptan oxygen base, ethylamino, fourth is amino or hot amino;
In formula (25), R 26Be 1,2-ethylenedioxy, 1,4-fourth dioxy base, second diamino or cyclohexyl diamino;
In formula (26), R 7And R 8Be respectively chlorine, hot amino, the hot amino of uncle, octadecane amino, T 1-ethylamino, T 1-Ding amino or T 1-dodecane amino, and R 9Be the divalence nitrogen-atoms that is replaced by ethyl, butyl or dodecyl;
In formula (27), q is 2,4 or 6, R 7Be chlorine, hot amino, amino, the T of octadecane 1-ethylamino, T 1-Ding amino or T 1-dodecane amino and R 10Be hydrogen;
In formula (28), d is 0 or 1, and h is 0-2, and k is 0 or 3, R 9For bivalent oxygen atom or by the divalence nitrogen-atoms of ethyl, butyl or dodecyl replacement, R 13Be hydrogen, methyl, ethyl, methoxy or ethoxy, and R 14Be hydrogen or trimethyl silyl;
In formula (29), R 27Be ethylene, cyclopropane, tetramethylene, eight methylene radical, 1 or 5-amino-1-aminomethyl-1,2,3,3-trimethyl-cyclohexane; Z is that to make the molecular weight of compound be the integer of 1500-3000, R 28Be methyl or ethyl, and G is ethylene, 1,2-encircles dihexyl, 1, and 3-encircles dihexyl, 1,4-ring dihexyl ,-CH (C 6H 5) CH 2-or-CH 2C (CH 3) 2-;
In formula (30), R 29Be pentadecyl, heptadecyl, fourth amino or hexamethylene amino.
3. compound as claimed in claim 1, wherein
In formula (6), when n is 1, R 3Be acryl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxyl group phosphinylidyne propionyl, methoxyl group phosphinylidyne butyryl radicals, methoxyl group phosphinylidyne pentanoyl or methoxyl group phosphinylidyne nonanoyl; Perhaps when n is 2, R 3Be succinyl, glutaryl-, adipyl, sebacoyl, 1, the own diamino formyl radical of 6-, anti-or suitable-5-formamyl-1-(methyl-carbamoyl methyl)-1,3,3-trimethyl-cyclohexane or Toluene-2,4-diisocyanate, 4-diamino formyl radical; Perhaps when n is 3, R 3Be 1,3,5-three (6-formamyl hexyl)-2,4,6-trioxy--S-triazine;
In formula (7), p is 1 or 2, when p is 1, and R 4Be hydrogen and R 5Be hydrogen or butyl; Perhaps when p is 2, R 4Be hydrogen and R 5Be 1, the 6-dihexyl;
In formula (9), R 7Be chlorine, hot amino or T 1-Ding amino; R 8Be chlorine or T 1-Ding amino; And R 9Be the divalence nitrogen-atoms that is replaced by butyl;
In formula (10), q is 6, R 7Be T 1-Ding amino; And R 10Be hydrogen;
In formula (11), n is 3, and p is 2, and R 11And R 12One of be T 2, another is a hydrogen;
In formula (12), k is 3, R 9Be bivalent oxygen atom, R 13Be hydrogen or methyl, and d is 0, x is 5 or 6, and when d was 1, x was 3 or 4;
In formula (13), d is 0 or 1, and h is 0-2, and k is 0 or 3, and y is 1-8, R 9Be bivalent oxygen atom, R 13Be hydrogen, methyl, ethyl, methoxy or ethoxy, and R 14Be hydrogen or trimethyl silyl;
In formula (15), q is 6, and y is 1-7, R 15Be T 1-Ding amino, R 16Be hydrogen, ethanoyl, ethylamino formyl radical, 2, two (the dibutylamino)-S-triazinyls, 2 of 4-, two (diethylin)-S-triazinyls of 4-, by T 1-Ding is amino to be replaced twice S-triazinyl or is replaced once and by T by diethylin or dibutylamino 1Amino S-triazinyl, the R that replaces once of-Ding 17Be dibutylamino, diethylin, T 1-Ding ammonia very or R 17Be T 3, R wherein 18Be ethanoyl or ethylamino formyl radical;
In formula (20), R 19Be hydrogen, octadecanoyl or hexadecanoyl;
In formula (22), R 21Be hydrogen, R 22Be hydrogen or butyl;
In formula (23), R 23Be hydrogen, R 24Be cyclohexyl;
In formula (26), R 7Be chlorine, hot amino or T 1-Ding amino, R 8Be chlorine or T 1-Ding amino, and R 9Be the divalence nitrogen-atoms that is replaced by butyl;
In formula (27), q is 6, R 7Be T 1-Ding amino, and R 9Be the divalence nitrogen-atoms that is replaced by butyl;
In formula (29), R 27Be ethylene, cyclopropane, tetramethylene or eight methylene radical; Z is that to make the molecular weight of compound be the integer of 1500-2000g/mo, R 28Be methyl;
In formula (30), R 29Be pentadecyl or heptadecyl.
4. compound as claimed in claim 1, wherein G 1And G 2Be methyl E-OH, L-OH and G-O-in the compound of formula (1)-(30), form by 2-methyl-2-propyl alcohol or hexalin.
5. compound as claimed in claim 1, wherein:
In the formula (6), when n is 1, R 3Be acryl, methacryloyl, glycidyl, octadecanoyl, hexadecanoyl, methoxyl group phosphinylidyne propionyl or methoxyl group phosphinylidyne butyryl radicals or methoxyl group phosphinylidyne pentanoyl; N is 2, R 3Be succinyl, glutaryl-, adipyl or sebacoyl;
In the formula (7), R 4Be hydrogen, and when p is 1, R 5Be hydrogen or butyl; Perhaps when p is 2, R 5Be cyclohexyl;
In the formula (9), R 7Be chlorine, hot amino or T 1-Ding amino; R 8Be T 1-Ding amino; And R 9Be the divalence nitrogen-atoms that is replaced by butyl;
In the formula (10), q is 6, R 7Be T 1-Ding amino; And R 10Be hydrogen;
In the formula (11), n is 3, and p is 2, and R 11And R 12One of be T 2, another is a hydrogen;
In the formula (12), d is 1, and k is 3, and x is 3 or 4, R 9Be bivalent oxygen atom, R 13Be methyl;
In the formula (13), k is 3, and y is 4-8, R 9Be bivalent oxygen atom, R 13Be hydrogen or methyl, d and h are 0, R 14Be hydrogen, or d be 1 and h be 0, R 14Be trimethyl silyl;
In the formula (14), m is 0, R 9Be bivalent oxygen atom, R 10Be hydrogen or methyl, z is that to make the molecular weight of compound be the integer of 1500-3000;
In the formula (15), q is 6, and y is 1-7, R 15Be T 1-Ding amino, R 16Be hydrogen, ethanoyl, ethylamino formyl radical, 2, two (the dibutylamino)-S-triazinyls, 2 of 4-, two (diethylin)-S-triazinyls of 4-, by T 1-Ding is amino to be replaced twice S-triazinyl or is replaced once and by T by diethylin or dibutylamino 1Amino S-triazinyl, the R that replaces once of-Ding 17Be dibutylamino, diethylin or T 3, R wherein 18Be ethanoyl or ethylamino formyl radical;
In the formula (20), R 19Be hydrogen, octadecanoyl or hexadecanoyl;
In the formula (21), R 20Be succinyl, glutaryl-, adipyl or sebacoyl;
In the formula (30), R 29Be heptadecyl.
6. compound as claimed in claim 1 is
(a) two [1-(2-hydroxy-2-methyl propoxy--2,2,6,6-tetramethyl piperidine-4-yl)] sebate;
(b) mixture of two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] adipic acid ester and two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] glutarate
(c) 1-(2-hydroxy-2-methyl propoxy-)-4-octadecane acidic group (acyloxy)-2,2,6, the 6-tetramethyl piperidine
(d) two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] adipic acid ester
(e) two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] glutarate
(f) two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] succinate
(g) mixture of two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] glutarate and two [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-yl] succinate
(h) 1-(4-octadecane acidic group-2,2,6,6-tetramethyl piperidine-1-oxygen base)-2-octadecane acidic group-2-methylpropane
(i) 1-(2-hydroxy-2-methyl propoxy-)-4-[9-(methoxycarbonyl) n-nonanoic acid base]-2,2,6, the 6-tetramethyl piperidine
(j) 1-(2-hydroxy-2-methyl propoxy-)-4-[5-(methoxycarbonyl) valeric acid base]-2,2,6, the 6-tetramethyl piperidine
(k) 1-(2-hydroxy-2-methyl propoxy-)-4-[3-(methoxycarbonyl) propionyloxy]-2,2,6, the 6-tetramethyl piperidine
(l) 1-(2-hydroxy-2-methyl propoxy-)-4-[4-(methoxycarbonyl) butyric acid base]-2,2,6, the 6-tetramethyl piperidine
(m) the 4-hydroxyl-1-(2-hydroxy-2-methyl propoxy-)-2,2,6 that ends up with methoxyl group, the polycondensate of 6-tetramethyl piperidine and hexamethylene vulcabond
(n) the 4-hydroxyl-1-(2-hydroxyl-oxyethyl group)-2,2,6 that ends up with methoxyl group, the polycondensate of 6-tetramethyl piperidine and hexamethylene vulcabond
(o) the 4-hydroxyl-1-(2-hydroxyl-1-phenyl ethoxy)-2,2,6 that ends up with methoxyl group, the polycondensate of 6-tetramethyl piperidine and hexamethylene diisocyanate
(p) 1-(2-hydroxy-2-methyl propoxy-)-4-n-Hexadecane acidic group-2,2,6, the 6-tetramethyl piperidine
(q) 1-(4-n-Hexadecane acidic group-2,2,6,6-tetramethyl piperidine-1-oxygen base)-2-n-Hexadecane acidic group-2-methylpropane
(r) 1-(2-hydroxy-2-methyl propoxy-)-4-[5-(methoxycarbonyl) valeric acid base]-2,2,6,6-tetramethyl piperidine, 1-(2-hydroxy-2-methyl propoxy-)-4-[4-(methoxycarbonyl) butyric acid base]-2,2,6, the 6-tetramethyl piperidine
(s) 1,3,5-three { [1-(2-hydroxy-2-methyl propoxy-)-2,2,6,6-tetramethyl piperidine-4-oxygen base] carbonylamino hexyl }-2,4,6-trioxa-S-triazine
(t) 4-hydroxyl-1-oxygen base-2,2,6, the reactant of 6-tetramethyl piperidine and 2-methyl-2-butanols,
(u) 4-hydroxyl-1-oxygen base-2,2,6, the product of transesterification reaction of 6-tetramethyl piperidine and 2-methyl-2-butanols and methyl stearate,
(v) 1-(2-hydroxy-2-methyl propoxy-)-4-[5-(methoxycarbonyl) valeric acid base]-2,2,6,6-tetramethyl piperidine and 1-(2-hydroxy-2-methyl propoxy-)-4-[4-(methoxycarbonyl) butyric acid base]-2,2,6, the mixture of 6-tetramethyl piperidine.
7. a composition comprises
(a) be subjected to the organic polymer of disadvantageous effect of heat, oxygen and light or recording materials and
(b) one or more of effective stable quantity are selected from the compound of formula (1)-(30) according to claim 1.
8. composition as claimed in claim 7, wherein component (a) is thermoplastic organic polymer, paint adhesive, color photographic materials or printing ink.
9. composition as claimed in claim 7 also comprises being selected from following component: solvent, pigment, dyestuff, softening agent, antioxidant, thixotropic agent, smooth auxiliary agent, other photostabilizer, metal passivator, metal oxide, organo phosphorous compounds, azanol, ultraviolet absorbers, sterically hindered amines and its mixture.
10. composition as claimed in claim 9, contained ultraviolet absorbers is selected from lower class: 2-(2-hydroxy phenyl)-2H-benzotriazole, 4-hydroxybenzoate, 2-hydroxyl-benzophenone, N, N '-phenylbenzene oxalamide, 2-hydroxy phenyl-S-triazine, or its mixture.
11.,, comprise the stablizer of the component (b) of 0.01-10wt% based on component (a) weight according to the composition of claim 7.
12. stable organic polymer or recording materials comprise the compound that adds or apply at least a formula as claimed in claim 1 (1)-(30) to described material with the method for fast light, oxygen and/or heat collapse.
13. the compound of the formula of claim 1 (1)-(30) is being stablized organic polymer or the recording materials purposes aspect fast light, oxygen and/or heat collapse.
14. the method for preparation formula IV compound:
Figure A0010651500221
Wherein
G 1And G 2The alkyl of 1-4 carbon atom, perhaps G respectively do for oneself 1And G 2Be pentamethylene together;
T is the divalence organic free radical, require to realize containing five or six-ring of hindered amine carbon atom and two by G 1And G 2The quaternary carbon atom that replaces;
E is the ring alkylidene group of cycloalkylidene, 5-12 carbon atom of alkylidene group, the 5-12 carbon atom of 2-18 carbon atom (b+1) valency alkylidene group, 3-19 carbon atom or the alkylidene group of the 2-4 carbon atom that phenyl replaced that replaced by phenyl or replaced by 1-2 1-4 carbon atom; And
B is 1,2 or 3; As long as b is no more than the quantity of saturated carbon atom among the E, and when b is 2 or 3, different carbon atoms are continuous among each hydroxyl and the E;
This method comprises:
In the presence of metal-salt that superoxide or organic hydroperoxide and catalytic amount are arranged or metal ligand complex compound, the N-oxygen base hindered amine of formula V and the alcohol of formula VI are reacted.
Figure A0010651500222
E-(OH) b????(VI)
15. as the method for claim 14, its Chinese style IV compound is corresponding with formula (1)-(30) of claim 1.
16. as the method for claim 14, wherein G 1And G 2All be methyl, T is a 2-hydroxyl-1,3-glyceryl or 2-oxo-1,3 glyceryl.
17. the method for claim 14, its Chinese style VI-E-(OH) b, when b is 1,, when b is 2, be 1 for 2-methyl-2-propyl alcohol or hexalin, 2-propylene glycol, 1, ammediol, 1,2-butyleneglycol, 1,4-butyleneglycol, 2,2-dimethyl-1, ammediol, 2,5-dimethyl-2,5-hexylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1, the 4-cyclohexanediol, and, when b is 3, be 1,1,1-three (methylol) ethane, 2-ethyl-2-(methylol)-1, ammediol, 1,2,4-trihydroxybutane or 1,2,6-hexanetriol.
18. as the method for claim 14, wherein superoxide is the addition compound of hydrogen peroxide or urea and hydrogen peroxide.
19. method as claim 14, wherein this metal is transition metal, particularly iron (II), iron (III), copper (I), copper (II), cobalt (II), cobalt (III), manganese (II), manganese (III), vanadium (II), vanadium (III), cerium (III) and the titanium (III) that is selected from IVA in the periodictable, VA, VIIA, VIIIA and IB family.
20. method as claim 19, wherein the counter ion of this transition metal are muriates, vitriol, acetylacetonate, acetate, Citrate trianion, oxalate, nitrate, perchlorate, prussiate, oxyhydroxide, phosphoric acid salt, pyrophosphate salt and oxide compound, and organic ligand can be selected from 2,2 '-dipyridyl, 2,2 ': 6 '; 2 "-four pyridyl, 1, the 10-phenanthroline, ethylenediamine tetraacetic acid (EDTA), disodium EDTA, pyridine, pyridine formic acid, 2-pyrazine carboxylic acid, by aniline or the aniline that is substituted and 1, the 2-diketone is as 2, the aromatic base diimine that the reaction of 3-dimethyl diketone generates, or triphenylphosphine oxidation thing.
21. the method for claim 14, wherein in 1 mole of nitryl among the formula V, with the compound of the formula VI of 5-100 mole as solvent, wherein the amount in 1 mole of nitryl superoxide among the formula V or organic hydroperoxide is the 1-20 mole, the amount of metal-salt or metal ligand complex compound is the 0.001-0.5 mole, does not use acid, if perhaps use acid, nearly 1 mole of its amount, this method is carried out under 20-100 ℃ temperature.
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