CN1091127C - Benzotriazole UV absorbers having enhanced durability - Google Patents

Benzotriazole UV absorbers having enhanced durability Download PDF

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CN1091127C
CN1091127C CN97122422A CN97122422A CN1091127C CN 1091127 C CN1091127 C CN 1091127C CN 97122422 A CN97122422 A CN 97122422A CN 97122422 A CN97122422 A CN 97122422A CN 1091127 C CN1091127 C CN 1091127C
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phenyl
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CN1183442A (en
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R·拉维克安德朗
A·D·德贝里斯
R·伊恩加
J·苏哈多尼克
J·P·沃尔夫
R·E·德特里夫森
M·G·伍德
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Novartis AG
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Abstract

Benzotriazole UV absorbers which are substituted at the 5-position of the benzo ring by an electron withdrawing group exhibit enhanced durability and very low loss rates when incorporated into automotive coatings.

Description

Weather resistance enhanced benzotriazole UV absorbers
The benzotriazole UV absorbers that is partly replaced by electrophilic on the benzo ring after it adds car paint, has enhanced weather resistance and low rate of loss.
For a long time, benzotriazole is the important uv-absorbing agent of a class always, and many industrial application are had commercial widely importance and practical value.In the former technology, many contents relevant with purposes with its production are arranged.Yet owing to require more and more strictness, demand is more and more, and people are seeking more stable, more competent benzotriazole always.Use the HAPS solvent, the progressive phase of making as dimethylbenzene, owing to relate to environmental problem and by non-HAPS solvent, as ester, ether or ketone replace, and the requirement higher to the car paint weather resistance, so press for more stable, the more competent benzotriazole of searching.In fact, what automotive industry was concerned about most is that UVA loses from automotive paints and coating, as sees people's such as J.L.Gerlock Proc.36th Annual Tech.Sym. (Cleveland CoatingSociety), on May 18th, 1993.
Vysokomol Soedin is at Ser.A, described the linear relationship of HYDROGEN BOND INTENSITY and light stability in the benzotriazole in 18 (3), 553 (1976).
People such as J.E.Pickett are at Angew.Makromol.Chem.232, have described the photolysis of benzotriazole UV absorbers in poly-(methyl methacrylate) thin layer in 229 (1995).If metalepsy does not make the intramolecular hydrogen bond fracture very crucial to stability, structural difference only can make rate of decomposition that little difference is arranged usually.People such as Pickett do not test any benzotriazole that contains electrophilic as described in the present invention and electron-donating group.
Technology conclusion was in the past, add strong hydrogen bonding and can make benzotriazole more stable, but how explanation does not realize.The invention discloses benzotriazole, but surprisingly this enhanced weather resistance is not total relevant with stronger hydrogen bond with enhancing weather resistance.In fact having a little less than the compound that strengthens weather resistance has usually, is not very strong hydrogen bond.
U.S.P.Nos.4,226,763; 4,278,589; 4,315,848; 4,275,004; 4,347,180; 5,554,760; 5,563,242; Described the benzotriazole of selecting in 5,574,166 and 5,607,987, replaced by a α-cumyl group on the 3-position of oxybenzene basic ring, it has very good weather resistance in car paint.These benzotriazoles have been represented the present situation of this technology.The present invention relates to the preparation method of benzotriazole, these benzotriazoles are compared with the benzotriazole of former technology has obviously good weather resistance and low rate of loss.
U.S.P.Nos.5,278,314; 5,280,124; In 5,436,349 and 5,516,914 the red shift benzotriazole has been described.By thioether, alkyl sulphonyl or phenyl sulfonyl partly replace these benzotriazoles on the 5-position of benzo ring.Requirement on the spectrum is satisfied in the benzotriazole red shift.The present invention also finds, also is that electrophilic group can further reduce rate of loss and strengthen weather resistance on the 5-position.
The present invention relates to benzotriazole UV absorbers, after it adds in the car paint, have enhanced stability and weather resistance and low rate of loss.
More particularly, the present invention relates to a kind of coating composition, make said composition stable with benzotriazole, after this benzotriazole adds said coating, embody enhanced weather resistance and low rate of loss, said composition contains:
(a) a kind of resin, this resin is selected from the thermoset acrylics melamine resin, the vinylformic acid urethane resin,
The epoxy carboxy resin, silane-modified acrylic melamine, with melamine crosslinked have a carboxylamine
The acrylic resin of ester side group group, or crosslinked with the melamine that contains carbamate groups
The acrylic acid or the like polyol resin,
(b) structural formula that accounts for resin solid weight 0.01 to 5% is A, B, a kind of benzo of C or D
Triazole,
Figure C9712242200081
Figure C9712242200091
In the formula
G 1, G 2Or T is electron-withdrawing group,
G 1Be hydrogen or halogen,
G 2Be halogen, nitro, cyano group, R 3SO-, R 3SO 2-,-COOG 3, CF 3-,-P (O) (C 6H 5) 2,-CO-G 3,-CO-NH-G 3,-CO-N (G 3) 2,-N (G 3)-CO-G 3,
Figure C9712242200092
G 3Be hydrogen, straight chain or branched-alkyl that 1 to 24 carbon atom is arranged, straight chain or branched chain thiazolinyl that 2 to 18 carbon atoms are arranged, the cycloalkyl that 5 to 12 carbon atoms are arranged, the benzene alkyl that 7 to 15 carbon atoms are arranged, phenyl, or the said phenyl or the said benzene alkyl that on phenyl ring, are replaced by 1 to 4 alkyl that 1 to 4 carbon atom arranged
R 1Be hydrogen, straight chain or branched-alkyl that 1 to 24 carbon atom is arranged, straight chain or branched chain thiazolinyl that 2 to 18 carbon atoms are arranged, the cycloalkyl that 5 to 12 carbon atoms are arranged, the benzene alkyl that 7 to 15 carbon atoms are arranged, phenyl, or the said phenyl or the said benzene alkyl that on phenyl ring, are replaced by 1 to 4 alkyl that 1 to 4 carbon atom arranged
R 2Be straight chain or the branched-alkyl that 1 to 24 carbon atom is arranged, straight chain or branched chain thiazolinyl that 2 to 18 carbon atoms are arranged, the cycloalkyl that 5 to 12 carbon atoms are arranged, the benzene alkyl that 7 to 15 carbon atoms are arranged, phenyl, or the said phenyl or the said benzene alkyl that on phenyl ring, are replaced by 1 to 3 alkyl that 1 to 4 carbon atom arranged; Perhaps R 2Be hydroxyl or-OR 4, R wherein 4Be straight chain or the branched-alkyl that 1 to 24 carbon atom is arranged; Or by one or more-OH ,-OCO-R 11,-OR 4,-NCO or-NH 2The said alkyl that group or their mixture replace; Or by one or more-O-,-NH-or-NR 4-group or their mixture are at interval and do not replace or by one or more-OH ,-OR 4Or-NH 2Said alkyl or said alkenyl that group or their mixture replace; Or R 2Be-SR 3,-NHR 3Or-N (R 3) 2Perhaps R 2Be
-(CH 2) m-CO-X-(Z) p-Y-R 15In the formula
X is-O-or-N (R 16)-,
Y is-O-or-N (R 17)-,
Z is C 2-C 12-alkylene (alkylene), by 1 to 3 nitrogen-atoms, Sauerstoffatom or their mixture C at interval 4-C 12-alkylene, perhaps Z is C 3-C 12-alkylene, butenylene, butynelene, hexamethylene alkylene or penylene, above each group all replaced by hydroxyl,
M is 0,1 or 2,
P is 1, perhaps works as X and Y to be respectively-N (R 16)-and-N (R 17)-time, p also is 0,
R 15For-CO-C (R 18)=C (H) R 19, perhaps as Y be-N (R 17)-time, R 15With R 17Common formation group-CO-CH=CH-CO-, wherein a R 18Be hydrogen or methyl, R 19Be hydrogen, methyl or-CO-X-R 20, R wherein 20Be hydrogen, C 1-C 12The group that-alkyl or structural formula are following
Figure C9712242200111
Symbol R in the formula 1, R 3, X, Z, m and p and same meaning defined above, R 16And R 17Be hydrogen independently of one another, C 1-C 12-alkyl is by 1 to 3 Sauerstoffatom C at interval 3-C 12-alkyl, or cyclohexyl C 7-C 15Aralkyl, and be under the situation of ethane support at Z, R 16With R 17Also can form the ethane support,
N is 1 or 2,
When n is 1, R 5Be Cl, OR 6Or NR 7R 8, or
R 5Be-PO (OR 12) 2,-OSi (R 11) 3Or-OCO-R 11, or quilt-O-,-S-or-NR 11-at interval and do not replace or quilt-OH or-OCO-R 11The straight chain or the branching C that replace 1-C 24Alkyl, the not C of replacement or quilt-OH replacement 5-C 12Cycloalkyl, the not straight chain or the branching C of replacement or quilt-OH replacement 2-C 18Alkenyl, C 7-C 15Aralkyl ,-CH 2-CHOH-R 13Or glycidyl,
R 6Be hydrogen, replace or by one or more OH, OR 4Or NH 2Straight chain or branching C that group replaces 1-C 24Alkyl, perhaps-OR 6For-(OCH 2CH 2) wOH or-(OCH 2CH 2) wOR 21, wherein w is 1 to 12, R 21Be the alkyl that 1 to 12 carbon atom is arranged,
R 7And R 8Be hydrogen independently of one another, the alkyl of 1 to 18 carbon atom arranged, or quilt-O-,-S-or-NR 11-straight chain or branching C at interval 3-C 18Alkyl, C 5-C 12Cycloalkyl, C 6-C 14Aryl or C 1-C 3Hydroxyalkyl, perhaps R 7And R 8With the N atom is tetramethyleneimine, piperidines, and piperazine or morpholine ring,
When n is 2, R 5Be divalent group-O-R 9-O-or-N (R 11)-R 10-N (R 11)-in one,
R 9Be C 2-C 8Alkylene, C 4-C 8The alkene support, C 4Alkynes support, the hexamethylene alkylene, quilt-O-or-CH 2-CHOH-CH 2-O-R 14-O-CH 2-CHOH-CH 2-straight chain or branching C at interval 4-C 10Alkylene,
R 10By-O-straight chain or branching C at interval 2-C 12Alkylene, the hexamethylene alkylene, or
Figure C9712242200112
Perhaps R 10And R 11Together form a piperazine ring with two nitrogen-atoms,
R 14Be straight chain or branching C 2-C 8Alkylene, quilt-O-straight chain or branching C at interval 4-C 10Alkylene, the cycloalkanes support, arylene, or R wherein 7And R 8Be hydrogen independently of one another, the alkyl of 1 to 18 carbon atom arranged, perhaps R 7And R 8Be the alkylene of 4 to 6 carbon atoms together, 3-oxa-pentamethylene, 3-imino-pentamethylene or 3-methyl-imino pentamethylene,
R 11Be hydrogen, straight chain or branching C 1-C 18Alkyl, C 5-C 12Cycloalkyl, straight chain or branching C 3-C 8Alkenyl, C 6-C 14Aryl or C 7-C 15Aralkyl,
R 12Be straight chain or branching C 1-C 18Alkyl, straight chain or branching C 3-C 18Alkenyl, C 5-C 10Cycloalkyl, C 6-C 16Aryl or C 7-C 15Aralkyl,
R 13Be H, quilt-PO (OR 12) 2The straight chain or the branching C that replace 1-C 18Alkyl, the phenyl that does not replace or replaced by OH, C 7-C 15Aralkyl, or-CH 2OR 12,
R 3It is the alkyl that 1 to 20 carbon atom is arranged, the hydroxyalkyl that 2 to 20 carbon atoms are arranged has the alkenyl of 3 to 18 carbon atoms, and the cycloalkyl of 5 to 12 carbon atoms is arranged, the aralkyl that 7 to 15 carbon atoms are arranged, the aryl of 6 to 10 carbon atoms or the said aryl that is replaced by 1 to 2 alkyl that 1 to 4 carbon atom arranged are arranged, or 1,1,2,2-tetrahydrochysene perfluoroalkyl, perfluor alkane wherein partly have 6 to 16 carbon atoms
L is the alkylene that 1 to 12 carbon atom is arranged, the alkylidene of 2 to 12 carbon atoms, and benzal, right-xylylene or cycloalkanes fork,
T is-SO--SO 2-,-SO-E-SO-,-SO 2-E-SO 2-,-CO-,-CO-E-CO-,-COO-E-OCO-,-CO-NG 3-E-NG 3-CO-or-NG 3-CO-E-CO-NG 3-,
Wherein E is the alkylene that 2 to 12 carbon atoms are arranged, and the cycloalkanes of 5 to 12 carbon atoms supports, and the hexamethylene alkylene interval or the end capped alkylene of 8 to 12 carbon atoms arranged,
When coating is exposed under the actinic rays, this benzotriazole shows enhanced weather resistance and low rate of loss, be lower than 0.22 absorbance unit as 1200 hours loss amounts of irradiation under Xenon-Arc Weather-Ometer, shine 1500 hours loss amounts and be lower than 0.27 absorbance unit, shine 2500 hours loss amounts and be lower than 0.40 absorbance unit.
Preferably, component (b) is that structural formula is the compound of A ' In the formula
G 2Be fluorine, chlorine, cyano group, R 3SO 2-, CF 3-,-CO-G 3,-COO-G 3Or-CO-N (G 3) 2
G 3For the alkyl of 1 to 12 carbon atom is arranged,
R 1Be hydrogen, the alkyl of 1 to 12 carbon atom is arranged, phenyl has the benzene alkyl of 7 to 15 carbon atoms, or the said phenyl or the said benzene alkyl that are replaced by 1 or 2 alkyl that 1 to 4 carbon atom arranged on phenyl ring,
R 2Be the alkyl that 1 to 12 carbon atom is arranged, phenyl has the benzene alkyl of 7 to 15 carbon atoms,
8. according to the composition of claim 1, it comprises the hindered amine of effective stable quantity in addition, is selected from: sebacic acid two (2; 2,6,6-tetramethyl piperidine-4-yl) ester; sebacic acid two (1,2,2; 6,6-pentamethyl-piperidin-4-yl) ester, (3; 5-di-t-butyl-4-hydroxyl-benzyl) butyl malonic acid two (1,2,2; 6,6-pentamethyl-piperidin-4-yl) ester, 4-benzoyl-2; 2,6, the 6-tetramethyl piperidine; 4-stearoyl-oxy-2,2,6; 6-tetramethyl--piperidines, 3-n-octyl-7,7; 9,9-tetramethyl--1,3; 8-three azepines-spiral shell [4.5] decane-2,4-diketone, nitrilotriacetic acid(NTA) three (2; 2,6,6-tetramethyl piperidine-4-yl) ester; 1,2-two (2,2; 6,6-tetramethyl--3-Oxypertine-4-yl) ethane, 2; 2,4,4-tetramethyl--7-oxa--3; 20-diaza-21-oxygen two spiral shells [5.1.11.2] heneicosane, 2, the hot amino of 4-two chloro-uncles 6--s-triazine and 4; 4 '-hexa-methylene two (amino-2,2,6; 6-tetramethyl--piperidines) polycondensation product, 1-(2-hydroxyethyl)-2,2; 6, the polycondensation product of 6-tetramethyl--4-hydroxy-piperdine and Succinic Acid, 4; 4 '-hexa-methylene two-(amino-2,2,6; the 6-tetramethyl piperidine) and the polycondensation product of glycol dibromide, 1; 2,3,4-butanetetra-carboxylic acid four (2; 2,6,6-tetramethyl-piperazine-4-yl) ester; 1,2,3; 4-butanetetra-carboxylic acid four (1,2,2; 6,6-pentamethyl-piperidin-4-yl) ester, 2; 4-two chloro-6-morpholino-s-triazines and 4,4 '-hexa-methylene two-(amino-2,2; 6,6-tetramethyl piperidine) polycondensation product, N; N ', N " N -four [(4, two (butyl-1; 2,2,6; the 6-pentamethyl-piperidin-4-yl)-amino-s-triazine-2-yls of 6-]-1,10-diamino-4,7-diaza decane; blended 1,2,3; 4-butanetetra-carboxylic acid [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] ester, blended 1; 2,3,4-butanetetra-carboxylic acid [1; 2,2,6; 6-pentamethyl-piperidin-4-yl/β, β, β '; β '-tetramethyl--3,9-(2,4; 8,10-four oxaspiros [5.5]-undecane) diethyl] ester, two (2; 2; 6,6-tetramethyl piperidine-4-carboxylic acid) eight methylene radical esters, 4; 4 '-ethylene two (2; 2,6,6-tetramethyl-piperazine-3-ketone); N-2; 2,6,6-tetramethyl piperidine-4-base-dodecyl Succinic Acid imide; N-1; 2,2,6; 6-pentamethyl-piperidin-4-yl-dodecyl Succinic Acid imide
When E was alkylene, it was for example ethane support, tetramethylene, hexa-methylene, 2-methyl isophthalic acid, 4-tetramethylene, hexa-methylene, eight methylene radical, decamethylene and ten dimethylenes; When E was the cycloalkanes support, it was for example pentamethylene support, hexamethylene alkylene, suberane support, cyclooctane support and cyclododecane support; When E is by the hexamethylene alkylene at interval or during end capped alkylene, it is saturated two bases of for example deriving and from limonene, is called dihydro limonene two bases here.
A preferred embodiment of the present invention is that structural formula is the compound of III, wherein R 1Be the tertiary butyl, n is 1, R 3Be phenyl, R 5For-OR 6, R wherein 6Octyl group group for straight chain or replacement.And another embodiment preferred of the present invention is a structural formula is the compound of C, and wherein n is 2, R 1Be the tertiary butyl, R 3Be phenyl, and R 5For-O-R 9-O-, wherein R 9For quilt-O-or-CH 2-CHOH-CH 2-O-R 14-O-CH 2-CHOH-CH 2-C at interval 2-C 24Alkylene.
When E was alkylene, it was for example ethane support, tetramethylene, hexa-methylene, 2-methyl isophthalic acid, 4-tetramethylene, hexa-methylene, eight methylene radical, decamethylene and ten dimethylenes; When E was the cycloalkanes support, it was for example pentamethylene support, hexamethylene alkylene, suberane support, cyclooctane support and cyclododecane support; When E is by the hexamethylene alkylene at interval or during end capped alkylene, it is saturated two bases of for example deriving and from limonene, is called dihydro limonene two bases here.
When containing a free carboxyl group part in this compound, R wherein 2For-CH 2CH 2COOR 6, R 6Be hydrogen, the basic metal of said acid or amine salt also are parts of the present invention, because this compounds has the enhanced water-soluble, can use such UV absorption agent in aqueous phase system.
R 6, R 7And R 8Can be following C 3-C 18Alkyl group, these alkyl groups quilt-O-,-S-, or-NR 11-at interval, perhaps also can be replaced by OH: methoxyethyl, ethoxyethyl, fourth oxygen ethyl, fourth oxygen propyl group, methyl ethylmercapto group, CH 3OCH 2CH 2OCH 2CH 2-, CH 3CH 2OCH 2CH 2OCH 2CH 2-, C 4H 9OCH 2CH 2OCH 2CH 2-, ethyl rosickyite base, octyl group rosickyite base, dodecyl propoxy-, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxyl butyl, 6-hydroxyl hexyl ,-CH 2CH 2-NH-C 4H 9,-CH 2CH 2CH 2NH-C 8H 17With-CH 2CH 2CH 2-N (CH 3)-CH 2CH (C 2H 5) C 4H 9,
R 6, R 7, R 8, R 11And R 12Can be following C 5-C 12Group of naphthene base: pentamethylene base, cyclohexyl, suberane base, cyclooctane base or cyclodecane base.For R 6, the also group that can be replaced by-OH.
R 7, R 8And R 11Can be following kiki alkenyl group: allyl group, methylallyl, the positive octenyl of 2-n-hexylene base or 4-.
Work as R 6During for alkenyl, it can be and R 7, R 8And R 11The same alkenyl, but also can be-CH=CH 2, positive 11-10-thiazolinyl or positive 18-9-thiazolinyl are for R 6, the group that it also can be replaced by-OH.
R 7And R 8Can be following C 7-C 15Aromatic alkyl group: phenmethyl, α-styroyl, 2-styroyl or 4-tert.-butylbenzene methyl.
Work as R 11, R 13Or R 12During for aralkyl, they can be independent of each other, with R 7Or R 8Identical meaning is arranged.
R 7, R 8And R 11Be following C independently of one another 6-C 14Aromatic yl group: phenyl, Alpha-Naphthyl, betanaphthyl.
Work as R 7And R 8Be C 1-C 3During hydroxyalkyl, they can be following groups: methylol, 2-hydroxyethyl or 2-hydroxypropyl.
Work as R 9And R 14Be C 2-C 8During alkylene, they can be following groups: ethane support, propane support, butane support, hexane support, octane support.
Work as R 10During for alkylene, R 10Can be same group, still, R 10Also can be more high molecular group, as decane support or dodecane support.
Work as R 9Be C 4-C 8During alkenylene group, an example of suitable group is: butenylene.
For R 9And R 14, suitable quilt-O-straight chain or branching C at interval 4-C 10Alkylene is following group :-CH 2CH 2OCH 2CH 2-,-CH (CH 3)-CH 2-O-CH 2-CH (CH 3)-CH 2CH 2OCH 2CH 2OCH 2CH 2-,-CH 2CH 2OCH 2CH 2OCH 2CH 2OCH 2CH 2-.
Work as R 14When supportting, comprise following groups for cycloalkanes: 1,3-hexamethylene alkylene, 1,4-hexamethylene alkylene.
Work as R 14During for arylene, particularly, it can be following group: 1, and 3-penylene, 1,4-penylene.
When Z is C 2-C 12During-alkylene, it is straight chain or branching.For example: ethane support, propane support, tetramethylene, hexa-methylene, eight methylene radical, ten dimethylenes, 1,1-ethane fork, 2,2-propane fork, 2,2-pentane fork or 2-ethyl hexa-methylene.C preferably 2-C 6-alkylene.
When Z is by oxygen C at interval 4-C 12During-alkylene, its example is :-CH 2-CH 2-O-CH 2-CH 2-,-CH 2-CH 2-O-CH 2-CH 2-CH 2-,-CH 2-CH 2-O-CH 2-CH 2-O-CH 2-CH 2-or-CH 2-CH 2-O-CH 2-CH 2-O-CH 2-CH 2-O-CH 2-CH 2-, when alkylene by nitrogen at interval, promptly be-N (R 16)-, be R wherein 16With previously defined the same, for example be-CH 2-CH 2-NH-CH 2-CH 2-CH 2-CH 2-,-CH 2-CH 2-CH 2-NH-(CH 2) 8-or-CH 2-CH 2-CH 2-N (CH 3-CH 2-CH (C 2H 5) (CH 2) 4-.
The C that is replaced by oh group as Z 3-C 12During-alkylene, Z is a 2-hydroxyl tetramethylene, 2-hydroxyl hexa-methylene, and 2-hydroxyl trimethylene specifically,
When Z was the hexamethylene alkylene, Z was for example 1,4-hexamethylene alkylene, specifically 1,2-hexamethylene alkylene.
When Z was penylene, Z was for example m-penylene or p-penylene.
M can be 0,1 or 2, but preferably 2.
P preferably 1, if but X is to be connected by nitrogen with Y, p also can be 0.
Work as R 1Be C 1-C 8During-alkyl, R 1For for example: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl, tert-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl or uncle's octyl group.The tertiary butyl preferably.
Work as R 16, R 17And R 20Be C 1-C 12During-alkyl, they can be and top R 1The group of same meaning also can be the nonyl of straight chain or branching in addition, decyl, undecyl, or dodecyl.
Work as R 16And R 17For by at interval alkyl of Sauerstoffatom the time, identical described in the Z of examples of applications and front.
Work as R 16And R 17Example during for aralkyl is: phenmethyl, and the Alpha-Methyl phenmethyl, the 1-styroyl,, α, alpha-alpha-dimethyl phenmethyl or 1-hydrocinnamyl.
If Z is the ethane support, R 16And R 17Also can together form the ethane support, this ethane support is equivalent to a bridged bond by the piperazine group.
When Y is-N (R 17)-time, R 15And R 17Together form a group-CO-CH=CH-CO-, therefore at group-X-(Z) p-on form substituting group
Figure C9712242200171
Yet preferred R 15For-CO-C (R 18)=CHR 14, R 18And R 19Preferably methyl, particularly hydrogen.R 2For-CH 2-CH 2-CO-O-C (G)=CH 2, G is hydrogen or methyl.The invention still further relates to structural formula is I, II, the novel benzotriazole of III or IV In the formula
G 1Be hydrogen or halogen,
G 2Be cyano group, E 3SO-, E 3SO 2-,-COOG 3, CF 3-,-P (O) (C 6H 5) 2,-CO-G 3,-CO-NHG 3Or-CO-N (G 3) 2,
G 3For the straight chain or the branched-alkyl of 1 to 24 carbon atom are arranged, straight chain or branched chain thiazolinyl that 2 to 18 carbon atoms are arranged, the cycloalkyl that 5 to 12 carbon atoms are arranged, the benzene alkyl that 7 to 15 carbon atoms are arranged, phenyl, or the said phenyl or the said benzene alkyl that on phenyl ring, are replaced by 1 to 4 alkyl that 1 to 4 carbon atom arranged
E 1Be hydrogen, the benzene alkyl of 7 to 15 carbon atoms is arranged, phenyl, or the said phenyl or the said benzene alkyl that on phenyl ring, are replaced by 1 to 4 alkyl that 1 to 4 carbon atom arranged,
E 2For the straight chain or the branched-alkyl of 1 to 24 carbon atom are arranged, straight chain or branched chain thiazolinyl that 2 to 18 carbon atoms are arranged, the cycloalkyl that 5 to 12 carbon atoms are arranged, the benzene alkyl that 7 to 15 carbon atoms are arranged, phenyl, or the said phenyl or the said benzene alkyl that on phenyl ring, are replaced by 1 to 3 alkyl that 1 to 4 carbon atom arranged; Perhaps E 2For hydroxyl or-OE 4, E wherein 4For the straight chain or the branched-alkyl of 1 to 24 carbon atom are arranged; Perhaps E 2For by one or more-OH ,-OCO-E 11,-OE 4,-NCO or-NH 2The said alkyl that group or their mixture replace; Perhaps by one or more-O-,-NH-or-NE 4-group or their mixture said alkyl or said alkenyl at interval, these alkyl and alkenyl can be unsubstituted or by one or more-OH ,-OE 4Or-NH 2Group or their mixture replace; Perhaps E 2For-SE 3,-NHE 3Or-N (E 3) 2Perhaps E 2For
-(CH 2) m-CO-X-(Z) p-Y-E 15In the formula
X is-O-or-N (E 16)-,
Y is-O-or-N (E 17)-,
Z is C 2-C 12-alkylene, by one to three nitrogen-atoms, Sauerstoffatom or their mixture C at interval 4-C 12-alkylene, perhaps Z is C 3-C 12-alkylene, butenylene, butynelene, hexamethylene alkylene or penylene, these groups are all replaced by hydroxyl,
M is 0,1 or 2,
P is 1, perhaps works as X and Y and is respectively-N (E 16) and-N (E 17)-time, p also is 0,
E 15For-CO-C (E 18)=C (H) E 19-, perhaps as Y be-N (E 17)-time, E 15With E 17Form one-CO-CH=CH-CO-group, wherein E 18Be hydrogen or methyl, E 19Be hydrogen, methyl or-CO-X-E 20, E wherein 20Be hydrogen, C 1-C 12The group that-alkyl or structural formula are following. E in the formula 1, G 2, X, Z, the meaning of m and p is with defined above identical, E 16And E 17Be hydrogen independently of one another, C 1-C 12-alkyl is by 1 to 3 Sauerstoffatom C at interval 3-C 12-alkyl, or be cyclohexyl or C 7-C 15Aralkyl is the situation of ethane support for Z, E 16And E 17Also can together form the ethane support,
N is 1 or 2,
When n is 1, E 5Be Cl, OE 6Or NE 7E 8, perhaps
E 5For-PO (OE 12) 2-,-OSi (E 11) 3Or-OCO-E 11, perhaps be quilt-O-,-S-or-NE 11C at interval 1-C 24Alkyl, these alkyl can be unsubstituted or quilt-OH or-OCO-E 11Replace the C of unsubstituted or quilt-OH replacement 5-C 12Cycloalkyl, straight chain or branching C that unsubstituted or quilt-OH replaces 2-C 18Alkenyl, C 7-C 15Aralkyl ,-CH 2-CHOH-E 13Or glycidyl,
E 6Be hydrogen, replace or by one or more OH, OE 4Or NH 2Straight chain or branching C that group replaces 1-C 24Alkyl, perhaps-OE 6For-(OCH 2CH 2) wOH or-(OCH 2CH 2) wOE 21, wherein w is 1 to 12, E 21For the alkyl of 1 to 12 carbon atom is arranged,
E 7And E 8Independently of one another is hydrogen, and the alkyl of 1 to 18 carbon atom is arranged, quilt-O-,-S-or-NE 11-straight chain or branching C at interval 3-C 18Alkyl, C 5-C 12Cycloalkyl, C 6-C 14Aryl or C 1-C 3Hydroxyalkyl, perhaps E 7And E 8Form tetramethyleneimine with the N atom, piperidines, piperazine or morpholine ring,
When n is 2, E 5Be divalent group-O-E 9-O-or-N (R 11)-E 10-N (E 11)-,
E 9Be C 2-C 8Alkylene, C 4-C 8The alkene support, C 4Alkynes support, the hexamethylene alkylene, quilt-O-or-CH 2-CHOH-CH 2-O-E 14-O-CH 2-CHOH-CH 2-straight chain or branching C at interval 4-C 10Alkylene,
E 10For can be by-O-straight chain or branching C at interval 2-C 12Alkylene, the hexamethylene alkylene, or Perhaps E 10With E 11Form a piperazine ring with two nitrogen-atoms,
E 14Be straight chain or branching C 2-C 8Alkylene, quilt-O-straight chain or branching C at interval 4-C 10Alkylene, cycloalkanes support, arylene or
Figure C9712242200211
E in the formula 7And E 8Independently of one another is hydrogen, the alkyl of 1 to 18 carbon atom is arranged, perhaps E 7And E 8Together be formed with the alkylene of 4 to 6 carbon atoms, 3-oxa-pentamethylene, 3-imino-pentamethylene or 3-methyl-imino pentamethylene,
E 11Be hydrogen, straight chain or branching C 1-C 18Alkyl, C 5-C 12Cycloalkyl, straight chain or branching C 3-C 8Alkenyl, C 6-C 14Aryl or C 7-C 15Aralkyl,
E 12Be straight chain or branching C 1-C 18Alkyl, straight chain or branching C 3-C 18Alkenyl, C 5-C 10Cycloalkyl, C 6-C 16Aryl or C 7-C 15Aralkyl,
E 13Be H, quilt-PO (OR 12) 2The straight chain or the branching C that replace 1-C 18-alkyl, the phenyl that does not replace or replaced by OH, C 7-C 15Aralkyl or-CH 2OE 12,
E 3For the alkyl of 1 to 20 carbon atom is arranged, the hydroxyalkyl that 2 to 20 carbon atoms are arranged has the alkenyl of 3 to 18 carbon atoms, and the cycloalkyl of 5 to 12 carbon atoms is arranged, the benzene alkyl that 7 to 15 carbon atoms are arranged, the aryl of 6 to 10 carbon atoms or the said aryl that is replaced by one or two alkyl that 1 to 4 carbon atom arranged are arranged, or 1,1,2,2-tetrahydrochysene perfluoroalkyl, perfluoroalkyl group wherein have 6 to 16 carbon atoms
L is the alkylene that 1 to 12 carbon atom is arranged, the alkylidene of 2 to 12 carbon atoms, and benzal, right-xylylene or cycloalkanes fork,
T is-SO--SO 2-,-SO-E-SO-,-SO 2-E-SO 2-,-CO-,-CO-E-CO-,-COO-E-OCO-or-CO-NG 5-E-NG 5-CO-,
Wherein E is the alkylene that 2 to 12 carbon atoms are arranged, and the cycloalkanes of 5 to 12 carbon atoms supports, and the hexamethylene alkylene interval or the end capped alkylene of 8 to 12 carbon atoms arranged,
G 5Be G 3Or hydrogen,
Condition is to work as G 2Be E 3SO-or E 3SO 2-time, E 1It or not the benzene alkyl.
This novel benzotriazole preferably structural formula is the compound of I '
Figure C9712242200221
In the formula
G 2Be cyano group, E 3SO 2-, CF 3-, COO-G 3-CO-NHG 3Or-CO-N (G 3) 2
G 3For the alkyl of 1 to 12 carbon atom is arranged,
E 1Be hydrogen, phenyl has the benzene alkyl of 7 to 15 carbon atoms, or the said phenyl or the said benzene alkyl that are replaced by 1 or 2 alkyl that 1 to 4 carbon atom arranged on phenyl ring,
E 2Be the alkyl that 1 to 12 carbon atom is arranged, phenyl has the benzene alkyl of 7 to 15 carbon atoms, or-CH 2CH 2COOG 4, G wherein 4Be hydrogen, the alkyl of 1 to 24 carbon atom is arranged, by the said alkyl that OH replaces, the said alkyl by 1 to 6-O-atomic separation was perhaps both replaced by OH, again by the said alkyl of 1 to 6-O-atomic separation,
E 3Be the alkyl that 8 to 18 carbon atoms are arranged, the aryl of 6 to 10 carbon atoms is arranged, or by 1 or 2 said aryl that the alkyl replacement of 1 to 4 carbon atom is arranged, condition is to work as G 2Be E 3SO-or E 3SO 2-time, E 1It or not the benzene alkyl.
Most preferably, be in the compound of I ' at structural formula,
G 2Be cyano group, E 3SO 2-, CF 3-,-CO-G 3Or-CO-N (G 3) 2,
G 3For the alkyl of 1 to 8 carbon atom is arranged,
E 1Be hydrogen, phenyl or α-cumyl,
E 2Be the alkyl that 4 to 12 carbon atoms are arranged,
E 3Be phenyl or octyl group, condition is to work as G 2Be E 3SO 2-time, E 1It or not α-cumyl.
Particularly preferably being at structural formula is in the compound of I ', G 2Be CF 3-, E 1Be α-cumyl, E 2Be the tertiary butyl or uncle's octyl group.
The invention still further relates to a kind ofly to heat, oxidisability or photoinduced Decomposition be stable composition all, wherein contains:
(a) a kind ofly easily be heated, the organic substance of oxidisability or the influence of photoinduced Decomposition,
(b) structural formula of stabilizing effective amount is I, II, the compound of III or IV.
This organic substance is preferably natural, semi-synthetic or synthetic polymer, particularly thermoplastic polymer.
This polymkeric substance is polyolefine and polycarbonate, particularly polyethylene or polypropylene most preferably; Polypropylene more particularly.
In another embodiment preferred of the present invention, this organic substance is a resin, this resin is selected from the thermoset acrylics melamine resin, the vinylformic acid urethane resin, the epoxy carboxy resin, silane-modified acrylic melamine, with the crosslinked acrylic resin that has carbamate side group group of melamine, or with the crosslinked acrylic acid or the like polyol resin of the melamine that contains carbamate groups.
Most preferred resin is thermoset acrylics melamine resin or vinylformic acid urethane resin.
And in another embodiment preferred of the present invention, this organic substance is a kind of recording materials.
Recording materials according to the present invention are applicable to pressure-sensitive copy system, utilize the photocopying system of microcapsule, thermography system, sensitive materials and spray ink Printing.
According to recording materials of the present invention since its in beyond thought improvement qualitatively, so its performance is very good, particularly aspect fastness to light.
Recording materials according to the present invention have the structure that is used for specific end use.These recording materials have a conventional carrier, for example are paper or the plastics films that scribbles one or more thin layers.According to the type of differing materials, these thin layers comprise suitable necessary component, for example for sensitive materials, can be silver emulsions, coupler, dyestuff and similar material.Be specially adapted to the material of spray ink Printing, on conventional carrier, have a thin layer strong especially the ink absorption ability.There is not the paper of coating to can be used for spray ink Printing yet.For this situation, paper is not only as the carrier while but also as the ink absorption layer.The material that is applicable to spray ink Printing is, for example, and U.S.Pat.No.5, the material described in 073,448 (this literary composition is incorporated herein by reference).
These recording materials also can be transparent, for example projection film.
Structural formula is I, II, the compound of III or IV can be in the production process of base mateiral as far as possible early adding wherein, for example in the production process of paper, join in the paper pulp.The Another application method is for being I with structural formula, II, and the aqueous solution of the compound of III or IV sprays base mateiral, or the bar structure formula is I, and II is in the compound adding coating composition of III or IV.
Be applicable to the particle that can not contain any scattered light in the coating composition of projection transparent record material, as colorant and weighting agent.
Dyestuff adhesive coating composition can contain a large amount of other additives, antioxidant for example, photostabilizer (also comprising the UV absorption agent that does not belong to UV absorption agent of the present invention), viscosity modifier, white dyes, biocides and static inhibitor.
The common preparation process of this coating composition is as follows:
With water soluble ingredient,, be dissolved in the water and be stirred in together as tackiness agent.With solid ingredient,, be dispersed in this aqueous media as weighting agent and other additive of having stated.Dispersion process is preferably finished by some equipment, as ultrasonic equipment, and turbine stirrer, homogenizer, colloidal mill, beans grinding machine, sand mill, high speed agitator and similar devices.Structural formula is I, II, and the compound of III or IV just can join in the coating composition at an easy rate.
According to structural formula in the recording materials of the present invention is that the preferred content of compound of I is 1 to 5000mg/m 2, particularly preferably be 50 to 1200mg/m 2
Already mentioned as us, these recording materials according to the present invention comprise very on a large scale.For example, structural formula is I, II, and the compound of III or IV can be used for pressure-sensitive copy system.These compounds both can join in the paper to prevent that light from destroying the precursor of micro-capsule dyestuff, can join the dyestuff of protecting the there to form in the tackiness agent of developer layer again.
At U.S.Pat.Nos.4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,5365,463; 4,551,407; Described the photocopying system that uses photosensitive microcapsules in 4,562,137 and 4,608,330, these photosensitive microcapsules pass through pressure develoment, at EP-A139, and 479; EP-A 162,664; EP-A 164,931; EP-A 237,024; Such photocopying system has also been described among EP-A 237,025 or the EP-A 260,129.In all these systems, these compounds can join in the dyestuff receiving layer.But these compounds also can be added in the donor layer, are broken to toner to prevent light.
Sensitive materials that can be stable is photosensitizing dye and the thin layer that contains these dyestuffs or its precursor, for example sensitized paper and sensitive film.Suitable material is, U.S.Pat.No.5 for example, the material described in 364,749 (this literary composition is incorporated herein by reference).Structural formula is I, and II, the compound of III or IV here are the UV filtering mediums as antistatic spark.In color sensitive material, it also prevents the photochemistry Decomposition of coupler and dyestuff.
The compounds of this invention can be used for all types of color sensitive materials.For example, can be used for chromatics paper, colour reversal paper, direct positive color material, color negative film, colour positive, colour reversal film or the like.Its preferred purposes is the color sensitive material that is used to contain the counter-rotating substrate or forms positive.
The color sensitive recording materials contain thoughts indigo plant usually and feel green and the red sensing coppering silver emulsion layer on carrier; if desired; also has a protective layer; preferably; these compounds are being felt green or are being felt in the red beds; or in the layer between green layer and sense red beds, perhaps on silver halide emulsion layer.
Structural formula is I, II, the compound of III or IV also can be used for based on photopolymerization, the break recording materials of principle of light effect of moulding or micro-capsule, perhaps for using temperature-sensitive and photosensitive diazonium salt, contain the leuco dye of oxygenant or contain the situation of the dyestuff lactone of Lewis acid, can in recording materials, the utilization structure formula be I also, II, the compound of III or IV.
In addition, these compounds can be used for the dye diffusion transfer printing, in the recording materials of thermal wax transfer and non-matrix printing, for using static, electricity is taken a picture, electrophoresis, printer and pen plotter that magnetic diagram and laser photoelectricity are taken a picture also can use these compounds in the recording materials.Above the said recording materials that are used for the dye diffusion transfer printing preferably, for example, at EP-A-507, the material described in 734.
These compounds also can be used for ink, preferably are used for spray ink Printing, as U.S.Pat.No.5, (this literary composition is incorporated herein by reference) described in 098,477.
Compound of the present invention has very outstanding stability to hydrolysis, processing and package stability, and after adding stable composition, good anti-extractability is arranged.
The method of producing The compounds of this invention is the method described in the former technology.Preparing the required intermediate majority of these compounds all is commodity.
In the preferred compound, one of them of X and Y is-O-; Particularly X and Y are-O-.
The polymkeric substance that can be stabilized generally comprises:
1. the polymkeric substance of monoolefine and diolefine, polypropylene for example, polyisobutene, poly-1-butylene, poly--4-methyl-1-pentene, polyisoprene or polyhutadiene, and the polymkeric substance of cycloolefin, for example, the polymkeric substance of cyclopentenes or norbornylene, polyethylene (can be crosslinked), for example, high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
Polyolefine, the polymkeric substance of the monoolefine that promptly in aforementioned paragraphs, exemplifies, preferably polyethylene and polypropylene, available diverse ways manufacturing, particularly following certain methods:
A) radical polymerization (under high pressure and high temperature, carrying out usually).
B) catalytic polymerization, catalyst for application contain IVb on the periodictable usually, Vb, VIb, or one or more metal of VIII family.These metals have monovalence or multivalence ground and typical oxide compound usually, halogenide, and alcoholate, ester, ether, amine, alkyl, thiazolinyl and/or aryl are with π key or the complexing of σ key.These metal complexs can the free form exist or are fixed on the activatory magnesium chloride, and titanium chloride (III) is on the substrates such as aluminum oxide or silicon oxide.These catalyzer are solvable or be insoluble in the medium of polyreaction.Can be directly used in polyreaction or further use activator, typical activator has metal alkylide, metal hydride, alkyl metal halide, metal alkoxide compound or Jin belong to Wan Ji oxane compounds, and above-mentioned metal is Ia on the periodictable, IIa and/or IIIa elements.These activators can further be used ester, ether, amine or the modification easily of silyl silicon ethers group.These catalyst systems are commonly referred to Philip (phillipa), Indiana standard oil (Standard Oil Indiana), Ziegler (Natta), TNZ (Du Pont), metallocenes or single site catalysts (SSC).
2.1) mixture of polymers of mentioning down, the mixture of polypropylene and polyisobutene for example, (PP/HDPE for example is PP/LDPE) with dissimilar poly mixtures (for example LDPE/HDPE) for polypropylene and poly mixture.
Monoolefine and diolefine to each other multipolymer or with the multipolymer of other vinyl monomers, for example, ethylene/propene copolymer, the mixture of linear low density polyethylene (LLDPE) and it and new LDPE (film grade) (LDPE), the propylene/1-butene multipolymer, propylene/isobutylene copolymers, ethene/butene-1 copolymer, the ethylene/hexene multipolymer, ethene/methylpentene multipolymer, ethene/heptene multipolymer, ethylene/octene, propylene/butadienecopolymer, iso-butylene/isoprene copolymer, ethylene/alkyl acrylate copolymer, the ethylene/methacrylic acid alkyl ester copolymer, multipolymer or the ethylene/acrylic acid copolymer and their salt (ionomer) of ethylene/vinyl acetate copolymer and they and carbon monoxide, ethene and propylene and another kind of diene such as hexadiene in addition, the terpolymer of dicyclopentadiene or ethylidene-precipitation sheet alkene; With the mixture of this analog copolymer and with 1) in the mixture of polymers mentioned, for example, polypropylene/ethylene-propylene copolymer, LDPE/ ethylene-vinyl acetate copolymer (EVA), LDPE/ ethylene-acrylic acid copolymer (EAA), LLDPE/EVA, LLDPE/EAA and alternative or unordered polyalkylene/carbon monoxide multipolymer and they and other polymkeric substance are the mixture of polymeric amide for example.
4. hydrocarbon resin (C for example 5-C 9), comprise its hydrogenation modification body (for example tackiness agent) and the mixture of polyalkylene and starch.
5. polystyrene gathers (p-methylstyrene), poly-(alpha-methyl styrene).
6. the multipolymer of vinylbenzene or alpha-methyl styrene and dienes or acrylate derivative, for example, phenylethylene/butadiene, styrene/acrylonitrile, the styrene/methacrylic acid alkyl ester, phenylethylene/butadiene/alkyl acrylate, phenylethylene/butadiene/alkyl methacrylate, phenylethylene/maleic anhydride, the multipolymer of styrene/acrylonitrile/methyl acrylate; Styrol copolymer and another kind of polymkeric substance be polyacrylic ester for example, the mixture of the high impact that diene polymer or ethylene/propylene/diene terpolymers are formed; With cinnamic segmented copolymer, as 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 connected on the polyhutadiene, vinylbenzene is connected on poly-(butadiene-styrene) or poly-(butadiene-acrylonitrile) multipolymer on; Vinylbenzene and vinyl cyanide (or methacrylonitrile) are connected on the polyhutadiene; Vinylbenzene, vinyl cyanide and methyl methacrylate are connected on the polyhutadiene; Vinylbenzene and maleic anhydride are connected on the polyhutadiene; Vinylbenzene, vinyl cyanide and maleic anhydride or maleimide are connected on the polyhutadiene; Vinylbenzene and maleimide are connected on the polyhutadiene; The alkyl ester of vinylbenzene and acrylic or methacrylic acid is connected on the polyhutadiene; Vinylbenzene and vinyl cyanide are connected on the terpolymer of ethylene/propylene/diene hydrocarbon; Vinylbenzene and vinyl cyanide are connected on polyalkyl acrylate or the polyalkyl methacrylate; Vinylbenzene and vinyl cyanide are connected on the multipolymer of acrylate/divinyl, and they and 6) under the mixture of the multipolymer listed, for example, be called ABS, MBS, these copolymer mixtures of ASA or AES polymkeric substance.
8. halogen-containing polymkeric substance, as neoprene latex, chlorinated rubber, the polyethylene of chlorination or chlorosulphonation, the multipolymer of ethene and ethylene chloride, the homopolymer of Epicholorohydrin and multipolymer, the polymkeric substance of halogen-containing vinyl compound particularly, for example, polyvinyl chloride, polyvinylidene dichloride, fluorinated ethylene propylene, poly(vinylidene fluoride), and their multipolymer, as vinylchlorid/1,1 Ethylene Dichloride, vinylchlorid/vinyl acetate or vinylidene chloride/vinyl acetate copolymer
9. by α, the polymkeric substance that beta-unsaturated acid and derivative thereof obtain is as polyacrylic ester and polymethacrylate; Polymethylmethacrylate, polyacrylamide and the polyacrylonitrile of impact resistance have been improved with butyl acrylate.
10. 9) under the monomer mentioned to each other or with the multipolymer of other unsaturated monomers, for example, the acrylonitrile/butadiene multipolymer, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or vinyl cyanide/ethylene halide base co-polymer or vinyl cyanide/alkyl methacrylate/butadiene terpolymer.
11. the polymkeric substance that obtains by unsaturated alkohol and amine or their acyl derivative or its acetal; for example; polyvinyl alcohol; polyvinyl acetate (PVA), polyvinyl stearate, polyvinyl benzoate; the polymaleic acid vinyl acetate; polyvinyl butyral acetal, poly-phthalic acid allyl ester or polyene propyl group trimeric cyanamide, and they with 1) multipolymer of the alkene mentioned under the item.
12. the homopolymer of cyclic ethers class and multipolymer, as polyalkylene glycol, polyethylene oxide, the multipolymer of poly(propylene oxide) or they and bisglycidyl ether.
13. polyacetal such as polyoxymethylene and those contain the polyoxymethylene of oxyethane as comonomer; Use thermoplastic resin urethane, the polyacetal of polyacrylic ester or MBS modification.
14. the mixture of polyphenylene oxide and polyphenylene sulfide and polyphenylene oxide and styrene polymer or polymeric amide
15. by the polyethers of end of tape hydroxyl, the polyisocyanates of polyester or polyhutadiene and fat or aromatics, and the urethane that gets of its precursor.
16. with diamines and dicarboxylic acid and/or the polymeric amide and the copolyamide that make by aminocarboxylic acid or corresponding lactam, for example, polymeric amide 4, polyamide 6, polyamide 6/6,6/10,6/9,6/12,4/6,12/12, polymeric amide 11, polymeric amide 12 is the aromatic poly of starting raw material by m-xylene diamine and hexanodioic acid; By hexamethylene-diamine and m-phthalic acid or/and the polymeric amide of terephthalic acid preparation, they can contain or not conform to has a kind of elastomerics as improving agent, for example gather-2,4,4-tri-methyl hexamethylene terephthalamide or poly-metaphenylene isophthaloyl amine, also have aforementioned polymeric amide and polyolefine, olefin copolymer, ionomer or chemical bonding or the elastomeric segmented copolymer of grafted; Or and polyethers, for example with polyoxyethylene glycol, the segmented copolymer of polypropylene glycol or polytetramethylene glycol, the polymeric amide or the copolyamide of also useful EPDM or ABS modification; With polymeric amide (RIM polymeric amide system) in course of processing polycondensation.
17. polyureas, polyimide, polyamide-imide class and polybenzimidazole class.
18. from dicarboxylic acid and glycol and/or the polyester that gets from hydroxycarboxylic acid or corresponding lactone, for example, polyethylene terephthalate, polybutylene terephthalate, poly terephthalic acid 1,4-hydroxymethyl-cyclohexane ester and poly-hydroxy-benzoic acid, and by the polyethers deutero-block copolyether ester of terminal hydroxyl; The polyester of also useful polycarbonate or MBS modification.
19. polycarbonate and polyestercarbonate class.
20. polysulfones, polyether sulfone and polyethers ketone.
21. by aldehyde and phenol, urea or trimeric cyanamide be at the deutero-cross-linking copolymer, as phenol/formaldehyde resin, and urea/formaldehyde resin and melamine/formaldehyde resin
22. the Synolac of dryness and non-dryness
23. by copolyesters class deutero-unsaturated polyester, these copolyesters are to be that linking agent makes by saturated and undersaturated dicarboxylic acid and polyhydroxy-alcohol and with the vinylic chemical compound.The halogen-containing low combustible modification body that also has them.
24. by substituted acrylate, for example, epoxy acrylate, urethane acrylate or the crosslinkable acrylic resin of polyester acrylate deutero-.
25. with melamine resin, urea resin, the Synolac of polymeric polyisocyanate or cross linking of epoxy resin, vibrin and acrylate resin.
26. by polyepoxide, as bisglycidyl base ether or cyclic aliphatic diepoxide deutero-cross-linked epoxy resin class.
27. natural polymer such as Mierocrystalline cellulose, rubber, gelatin and, rhodia for example, cellulose propionate and cellulose butyrate, or cellulose ethers such as methylcellulose gum by the corresponding derivatives class of these polymkeric substance through chemical modification; Also have rosin and derivative thereof.
28. the blend of aforementioned polymkeric substance (composition polymer), for example, PP/EPDM, polymeric amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, the PVC/ polyacrylic ester, POM/ thermoplasticity PUR, PC/ thermoplasticity PUR, POM/ polyacrylic ester, POM/MBS, PPO/HIPS, PPO/PA6.6 and multipolymer, PA/HDPE, PA/PP, PA/PPO.
29, naturally occurring and synthetic organic materials, these raw materials are the pure monomeric compound or the mixture of these compounds, for example, mineral oil, animal and plant fat, oil and wax, or with synthetic ester class (for example, phthalic ester, adipic acid ester, phosphoric acid ester or trimellitate) be the oil on basis, fat and wax also have synthetic ester and the mineral oil mixture by any weight ratio, those of allusion quotation are used as the mixture of spinning component, and the water miscible liquid of these materials.
30. natural or elastomeric water miscible liquid, for example, natural latex or carboxylated styrene/butadiene copolymers latex.
31. polysiloxane is as the soft polysiloxane of describing among the USP 4259467 of wetting ability; With hard poly-organopolysiloxane as describing among the USP4355147.
32. polyketone imines and unsaturated acrylic acid or the like polyacetoacetate resin or with the combining of unsaturated acrylic resin.Unsaturated acrylic resin comprises urethane acrylate, polyether acrylate, has the vinyl of unsaturated side group or the melamine of acryl multipolymer and acrylated.The polyketone imines prepares from polyamines and ketone in the presence of acid catalyst.
33. contain the radiation curable compositions of ethylenically unsaturated monomers or oligopolymer and many unsaturated aliphatics oligopolymer.
34. the epoxy melamine resin is as the crosslinked stable Resins, epoxy such as the LSE-4103 (Monsanto) of light of high solid content melamine resin of the common etherificate by epoxide functional groups.
Usually, The compounds of this invention uses with about amount of 0.01 to about 5wt% of the composition that is stabilized, although this amount can be with concrete matrix and application change.Favourable scope is about 0.05 to about 3wt%, and especially 0.05 to about 1wt%.
Stablizer of the present invention is easy to introduce in the organic polymer with routine techniques, and introducing is to add in any appropriate stage from this material produce moulded products.For example, stablizer can dry powder form and mixed with polymers, or the suspension of stablizer or emulsion are mixed with solution, suspension or the emulsion of polymkeric substance.The polymer composition of the stabilization that the present invention obtains can at random contain about 0.01 to about 5%, and preferred about 0.025 to about 2%, especially about 0.1 different conventional additive to about 1% weight, material or its mixture as listed below.
1. antioxidant
1.1. alkylation monobasic phenols, 2,6 di tert butyl 4 methyl phenol for example, the 2-tertiary butyl-4, the 6-xylenol, 2,6-two-tertiary butyl-4-ethylphenol, 2,6-di-t-butyl-4-normal-butyl phenol, 2,6-two-tertiary butyl-4-isobutyl-phenol, 2,6-two cyclopentyl-4-methylphenol, 2-(Alpha-Methyl cyclohexyl)-4,6-xylenol, 2,6-two-octadecyl-4-methylphenol, 2,4,6-thricyclohexyl phenol, 2,6-two-tertiary butyl-4-methoxymethyl phenol.
1.2. the alkylation hydroquinones, for example, 2,6-di-t-butyl-4-methoxyphenol, 2,5 di tert butylhydroquinone, 2,5-two-amyl hydroquinone, 2,6-phenylbenzene-4-octadecane oxygen base phenol.
1.3. hydroxylation phenyl ether sulphur class, for example, 2,2 '-sulphur connects two (the 6-tertiary butyl-4-methylphenol), 2,2 '-sulphur connects two (4-octyl phenol), 4,4 '-sulphur connects two (the 6-tertiary butyls-3-methylphenol), 4,4 '-sulphur connects two (the 6-tertiary butyl-2-methylphenol).
1.4. alkylidene bisphenols, for example, 2,2 '-methylene-bis (the 6-tertiary butyl-4-cresylol), 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 (4,2,2 6-two-tert.-butyl phenol), '-ethylidene two (4,6-two-tert.-butyl phenol), 2,2 '-ethylidene two (the 6-tertiary butyl-4-isobutyl-phenol), 2,2 '-methylene-bis [6-(α-Jia Jibianji)-4-nonylphenol], 2,2 '-methylene-bis [6-(α, α-Er Jiajibianji)-4-nonylphenol], 4,4 '-methylene-bis (2,6-di-tert-butyl phenol), 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-hydroxybenzyl)-4-methylphenols of 6-, 1,1,3-three (5-tertiary butyl-4-hydroxy-2-aminomethyl phenyl) butane, 1, two (5-tertiary butyl-4-hydroxy-2-methyl-phenyl) the 3-n-dodecane sulfenyl butane of 1-, two [3,3-pair (3 '-tertiary butyl-4 '-hydroxy phenyl) the butyric acid glycol ester, two (3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) Dicyclopentadiene (DCPD), terephthalic acid two [2-(3 '-tertiary butyl-2 '-hydroxyl-5 '-methyl-benzyl)-the 6-tertiary butyl-4-aminomethyl phenyl] ester.1.5. benzyl compounds, for example: 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-2,4, the 6-Three methyl Benzene, two (3, the 5-di-tert-butyl-4-hydroxyl benzyl)-thioethers, 3, the different monooctyl ester of 5-di-tert-butyl-4-hydroxyl benzyl-ethyl thioglycollic acid, two (4-tertiary butyls-3-hydroxyl-2, the 6-dimethyl benzyl) two mercaptan terephthalate, 1,3,5-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) isocyanuric acid ester, 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) isocyanuric acid ester, 3,5-di-tert-butyl-4-hydroxyl benzyl di(2-ethylhexyl)phosphate (octadecyl) ester, 3, the calcium salt of 5-di-tert-butyl-4-hydroxyl benzyl monoethyl phosphate.1.6. the acyl amino phenols, for example: 4-hydroxyl-lauroyl aniline, 4-hydroxyl-stearanilide, 2, two (hot the sulfenyl)-6-(3,5-di-t-butyl-4-hydroxyl-anilino) of 4--s-triazine, N-(3,5-di-t-butyl-4-hydroxyl-phenyl) carboxylamine monooctyl ester.1.7. β-(3,5-di-t-butyl-4-hydroxyl-phenyl) ester of propionic acid and monohydroxy-alcohol or polyvalent alcohol, for example: same methyl alcohol, Stearyl alcohol, 1,6-hexylene glycol, neopentyl alcohol, thiodiglycol, trolamine, glycol ether, triglycol, tetramethylolmethane,, three (hydroxyethyl) isocyanuric acid ester, two (hydroxyethyl) oxalic acid diamide, tri-isopropanolamine.1.8. the ester of β-(5-tertiary butyl-4-hydroxy-3-methyl-phenyl) propionic acid and monohydroxy-alcohol or polyvalent alcohol, for example: same methyl alcohol, Stearyl alcohol, 1,6-hexylene glycol, neopentyl alcohol, thiodiglycol, trolamine, glycol ether, triglycol, tetramethylolmethane,, three (hydroxyethyl) isocyanuric acid ester, two (hydroxyethyl) oxalic acid diamide, tri-isopropanolamine.1.9. β-(3; 5-di-t-butyl-4-hydroxyl-phenyl) acid amides of propionic acid; for example: N; N '-two (3; 5-di-t-butyl-4-hydroxyl-hydrocinnamoyl) hexamethylene-diamine, N, N '-two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamoyl) trimethylene diamines, N; N '-two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamoyl) hydrazine.1.10 diarylamine, for example: diphenylamine, N-phenyl-1-naphthylamine, N-(uncle's 4-octyl phenyl)-1-ALPHA-NAPHTHYL AMINE, 4,4 '-two uncle's octyl group-diphenylamines, N-phenyl-benzyl amine and 2,4, the reaction product of 4-2,4,4-Trimethyl-1-pentene, diphenylamine and 2,4, the reaction product of 4-2,4,4-Trimethyl-1-pentene, N-phenyl-1-naphthylamine and 2,4, the reaction product of 4-2,4,4-Trimethyl-1-pentene.2. uv-absorbing agent and light stable 2.1. 2-(2 '-hydroxyl-phenyl) benzotriazole category, for example: 5 '-methyl-, 3 ', 5 '-di-t-butyl-, 5 '-tertiary butyl-, 5 '-(1,1,3,3-tetramethyl--butyl)-, 5-chloro-3 ', 5 '-di-t-butyl, 5-chloro-3 '-tertiary butyl-5 '-methyl-, 3 '-sec-butyl-the 5 '-tertiary butyl-, 4 '-octyloxy, 3 ', 5 '-two tert-pentyls, 3 ', 5 '-two (α, α-Er Jiajibianji), 3 '-tertiary butyl-5 '-(2-(σ-hydroxyl-eight (ethylene oxy) carbonyl-ethyl)-, 3 '-dodecyl-5 '-methyl-and 3 '-tertiary butyl-5 '-(2-carbonyl octyloxy) ethyl-and 5 '-methyl-derivatives of dodecylization.
2.2.2-the hydroxy benzophenone class, for example, its 4-hydroxyl, the 4-methoxyl group, the 4-octyloxy, 4-oxygen in last of the ten Heavenly stems base, the 4-dodecyloxy, the 4-benzyloxy, 4,2 ', 4 '-trihydroxy-and 2 '-hydroxyl-4,4 '-the dimethoxy derivatives class.
2.3. replace and unsubstituted benzoates, for example, Whitfield's ointment 4-tert-butyl-phenyl ester, the Whitfield's ointment phenylester, Whitfield's ointment octyl phenyl ester, Resorcinol dibenzoate, Resorcinol two (4-p t butylbenzoic acid ester), the Resorcinol benzoic ether, 3,5-di-tert-butyl-4-hydroxybenzoic acid-2,4-di-tert-butyl-phenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid cetyl ester.
2.4. acrylate, for example, alpha-cyano-β, β-diphenyl-ethyl acrylate, alpha-cyano-β, β-diphenyl 2-Propenoic acid-2-ethylhexyl ester, α-methoxycarbonyl methyl cinnamate, alpha-cyano-Beta-methyl-p-methoxycinnamic acid methyl esters, alpha-cyano-Beta-methyl-p-methoxycinnamic acid butyl ester, α-methoxycarbonyl-p-methoxycinnamic acid methyl esters and N-(beta-carbomethoxy-3-β-acrylonitrile base)-2-methyl indoline.
2.5. the nickel compound class, for example, 2,2 '-sulphur connects the nickel complex of two [4-(1,1,3, the 3-tetramethyl butyl) phenol], as 1: 1 or 1: 2 title complex, has or do not have additional ligand (as n-Butyl Amine 99, trolamine or N-cyclohexyl diethanolamine); Nickel dibutyl dithiocarbamate, the nickel salt of an alkyl esters, for example, 4-hydroxyl-3, methyl, ethyl or the butyl ester of 5-di-t-butyl benzylphosphonic acid; The nickel complex of ketoxime, for example, the nickel complex of 2-hydroxy-4-methyl phenyl undecyl ketoxime; Has or do not have the nickel complex of the 1-phenyl-4-lauroyl-5-hydroxypyrazoles of additional ligand.
2.6. sterically hindered amine, for example, sebacic acid two (2,2,6, the 6-tetramethyl-piperidyl) ester, sebacic acid two (1,2,2,6,6-pentamethyl-piperidyl) ester, sebacic acid two (1-octyloxy-2,2,6,6-tetramethyl--4-piperidyl) ester, n-butyl-3,5-di-tert-butyl-4-hydroxyl benzyl propanedioic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) ester, 1-(2-hydroxyethyl) 2,2,6, the condenses of 6-tetramethyl--4-hydroxy piperidine and Succinic Acid, N, N '-two (2,2,6,6-tetramethyl--4-piperidyl) hexamethylene-diamine and uncle 4-hot amino-2, the condenses of 6-two chloro-1,3,5-triazines, nitrilotriacetic acid(NTA) three (2,2,6, the 6-tetramethyl-piperidyl) ester, 1,2,3,4 fourth tetracids four (2,2,6,6-tetramethyl--4-piperidyl) ester, 1,1 '-(1, the 2-ethylidene) two (3,3,5, the 5-tetramethylpiperidone).2.7. oxamide, for example, 4,4 '-two octyloxies-N, oxanilide N, 2,2 '-two octyloxies-5,5 '-di-t-butyl-N, oxanilide N, 2,2 '-two-dodecyloxy-5,5 '-di-t-butyl-N, oxanilide N, 2-oxyethyl group-2 '-ethyl-oxanilide, N, N '-two (3-dimethylamino-propyl) oxamide, the 2-oxyethyl group-5-tertiary butyl-2 '-ethyl-oxanilide and it with 2-oxyethyl group-2 '-ethyl-5,4 '-di-t-butyl-N, the mixture of oxanilide N and adjacent and to methoxyl group disubstituted-mixture of oxanilide, adjacent and right-oxyethyl group is disubstituted-mixture of oxanilide.2.8. hydroxy phenyl-s-triazine, for example: 2, two (2, the 4-the 3,5-dimethylphenyl)-4-(2-hydroxyl-4-octyloxyphenyl) of 6--s-triazine; 2, two (2, the 4-the 3,5-dimethylphenyl)-4-(2,4-dihydroxyl-phenyl) of 6--s-triazine; 2, two (2, the 4-the dihydroxy phenyl)-6-(4-chloro-phenyl) of 4--s-triazine; 2, two [2-hydroxyl-4-(2-hydroxyl-oxyethyl group)-the phenyl]-6-(4-chloro-phenyl) of 4--s-triazine; 2, two [2-hydroxyl-4-(2-hydroxyl-4-(2-hydroxyl-oxyethyl group))-phenyl]-6-(2,4-dimethyl-phenyl)-s-triazines of 4-; 2, two [2-hydroxyl-4-(2-hydroxyl-oxyethyl group)-the phenyl]-6-(4-bromo-phenyl) of 4--s-triazine; 2, two [2-hydroxyl-4-(2-acetyl oxygen oxyethyl group)-phenyl]-6-(4-chloro-the phenyl)-s-triazines of 4-; 2, two (2,4-dihydroxyl-phenyl)-6-(2,4-dimethyl-phenyl) of 4--s-triazine,
3. metal deactivator, for example, N, N '-phenylbenzene oxamide, N-salicylic aldehyde-N '-salicylyl hydrazine; N, N '-two (salicyloyl) hydrazine, N, N '-two (3,5-di-t-butyl-4-hydroxybenzene propionyl) hydrazine; 3-salicylyl amino-1,2,4-triazole, two (benzylidene) oxalyl hydrazine.
4. phosphorous acid esters and phosphinate, for example, triphenyl phosphite, phosphorous acid diphenyl alkyl ester, phosphorous acid phenyl dialkyl ester, tricresyl phosphite (nonyl phenyl) ester, phosphorous acid-three-dodecyl ester, phosphorous acid-three-stearyl, diphosphorous acid distearyl pentaerythritol ester, tricresyl phosphite (2, the 4-tert-butyl-phenyl) ester, diphosphorous acid diiso decyl pentaerythritol ester, diphosphorous acid two (2,4,6-tri-tert phenyl) pentaerythritol ester, two (2, the 4-di-t-butyl-6-aminomethyl phenyl) pentaerythritol esters of diphosphorous acid, diphosphorous acid two (2, the 4-di-tert-butyl-phenyl) pentaerythritol ester, three tricresyl phosphite stearyl sorbitol esters, 4,4 '-biphenylene two phosphonous acid-four (2, the 4-di-tert-butyl-phenyl) ester.
5. peroxide scavenger, for example β-sulphur connects ester such as lauryl, octadecane ester, tetradecane ester or the tridecane ester of dipropionic acid, the zinc salt of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, two (octadecyls), two sulphur, tetramethylolmethane four (β-dodecane thiohydracrylic acid ester).
6. azanol class, for example, N, N-diphenyl-methyl azanol, 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 is derived from the N of hydrogenated tallow amine, N-dialkyl group azanol.
7. nitrone, N-phenmethyl-α-phenyl nitrone for example, 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 is derived from the N that is made by hydrogenated tallow amine, the nitrone of N-dialkyl group azanol.
8. polymeric amide stablizer, for example composition of mantoquita and iodide and/or phosphorus compound and manganous salt.
9. alkaline co-stabilizer, melamine for example, Polyvinylpyrolidone (PVP), dicyanamide, triallyl cyanurate, urea derivatives, hydrazine derivative, amine, polymeric amide, urethane, the an alkali metal salt of higher fatty acid and alkaline earth salt, as calcium stearate, Zinic stearas, Magnesium Stearate, natrium ricinoleicum and potassium palmitate, pyrocatechol antimony, or pyrocatechol zinc.
10. nucleator, for example 4-p t butylbenzoic acid, hexanodioic acid, diphenyl acetic acid.
11. filler and toughener, lime carbonate for example, silicate, glass fibre, asbestos, talcum, kaolin, mica, barium sulfate, metal oxide and oxyhydroxide, carbon black, graphite.
12. other additive, softening agent for example, lubricant, emulsifying agent, pigment,, optical whitening agent, fire retardant, static inhibitor, whipping agent and sulfur synergist connect the dipropionic acid dilaurate or sulphur connects dipropionic acid two (octadecyl) ester as sulphur.
13. Benzopyranone kind and indoline ketone, for example be disclosed in US-A-4 325863, US-A-4 338 244, compound among the US-A-5 175 312, or 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-(4-(2-hydroxy ethoxy) phenyl) benzofuran-2-ones), 5,7-di-t-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-penta acyloxy phenyl)-5,7-di-t-butyl-benzofuran-2-ones.Co-stabilizer except that 13 times listed benzofuranones is added with for example 0.01～10% concentration, and this concentration is with respect to the gross weight for the treatment of stable material.
Further preferred compositions comprises other additive, especially phenolic antioxidant, photostabilizer or processing stabilizers except component (a) with (b).
Particularly preferred additive is phenolic antioxidant (in lising the 1st), space hindered amine (in lising the 2.6th), phosphorous acid ester and phosphinate (in lising the 4th) and peroxide scavenger (in lising the 5th).
Other also is that particularly preferred additive (stablizer) is a benzofuran-2-ones, described in USA4325863, USA4338244 or USA5175312.
Significant especially phenolic antioxidant is selected from: 3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid Octadecane ester, four (3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid) neopentane four esters, 3, the two Octadecane esters of 5-di-t-butyl-4-hydroxyl-benzylphosphonic acid, 1,3,5-three (3,5-di-t-butyl-4-hydroxyl-benzyl) isocyanuric acid ester, two (3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid) sulphur diethyl ester, 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl-benzyl) benzene, two (3-methyl-5-tertiary butyl-4-hydroxy phenylpropionic acid) (3,6-two oxa-s eight methylene radical) ester, 2,6-di-t-butyl-p-cresol, 2,2 '-ethylidene-two (4, the 6-di-tert-butylphenol), 1,3,5-three (2,6-dimethyl-4-the tertiary butyl-3-hydroxyl-benzyl) isocyanuric acid ester, 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-hydrocinnamamide oxygen) ethyl] isocyanuric acid ester, 3,5-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) rice phenol, two (3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid) hexa-methylene ester, 1-(3,5-di-t-butyl-4-hydroxyl-anilino)-3,5-two hot sulfenyl-s-triazines, N, N '-hexa-methylene-two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), two (3,5-di-t-butyl-4-hydroxyl-benzylphosphonic acid ethyl ester) calcium, two [3,3-two (3-tert-butyl-hydroxy phenyl) butyric acid diethyl ester, 3,5-di-t-butyl-4-hydroxyl-dibenzylsulfide guanidine-acetic 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)-ethyl]-oxamide.
Most preferred phenolic antioxidant is four (3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid) neopentane four esters, 3, and 5-di-t-butyl-4-hydroxyl-phenylpropionic acid Octadecane ester, 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl-benzyl) benzene, 1,3,5-three (3,5-di-t-butyl-4-hydroxyl-benzyl) isocyanuric acid ester, 2,6-di-t-butyl-p-cresol, 2,2 '-ethylidene-two (4, the 6-di-tert-butylphenol).
Significant especially hindered amine is selected from: sebacic acid two (2,2,6; 6-tetramethyl piperidine-4-yl) ester, sebacic acid two (1,2; 2,6,6-pentamethyl-piperidin-4-yl) ester; (3,5-di-t-butyl-4-hydroxyl-benzyl) butyl malonic acid two (1,2; 2,6,6-pentamethyl-piperidin-4-yl) ester; 4-benzoyl-2,2,6; the 6-tetramethyl piperidine, 4-stearoyl-oxy-2,2; 6,6-tetramethyl--piperidines, 3-n-octyl-7; 7,9,9-tetramethyl--1; 3,8-three azepines-spiral shell [4.5] decane-2,4-diketone; nitrilotriacetic acid(NTA) three (2,2,6; 6-tetramethyl piperidine-4-yl) ester, 1,2-two (2; 2,6,6-tetramethyl--3-Oxypertine-4-yl) ethane; 2,2,4; 4-tetramethyl--7-oxa--3,20-diaza-21-oxygen two spiral shells [5.1.11.2] heneicosane, 2; the hot amino of 4-two chloro-uncles 6--s-triazine and 4,4 '-hexa-methylene two (amino-2,2; 6,6-tetramethyl--piperidines) polycondensation product, 1-(2-hydroxyethyl)-2; 2,6, the polycondensation product of 6-tetramethyl--4-hydroxy-piperdine and Succinic Acid; 4,4 '-hexa-methylene two-(amino-2,2; 6,6-tetramethyl piperidine) and the polycondensation product of glycol dibromide; 1,2,3; 4-butanetetra-carboxylic acid four (2,2,6; 6-tetramethyl piperidine-4-yl) ester, 1,2; 3,4-butanetetra-carboxylic acid four (1,2; 2,6,6-pentamethyl-piperidin-4-yl) ester; 2,4-two chloro-6-morpholino-s-triazines and 4,4 '-hexa-methylene two-(amino-2; 2,6,6-tetramethyl piperidine) polycondensation product; N, N ', N "; N -four [(4, two (butyl-1,2; 2,6, the 6-pentamethyl-piperidin-4-yl)-amino-s-triazine-2-yls of 6-]-1; 10-diamino-4,7-diaza decane, blended 1; 2,3, the 4-butanetetra-carboxylic acid [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] ester, blended 1,2; 3; 4-butanetetra-carboxylic acid [1,2,2; 6; 6-pentamethyl-piperidin-4-yl/β, β, β '; β '-tetramethyl--3; 9-(2,4,8; 10-four oxaspiros [5.5]]-undecane) diethyl] ester; two (2,2,6; 6-tetramethyl piperidine-4-carboxylic acid) eight methylene radical esters; 4,4 '-ethylene two (2,2; 6; 6-tetramethyl-piperazine-3-ketone), N-2,2; 6; 6-tetramethyl piperidine-4-base-dodecyl Succinic Acid imide, N-I, 2; 2; 6,6-pentamethyl-piperidin-4-yl-dodecyl Succinic Acid imide, N-1-ethanoyl-2; 2; 6,6-tetramethyl piperidine-4-base-dodecyl-Succinic Acid imide, 1-ethanoyl-3-dodecyl-7; 7; 9,9-tetramethyl--1,3; 8-thriazaspiro [4.5] decane-2; the 4-diketone, two (the 1-octyloxies-2,2 of sebacic acid; 6; 6-tetramethyl piperidine-4-yl) ester, two (the 1-cyclohexyloxies-2,2 of Succinic Acid; 6; 6-tetramethyl-piperazine-4-yl) ester, 1-octyloxy-2,2; 6; 6-tetramethyl--4-hydroxy-piperdine, poly-{ [the hot amino of uncle 6--s-triazine-2,4-two bases] [2-(1-cyclohexyloxy-2; 2; 6,6-tetramethyl piperidine-4-yl) imino--hexa-methylene-[4-(1-cyclohexyloxy-2,2; 6; 6-tetramethyl piperidine-4-yl) imino-] } and 2,4; 6-three [N-(1-cyclohexyloxy-2; 2,6,6-tetramethyl piperidine-4-yl)-normal-butyl amino]-the s-triazine.
Most preferred hindered amine compound is a sebacic acid two (2,2,6,6-tetramethyl piperidine-4-yl) ester, sebacic acid two (1,2,2,6,6-pentamethyl-piperidin-4-yl) ester, (3,5-di-t-butyl-4-hydroxyl-benzyl) butyl malonic acid two (1,2,2,6,6-pentamethyl-piperidin-4-yl) ester, 1-(2-hydroxyethyl)-2,2,6, the polycondensation product of 6-tetramethyl--4-hydroxy-piperdine and Succinic Acid, 2, the hot amino of 4-two chloro-uncles 6--s-triazine and 4,4 '-hexa-methylene two (amino-2,2,6,6-tetramethyl--piperidines) polycondensation product, N, N ', N ", N -four [(4, two (butyl-1; 2,2,6; 6-pentamethyl-the piperidin-4-yl)-amino of 6-)-s-triazine-2-yl]-1,10-diamino-4,7-diaza decane; sebacic acid two (1-hot amino-2,2,6; 6-tetramethyl-piperazine-4-yl) ester, two (the 1-cyclohexyloxies-2,2; 6 of Succinic Acid, 6-tetramethyl piperidine-4-yl) ester, 1-octyloxy-2,2,6,6-tetramethyl--4-hydroxy-piperdine, poly-{ [the hot amino of uncle 6--s-triazine-2,4-two bases] [2-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) imino--hexa-methylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) imino-] } and 2,4,6-three [N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperazine-4-yl)-normal-butyl amino]-the s-triazine.
The present composition can contain another kind of UV absorption agent in addition, and it is selected from s-triazine, N, N '-oxalyl pentanoic, hydroxy benzophenone, benzoic ether and α-Qing Jibingxisuanzhi.
Particularly the present composition can contain at least a other the 2-hydroxyphenyl-2H-benzotriazole of stabilizing effective amount in addition; Another kind of triaryl-s-triazine; Or hindered amine or its mixture.
2-hydroxyphenyl-2H-benzotriazole is preferably selected from: 2-(2-hydroxyl-3, the 5-di-tert-pentyl-phenyl)-the 2H-benzotriazole, 2-[2-hydroxyl-3,5-two (α, α-Er Jiajibianji) phenyl]-the 2H-benzotriazole, 2-[2-hydroxyl-3-(α, α-Er Jiajibianji)-5-octyl phenyl]-the 2H-benzotriazole, the 2-{2-hydroxyl-3-tertiary butyl-5-[2-(σ-hydroxyl-eight (ethylene oxide,1,2-epoxyethane) carbonyl) ethyl] phenyl]-the 2H-benzotriazole; With the 2-{2-hydroxyl-3-tertiary butyl-5-[2-(carbonyl octyloxy) ethyl] phenyl }-the 2H-benzotriazole.
Other triaryl-s-triazine preferably from: 2, two (2,4-dimethyl-phenyl)-6-of 4-(the hot oxygen phenyl of 2-hydroxyl-4-)-s-triazine; 2,4-phenylbenzene-6-(the own oxygen phenyl of 2-hydroxyl-4-)-s-triazine; 2, two (2,4-dimethyl-phenyl)-6-[2-hydroxyl-4-(the 3-dodecane oxygen/tridecane oxygen-2-hydroxyl third oxygen) phenyl of 4-]-the s-triazine; And 2-(2-hydroxyl ethylamino)-4, two [N-butyl-N-(1-hexamethylene oxygen-2,2,6,6-tetramethyl piperidine-4-yl) amino]-s-triazines of 6-.
The alkyd varnish that available the present invention stablizes with the effect that prevents light and moisture is traditional baking finish, this lacquer especially is applied to automotive coatings (automobile finish), for example (see H.Wagner and H.F.Sarx based on the lacquer of alkyd/melamine resin and alkyd/acrylic/melamine resin, " Lackkunstharze " (1977), P99～123).Other linking agent comprises biuret (glycouril) resin, blocked isocyanate or Resins, epoxy.
Be suitable for metal finish paint and solid colored paint with the stable lacquer of the present invention, especially colour-separation drafting lacquer and various coil coating.The lacquer that the present invention is stable is preferably used in a conventional manner, and two kinds of methods are arranged, perhaps by the single coating method, or by two coating processes.In back one method, the undercoat that contains colorant is used earlier, applies the finishing coat of the clear lacquer then thereon.
It should be noted that also compound of the present invention is applicable to non-acid catalyzed thermosetting resin,, at random use silicon, isocyanic ester or isocyanurate-modified as epoxy, epoxy-polyester, vinyl, alkyd, acrylic acid or the like and vibrin.Use traditional linking agent, as cross-linked epoxy and epoxy-vibrin such as acid, acid anhydrides, amine.Correspondingly, epoxide can be used as the linking agent of different acrylic acid or the like or vibrin system, the modification by the reactive group that exists on the skeleton of described system.
When using in two tricoat finish, The compounds of this invention can add in the Clear coating, or not only adds in the Clear coating but also added in the undercoat of colorant.
When, water miscibility water-soluble when needs or water dispersible coating, the ammonium salt of the acidic group that exists in the resin forms.Alkoxide component reaction by glycidyl methacrylate and selection can prepare the powdery coating composition.
Benzotriazole of the present invention is by being used to prepare the traditional method preparation of these class methods.Common program relates to the diazotization of the o-Nitraniline of replacement, and subsequently with the diazonium salt that is substituted phenol coupling gained, and reducing couple pyridine intermediate is to corresponding required benzotriazole.The raw material of these benzotriazoles mainly is several of beginning, maybe can be by the ordinary method preparation of organic synthesis.
Be specially adapted to automotive coatings though the present invention has the benzotriazole of enhanced weather resistance, can expect, they also are specially adapted to other and require weather resistance enhanced application scenario, as solar film (solar film) etc.
Following examples only are illustrative purposes.
The preparation of embodiment 15-trifluoromethyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole is the diazotization of 4-amino-3-nitro-benzo trifluoride a)
In being housed, churned mechanically 500ml there-necked flask adds 41.2g 4-amino-3-nitro-benzo trifluoride, 52ml concentrated hydrochloric acid and 100ml distilled water.The solution that stirs is cooled to 5 ℃, adds 17.3g then and be dissolved in Sodium Nitrite in the 50ml water.This solution was stirred 2 hours under 0～5 ℃ of condition, filter then ,-10 ℃ of storages.B) monoazo adducts
Adding 40g in churned mechanically 1000ml flask is housed is dissolved in sodium hydroxide in the 200ml methyl alcohol and 32.4g and is dissolved in 2-α-cumyl-uncle 4--octyl phenol in the 50ml dimethylbenzene.Solution is cooled to 5 ℃, then under 0～5 ℃ of condition, in 2 hour time, be added in the diazotization solution of the 4-amino-3-nitro-benzo trifluoride of preparation in a part.Add 100ml dimethylbenzene then, water, aqueous hydrochloric acid, water, sodium bicarbonate aqueous solution and wash organic phase at last with water.Removal of solvent under reduced pressure, residue is with chromatogram purification (silica gel, heptane: ethyl acetate=95: 5) obtain the adducts of 42.1g dark red paste.C) reduction of monoazo adducts
The monoazo adducts and the 400ml ethanol that in the 1000ml flask, add 20g sodium hydroxide, 40ml water, 42.1g preparation in the b part.With mixture heating up to 80 ℃, add the 27g formamidine sulfinic acid then while stirring.1.5 with the solution cool to room temperature, add 100ml water again after hour.With concentrated hydrochloric acid the pH value is adjusted to pH7.Under vacuum, remove ethanol, use the dichloromethane extraction water layer, under vacuum, boil off solvent then, residue is used chromatogram purification (silica gel, normal heptane: toluene, 9: 1) and used alcohol crystal.Thereby obtain the described compound of 5.6g title, this compound is a light yellow solid, 119～121 ℃ of fusings.
The preparation of embodiment 25-fluoro-2-(2-hydroxy-3-alpha-cumyl--uncle 5--octyl phenyl)-2H-benzotriazole
Title compound can use 31.2g 4-fluoro-2-nitro-aniline to prepare according to embodiment 1 described step.In step c, need add the 9g formamidine sulfinic acid and finish reduction reaction, thick product (the heptane: toluene of on silica gel, purifying, 1: 1) obtain the linen title compound solid of 4.5g, then through the second dried meat: the toluene recrystallization purifying obtains the 1.1g title compound, and this compound is 93～96 ℃ of fusings.
The preparation of embodiment 35-chloro-2-(2-hydroxy-3-alpha-cumyl--uncle 5--octyl phenyl)-2H-benzotriazole
According to a part and the described step of b part among the embodiment 1, use 339.3g 4-chloro-2-nitro-aniline to prepare the monoazo intermediate product that can generate title compound.Crude product comes purifying with recrystallization in methyl alcohol, thereby obtains 70.9g scarlet monoazo adducts.C) reduction of monoazo adducts
With the mixture heating up to 95 of 11.8g sodium hydroxide and 138g 2-butanols ℃.Stir at 90 fens clock time inner edges that the limit adds the above-mentioned monoazo adducts of 60.1g and 1.3g is dissolved in 2 in the 90ml 2-butanols, 3-two chloro-1, the solution that the 4-naphthoquinones is formed adds reaction mixture heat extraction by product 2-butanone then and adds the 2-butanols to replenish distillate.Reaction mixture is cooled to 85 ℃, and sulfuric acid and salt water washing with 2.5N concentrate then.Residue methyl alcohol: the dimethylbenzene recrystallization obtains the 45.6g title compound, and this compound is a light yellow solid, 104～105 ℃ of fusings.
The preparation of embodiment 45-phenyl sulphur-2-(2-hydroxy-3-alpha-cumyl--uncle 5--octyl phenyl)-2H-benzotriazole
In the mixture of 75g 5-chloro-2-(2-hydroxy-3-alpha-cumyl--uncle 5--octyl phenyl)-2H-benzotriazole under being heated to 90 ℃ of conditions, that stir and 105g N-Methyl pyrrolidone, add the potassium hydroxide aqueous solution of 44.3g 45% at 15 minutes in the clock time earlier, added the 20.4g thiophenol at 15 minutes in the clock time then.Reaction mixture is heated to 170～175 ℃ then, reacted 4 hours, the water in the mixture is removed by distillation.Then reaction mixture is cooled to 100 ℃, adds dimethylbenzene and water, the spirit of salt aqueous solution with 15% is regulated and is made the mixture that obtains be acid.Isolate organic phase, wash with water then and concentrate.Thereby crude product obtains the 82g title compound with recrystallizing methanol, and this compound is a light yellow solid, 124～125 ℃ of fusings.
The preparation of embodiment 55-benzene sulfonyl-2-(2-hydroxy-3-alpha-cumyl--uncle 5--octyl phenyl)-2H-benzotriazole
In the 1000ml flask, be added in 75.2g 5-phenyl sulphur-2-(2-hydroxy-3-alpha-cumyl--uncle 5--octyl phenyl)-2H-benzotriazole, 102g dimethylbenzene, 0.9g sodium tungstate dihydrate and the 18.4g formic acid of preparation among the embodiment 4.With mixture heating up to 50 ℃, slowly add the hydrogen peroxide of 36.3g 50% then while stirring, thereby make temperature be no more than 85 ℃.And then add dimethylbenzene and water, and isolate organic phase, wash organic phase with sodium sulfite aqueous solution, concentrate after washing twice with water then.Thick product carries out recrystallization in methyl alcohol, obtain the 75.2g title compound, and this compound is a light yellow solid, 170～171 ℃ of fusings.
The preparation of embodiment 65-nonyl sulphur-2-(2-hydroxy-3-alpha-cumyl--uncle 5--octyl phenyl)-2H-benzotriazole
According to embodiment 4 described steps, just can prepare title compound with 30g 5-chloro-2-(2-hydroxy-3-alpha-cumyl--uncle 5--octyl phenyl)-2H-benzotriazole and 17.6g nonyl mercaptan.
The preparation of embodiment 75-nonyl sulphonyl-2-(2-hydroxy-3-alpha-cumyl--uncle 5--octyl phenyl)-2H-benzotriazole
5-nonyl sulphur-2-(2-hydroxy-3-alpha-cumyl--uncle 5--octyl phenyl)-2H-benzotriazole of preparation is without the purifying of sulfo-intermediate product in embodiment 6, and directly use the hydrogen peroxide of 8.7g formic acid, 0.7g sodium tungstate dihydrate and 17.6g 50% that it is oxidized to sulfone, thereby obtain title compound, this compound is yellow resin, and its molion m/e is 631
The preparation of embodiment 85-chloro-2-(2-hydroxyl-3-phenyl-uncle 5--octyl phenyl)-2H-benzotriazole
According to a part and the described step of b part among the embodiment 1, use 4-chloro-2-nitro-aniline and 2-phenyl-uncle 4--octyl group-phenol to prepare the monoazo intermediate product that can generate title compound.Crude product comes purifying with recrystallization in methyl alcohol, thereby obtains scarlet monoazo adducts.
According to embodiment 3 described reduction steps, with monoazo adducts and 19.9g sodium hydroxide and the 2.4g 2 that 65g as above prepares, 3-two chloro-1,4-naphthoquinones prepared in reaction title compound.Crude product comes purifying (hexane: ethyl acetate, 5: 1) with silica gel chromatography, obtains a kind of component, and its main component is a title compound, and the molion m/e of this compound is 433.
The preparation of embodiment 95-phenyl sulphur-2-(2-hydroxyl-3-phenyl-uncle 5--octyl phenyl)-2H-benzotriazole
According to embodiment 4 described steps, can prepare title compound with the compound of 20g embodiment 8 preparations, potassium hydroxide aqueous solution, 10.3g thiophenol and the 100g N-methyl-pyrrolidone of 20.4g 45%.Use toluene to come purifying as elutriant through silica gel chromatography, the title compound of purifying is a kind of oily matter.
The preparation of embodiment 105-benzene sulfonyl-2-(2-hydroxyl-3-phenyl-uncle 5--octyl phenyl)-2H-benzotriazole
According to embodiment 5 described steps, can prepare title compound with aqueous hydrogen peroxide solution and the 0.6g sodium tungstate dihydrate of the compound of 20g embodiment 9 preparation, 6.4g formic acid, 15.0g 50%.2.5g crude product obtains the title compound of 2.0g purifying through dimethylbenzene/recrystallizing methanol purifying, this compound is a buff powder, and it is 204～206 ℃ of fusings.
The preparation of embodiment 115-chloro-2-(2-hydroxyl-3,5-phenyl-dialkyl phenyl organic)-2H-benzotriazole mixture (alkyl is C4 independently, C8, C12 and C16)
Under nitrogen environment, with 65.4g 5-chloro-2-(2-hydroxyl-3, the 5-dialkyl phenyl organic)-mixture of the methylsulphonic acid of 2H-benzotriazole, 45ml dodecylene and 13ml is heated to 170 ℃ together, in 4.5 hours time, add the 135ml dodecylene then again, reaction mixture is cooled to 100 ℃, use 400g trash ice chilling then, use ethyl acetate extraction again three times.Merge organic phase, water, sodium bicarbonate aqueous solution, water and salt solution wash in turn, use anhydrous magnesium sulfate drying then, concentrate at last.The polymeric residue is removed through bubbling (bulbto bulb) distillation under the vacuum of 0.2mm, condition that upper temperature limit is 210 ℃, and unreacted starting materials is removed through distillation (0.04mm, 160 ℃), obtains the title mixture of 45g yellow oily.
The preparation of embodiment 125-phenyl sulphur-2-(2-hydroxyl-3,5-dialkyl phenyl organic)-2H-benzotriazole mixture (alkyl is C4 independently, C8, C12 and C16)
According to the step of embodiment 4, the mixture, 11.2g potassium hydroxide and the 12.3ml thiophenol that prepare in embodiment 11 with 40g prepare the title mixture.
The preparation of embodiment 135-benzene sulfonyl-2-(2-hydroxyl-3,5-dialkyl phenyl organic)-2H-benzotriazole mixture (alkyl is C4 independently, C8, C12 and C16)
The mixture heating up that crude product, 350ml Virahol, 14.7ml formic acid and the 1.8ml vitriol oil of preparation among the embodiment 12 are formed refluxes, and drips the hydrogen peroxide of 30ml 50% then in 2 hours time.Refluxed through 3 hours again,, add 10% sodium sulfite aqueous solution and sodium bicarbonate aqueous solution then the reaction mixture cooling.Virahol is removed in evaporation, the residue dichloromethane extraction, and the organic phase water washs then through anhydrous magnesium sulfate drying.Thereby with solution concentration is 45g thickness prange buttery crude product, and this crude product of 30g through silica gel chromatography (heptane: ethyl acetate, 4: 1) purifying, is obtained 28.9g yellow oily title mixture.
The preparation of embodiment 145-two phenenyl phosphinyl-2-(2-hydroxyl-3,5-tri-tert phenyl)-2H-benzotriazole
In the flame-dried three mouthfuls of round-bottomed flasks of 500ml that are equipped with condenser, magnetic stirring apparatus and thermometer, add 100ml methyl-sulphoxide, 7.41g (0.066mol) potassium tert.-butoxide and 11.17g (0.060mol) diphenylphosphine with syringe.In above-mentioned red mixture, add by 10.56g (0.030mol) 5-chloro-2-(2-hydroxyl-3 at once, the 5-di-tert-butyl-phenyl)-the 2H-benzotriazole is dissolved in the slurry that forms in the 50ml methyl-sulphoxide, the brown solution of gained stirred 3.5 hours under 135 ℃ of conditions, then cool to room temperature.Mixture adds ethyl acetate then with the saturated ammonium chloride chilling of a part, isolates organic phase, and water is given a baby a bath on the third day after its birth inferior, with the salt washing once, uses anhydrous magnesium sulfate drying then.In solution, add 50% hydrogen peroxide, with heat release.Mixture was left standstill 30 minutes, with 10% sodium metabisulfite solution washing once, once, use anhydrous magnesium sulfate drying at last successively with saturated sodium bicarbonate solution washing three times, the water washing of usefulness salt.Mixture filters with silicagel column, removes under reduced pressure and desolvates, and obtains the yellow crude product of 8.0g.Handle this crude product with middle pressure chromatogram (heptane: ethyl acetate, 1: 1), obtain the title compound of 4.2g (productive rate is 27%), this compound is a yellow solid, 98～100 ℃ of fusings.
The preparation of embodiment 155-two phenenyl phosphinyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole
According to the step of embodiment 14, use 5-chloro-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole as initial benzotriazole intermediate, just can prepare title compound.
Embodiment 16～26
According to the basic step of embodiment 1, can prepare following suc as formula other 2H-benzotriazole cpd shown in the I '.
Embodiment G2 E1 E2
16 CF3 Phenyl Uncle's octyl group
17 CF3 α-cumyl The tertiary butyl
18 CN α-cumyl Uncle's octyl group
19 CN α-cumyl Nonyl
20 CN α-cumyl The tertiary butyl
21 COOCH3 α-cumyl Dodecyl
22 F Phenyl Uncle's octyl group
23 CF3 α-cumyl Nonyl
24 CF3 α-cumyl Dodecyl
25 CON(Bu)2 α-cumyl Uncle's octyl group
26 COOCH3 Phenyl Uncle's octyl group
The preparation of embodiment 275-octyl group sulphur-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole
According to the step of embodiment 6, use 5-chloro-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole and octyl mercaptan just can prepare title compound
The preparation of embodiment 285-octyl group sulphonyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole
5-octyl group sulphur-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl phenyl)-2H-benzotriazole of preparation in embodiment 27 without the purifying of sulfo-intermediate, uses general method as described in example 7 above to be oxidized to sulfone.
The preparation of embodiment 295-chloro-2-(2, the 4-dihydroxy phenyl)-2H-benzotriazole
According to the basic step of part a and b among the embodiment 1, just can prepare the monoazo intermediate of 34.7g title compound by 4-chloro-2-nitro-aniline of 17.3g, this intermediate is the wet cake of scarlet monoazo adducts.The reduction of monoazo adducts
The mixture heating up to 30 of the wet cake of the monoazo adducts that 20g sodium hydroxide, 500ml water and 26.3g are prepared above ℃, in 2 hour time, added the 33.0g zinc powder, in 1 hour time, dripped 180g 40% sodium hydroxide solution then, mixture stirred 96 hours at ambient temperature, residual zinc powder removes by filter, and with aqueous solution pH5～6 that neutralize, the slurry of gained filters, the filter cake water of gained carefully washs, and drying obtains the 22.5g crude product then.This crude product obtains the 9.6g title compound through acetone Soxhlet extraction.
The preparation of embodiment 305-chloro-2-(2-hydroxyl-4-octyloxyphenyl)-2H-benzotriazole
5-chloro-2-(2,4-two-hydroxyl-phenyl)-2H-benzotriazole of 6.5g, the 1-bromo-octane of 7.1g, the Anhydrous potassium carbonate of 5.2g and the mixture heating up of 100ml acetone were refluxed 24 hours.In the mixture of gained, add water and the ethyl acetate of 100ml, isolate the crude product of 10.6g, use sherwood oil as eluent, obtain the title compound of 0.9g with the column chromatography purifying, the structure usefulness H nucleus magnetic resonance and the mass spectrum of this compound are definite.
The preparation of embodiment 315-trifluoromethyl-2-(2,4-dihydroxyl-phenyl)-2H-benzotriazole
According to the basic step of embodiment 29, just can obtain the title compound of 6.4g with 4-amino-3-nitro of 10.3g-phenylfluoroform reaction, the structure of title compound is definite by the H nucleus magnetic resonance.
The preparation of embodiment 325-trifluoromethyl-2-(2-hydroxyl-4-octyloxyphenyl)-2H-benzotriazole
According to the basic step of embodiment 30, use 5-trifluoromethyl-2-(2,4-dihydroxyl-phenyl)-2H-benzotriazole reaction of 5.6g just can obtain title compound.Crude product column chromatography purifying obtains the title compound of 1.1g, and this compound is a white solid, and it is 79～81 ℃ of fusings.The structure of this compound is determined with H nucleus magnetic resonance and mass spectrum.
Embodiment 335-trifluoromethyl-2-[2-hydroxyl-4-(3-butoxy-2-hydroxyl propoxy-)-phenyl]-preparation of 2H-benzotriazole
Under nitrogen environment, 5-trifluoromethyl-2-(2,4-dihydroxyl-phenyl)-2H-benzotriazole that 2.3g is prepared in embodiment 31, the butyl glycidyl base ether of 1.3ml and 100mg be dissolved in that ethyl triphenyl phosphonium bromide in the 50ml dimethylbenzene forms mixture heating up refluxed 14 hours.Add 25ml water and 25ml ethyl acetate again, thereby isolate the crude product of 3g.Obtain the title compound of 2.1g with the heptane recrystallization, the structure of this compound is determined with nucleus magnetic resonance.
The preparation of embodiment 345-trifluoromethyl-2-(2-hydroxyl-4-aminophenyl)-2H-benzotriazole
According to the basic step of embodiment 1 and embodiment 29, just can prepare title compound with 4-amino-3-nitro-phenylfluoroform and 3-amino-phenol.The structure of this product is determined with nucleus magnetic resonance.
Embodiment 355-trifluoromethyl-2-[2-hydroxyl-4-(2-ethyl-hexanamido) phenyl]-preparation of 2H-benzotriazole
Be dissolved in the mixture of the triethylamine composition in the 75ml toluene at the 5-of 4g trifluoromethyl-2-(2-hydroxyl-4-amino-phenyl)-2H-benzotriazole and 1.4g, drip the 2-ethyl-caproyl chloride that is dissolved in the 125ml toluene.The mixture that obtains with the 100ml treatment reaction then, the crude product that is generated comes purifying with column chromatography, obtains the title compound of 1.9g, and this compound is 179～181 ℃ of fusings, and its structure is determined with nucleus magnetic resonance.
A) 4-amino-3-nitro-benzoic the esterification of preparation of embodiment 365-methoxycarbonyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl group-phenyl)-2H-benzotriazole
In a there-necked flask that churned mechanically 2L is housed, add 700ml methyl alcohol, 20g dimethylbenzene, the 14g vitriol oil and 100g 4-amino-3-nitro-phenylformic acid.With this mixture solution reflux 33 hours, mixture is cooled to 35 ℃ then, and is neutralized to pH7.8.Add 1L water, collect the solid that generates and use 500ml water washing, dried overnight to obtain 4-amino-3-nitro-methyl benzoate of 100.9g.B) diazotization of 4-amino-3-nitro-methyl benzoate
The sulfuric acid that adds 177g 96% in the churned mechanically there-necked flask of being equipped with of a 1L slowly added the 11g Sodium Nitrite then in 90 minutes.With mixture heating up to 30 ℃ initiation reaction.Temperature remains below 70 ℃, mixture is cooled to 15 ℃ then, added 30g 4-amino-3-nitro-methyl benzoate and make temperature remain on 15～20 ℃ in 2 hours.Mixture is cooled to 0 ℃, adds 200g ice and make solution be suitable for linked reaction to form Monoazo compound.C) monoazo adducts
In the there-necked flask of a 2L that mechanical stirrer and filling tube be housed, add 52g 2-α-cumyl-4-tert-octyl phenol, 20g water, 315g methyl alcohol, 7g dimethylbenzene and 150g sodium hydroxide.Mixture is cooled to-5 ℃, in 2 hour time, is added in the diazonium salt solution for preparing among the step b while cooling off, keep temperature to be lower than 3 ℃.After diazonium salt solution adds, the pH value is adjusted to 6.5～7.0, then mixture is poured in the 500ml dimethylbenzene.Under 60 ℃ of conditions, it is washed three times with 500ml water.Remove removal xylene by distillation, obtain the monoazo adducts that 186g contains residual dimethylbenzene.D) reduction of monoazo adducts
Be equipped with at 500ml and add 2 of monoazo adducts, 125g2-butanols and 1.7g that 186g prepares, 3-two chloro-1,4-naphthoquinones in the flask of mechanical stirrer in step c.With mixture heating up to 90 ℃, then resulting reaction soln is poured in another flask by filling tube.In said second flask, add 175g2-butanols and 18.6g sodium hydroxide, flask is heated to 95 ℃ then, in 2 hours time, add monoazo solution, boil off methyl ethyl ketone and 2-butanols simultaneously.Add the 100g2-butanols, boil off azeotrope.With the mixture cooling, add 300g dimethylbenzene and 200ml water then.Sulfuric acid with 20% adjusts to 7～7.5 with the pH value.Under 60 ℃ of conditions, isolate water, twice of 200ml water washing of organic phase.Remove removal xylene by distillation, the residue that is generated crystallization in methyl alcohol, thus obtaining the 8.8g title compound, this compound is 141～143 ℃ of fusings.
Embodiment 375-[N, N-di-n-butyl-formamyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl group)-phenyl]-a) saponification of 5-methoxycarbonyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl group-phenyl)-2H-benzotriazole of preparation of 2H-benzotriazole
Be equipped with in the there-necked flask of mechanical stirrer, thermometer, condenser and nitrogen inlet at a 250ml, add 1.8g potassium hydroxide and 40ml methyl alcohol.With mixture heating up to 40 ℃ with the dissolved hydrogen potassium oxide.In solution, add again 2.7g be dissolved in the 40ml methyl alcohol in embodiment 36 preparation 5-methoxycarbonyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl group-phenyl)-2H-benzotriazole.With reaction mixture refluxed 6 hours.Cooling mixture is used the spirit of salt acidifying then.Add ether and ethyl acetate, isolate organic phase, through anhydrous sodium sulfate drying.After vacuum is sloughed solvent, isolate 2.5g5-carboxyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl group-phenyl)-2H-benzotriazole.B) 5-chloroformyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl group-phenyl)-2H-benzotriazole
5-carboxyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl group-phenyl)-2H-benzotriazole that 2.5g is prepared in step a adds in the flask that agitator, thermometer, reflux exchanger, Dean-stark water trap and nitrogen inlet are housed of a 250ml.Add 100ml toluene, the backflow mixture is to remove minor amount of water.Cooling mixture adds 0.76g then and is dissolved in oxalyl chloride in the 15ml toluene, and reaction mixture slowly is heated to 60 ℃, keeps 8 hours up to discharging all hydrogenchloride at 60～65 ℃, thereby obtains the acid chloride of title compound.C) 5-[N, N-di-n-butyl-formamyl-2-(2-hydroxy-3-alpha-cumyl--uncle's 5-octyl group)-phenyl]-the 2H-benzotriazole
In being equipped with the flask of mechanical stirrer, drying tube, thermometer and dropping funnel, a 500ml adds 0.8g Di-n-Butyl Amine, 6ml pyridine and 25ml toluene.Mixture is cooled to 0 ℃.The acid chloride solution that will prepare in step b places in the dropping funnel then, in-5～10 ℃ temperature range, join in the reaction mixture in 30 minutes time.Under this temperature, reaction mixture was stirred 1.5 hours, then standing over night at ambient temperature.Filtering and mixing thing and vacuum extraction obtain the thick product solid of 3.0g.Thick solid phase prod obtains the 1.2g title compound through chromatogram purification, and this compound is a brown solid, 131～133 ℃ of fusings.The structure of this compound proves through nucleus magnetic resonance and mass spectrum m/z596.
Embodiment 385-trifluoromethyl-2-(2-hydroxyl-uncle's 5-octyl group-phenyl)-2H-benzotriazole
According to the basic step of embodiment 1, utilize 4-amino-3-nitro-phenylfluoroform and uncle's 4-octyl group-phenol reactant, purifying just can prepare title compound on silica gel chromatography then.Products therefrom just can prepare title compound through heptane or recrystallizing methanol, and this compound almost is a white solid, and it is 80～81 ℃ of fusings.Application Example 39
Various for determining by of the effect of the 2H-benzotriazole UV absorbers of electron-withdrawing group and electron donating group-substituted to the thermostability and the loss speed of high solid thermosetting acrylic coating, carried out following experiment.
By with a kind of experiment with many alcohol resins of vinylformic acid and hexamethoxy methyl cyanuramide (Resimene 747, Monsanto) mix by solids ratio 60/40, make high solid thermoset acrylics Clear paint.The dodecylbenzene sulfonic acid catalyst that adds 0.70wt%, the glidant Modaflow of adding 0.25wt% (Monsanto) to form a kind of typical acrylic melamine resin system.
With dimethylbenzene the viscosity drop of Clear coating sample was low to moderate 26～27 seconds that use the Zahn#2 cup, and by conventional air-atomizing method, spray pressure is 50psi (3.5kg/cm2), is applied in 1 " * 3 " (on the quartzy slide glass of 2.54cm * 7.62cm).At 260 (127 ℃) baking slide glass 30 minutes to be cured, with two (1-octyloxy-2,2,6, the 6-tetramethyl piperidine-4-yl) ester (TINUVIN of 1wt% hindered amine as light stabilizer sebacic acid 123, Ciba-Geigy) stable transparent coating.With 5mmol% weight various test benzotriazole UV absorbers are added Clear coating.Thickness is 1.15～1.41 mils (0.029～0.036mm) on the slide glass.
With the 6500w controlled radiation rete on the quartzy slide glass is worn out in Xenon Arc Weather-Ometer instrument by following condition, and quartzy and outer borate S type filter in using.Radiation period is as follows: do not carry out 40 minutes direct radiations of water spray, 20 minutes illumination subsequently and preceding spraying, the out-of-the-way light of 60 minutes optical radiation subsequently and 60 minutes subsequently and tail spraying (condensation).At 340nm, 1.98KJ/h, 0.55W/M 2The following placement.Be controlled at 70 ± 2 ℃ in periodicity of illumination black panel temperature.The relative humidity of periodicity of illumination is 50～55%, out-of-the-way photoperiodic be 100%.Absorbancy as the long wave UV of xenon arc digestion time function band is recorded in the following table.
In order to follow the tracks of the loss of UV absorption agent in the Clear coating, measure begin and at interval aging of certain hour after the UV spectrum.Use the reference beam decay technique, the upper limit of UV spectrophotometer linear measurement absorbancy reaches 5.5 absorbance units.
The degradation products of UV absorption agent is to the not contribution of UV spectrum.This can be by following the tracks of in the absorbancy of about 300nm band and recently detecting of the absorbancy of being with at about 340nm, should be when aged samples than not changing, the UV spectrum of the aging film of this explanation also is very little corresponding to the amount of UV absorption agent residual in the film even light degradation product has spectrographic contribution.
Data in following table be based on contain expose 1211 hours suc as formula the Clear paint of the test benzotriazole UV absorbers shown in the A after resulting data.
Compound Unit absorbancy loss G 2 R 1 R 2
A 1.7982 Hydrogen -PO(OEt) 2 Uncle's octyl group
B 1.6300 Hydrogen Nitro Uncle's octyl group
C 1.4863 Phenyl-S- The tertiary butyl -CH 2-CH 2COOC 8H 17
D 1.4002 Hydrogen Hydrogen -CH 2-CH 2COOCH 3
E 1.1872 Methoxyl group The tertiary butyl Methyl
F 0.5259 Hydrogen The tertiary butyl -CH 2-CH 2COOCH 3
G 0.4527 Hydrogen Hydrogen α-cumyl
H 0.4420 Hydrogen The tertiary butyl -CH 2-CH 2-COOC 8H 17
I 0.4299 Hydrogen Uncle's octyl group α-cumyl
J 0.4134 Hydrogen Hydrogen Uncle's octyl group
K 0.3777 Hydrogen Uncle's octyl group Uncle's octyl group
L 0.3712 Hydrogen The tertiary butyl -CH 2CH 2CH 2OH
M 0.3433 Hydrogen α-cumyl CH 2-CH 2COOCH 3
N 0.3098 Cyano group The tertiary butyl The tertiary butyl
O 0.2689 Phenyl-SO 2- The tertiary butyl -CH 2-CH 2COOC 8H 17
P 0.2576 Hydrogen α-cumyl α-cumyl
Q 0.2492 Hydrogen α-cumyl Uncle's octyl group
Just can obtain some about the photostabilization of 2H-benzotriazole UV absorbers and the tangible conclusion of the sunproof replacement character of influence by observing these data.
Work as R 1When being α-cumyl or phenyl and G 2When being electron-withdrawing group such as benzenesulfonyl or cyano group, can increase photostabilization.
R 2The character of group is little to the light stability influence of benzotriazole UV absorbers.
From these are observed, can design ideal benzotriazole UV absorbers, wherein G in theory 2Be an electron-withdrawing group, R 1Be an effective macoradical, R 2It is a heat-staple part.Such ideal benzotriazole cpd can be: G 2Be benzenesulfonyl, R 1Be α-cumyl and R 2It is uncle's octyl group.This benzotriazole is in U.S. Patent No. 5,280, and is briefly claimed in 124.Data acknowledgement in following examples 40 this prediction, and this " ideal " compound shows low-down loss speed really, its loss speed is starkly lower than the present loss speed in this area.
Embodiment 40
Basic step according to embodiment 39, a series of other experimental compounds are made into high solid thermoset acrylics melamine resin, its concentration is 1.93～3wt%, makes the experiment benzotriazole have identical volumetric molar concentration and make that initial absorbancy is about 2.0 absorbance units when identical thickness.
Experiment plate is with X180 cycle (0.45W/M 2) be exposed in the Xenon-Arc Weather-Ometer instrument, the absorbancy at initial stage was measured once every about 250 hours in preceding 2000 hours, measured once every 500 hours thereafter.Each Clear paint all contains the hindered amine as light stabilizer of 1wt%, two (1-octyloxy-2,2,6, the 6-tetramethyl piperidine-4-yl) esters of sebacic acid.
Data in following table be based on contain expose 1253 hours suc as formula the Clear paint of the test benzotriazole UV absorbers shown in the A after resulting data.
Compound Unit absorbancy loss G 2 R 1 R 2
R 0.2424 Hydrogen Phenyl α-cumyl
Q 0.2351 Hydrogen α-cumyl Uncle's octyl group
S 0.1271 CF3 α-cumyl Uncle's octyl group
T 0.1827 Phenyl-SO 2 The tertiary butyl The tertiary butyl
Data in following table be based on contain expose 1489 hours suc as formula the Clear paint of the test benzotriazole UV absorbers shown in the A after resulting data.
Compound Unit absorbancy loss G 2 R 1 R 2
R 0.3724 Hydrogen Phenyl α-cumyl
Q 0.287 Hydrogen α-cumyl Uncle's octyl group
S 0.1547 CF 3 α-cumyl Uncle's octyl group
T 0.2654 Phenyl-SO 2 The tertiary butyl The tertiary butyl
Data in following table be based on contain expose 2521 hours suc as formula the Clear paint of the test benzotriazole UV absorbers shown in the A after resulting data.
Compound Unit absorbancy loss G 2 R 1 R 2
R 0.4824 Hydrogen Phenyl α-cumyl
Q 0.4054 Hydrogen α-cumyl Uncle's octyl group
S 0.2192 CF 3 α-cumyl Uncle's octyl group
T 0.3570 Phenyl-SO 2 The tertiary butyl The tertiary butyl
Can know from above 3 tables and to see that the compound S of electron-withdrawing group is arranged in the 5-position of benzo ring, and especially T is more durable than the benzotriazole that does not have this group on the benzo ring significantly.
Data in the following table be based on contain expose 1264 hours suc as formula the Clear paint of the test benzotriazole UV absorbers shown in the A after resulting data.
Compound Unit absorbancy loss G 2 R 1 R 2
Q 0.2293 Hydrogen α-cumyl Uncle's octyl group
S 0.0921 CF 3 α-cumyl Uncle's octyl group
T 0.1965 Phenyl-SO 2 The tertiary butyl The tertiary butyl
U 0.0944 Phenyl-SO 2 α-cumyl Uncle's octyl group
V 0.1719 Chlorine α-cumyl Uncle's octyl group
W 0.1655 Fluorine α-cumyl Uncle's octyl group
X 0.1796 Hydrogen Phenyl Uncle's octyl group
Data in the following table be based on contain expose 1518 hours suc as formula the Clear paint of the test benzotriazole UV absorbers shown in the A after resulting data.
Compound Unit absorbancy loss G 2 R 1 R 2
Q 0.2662 Hydrogen α-cumyl Uncle's octyl group
S 0.1116 CF 3 α-cumyl Uncle's octyl group
T 0.2423 Phenyl-SO 2 The tertiary butyl The tertiary butyl
U 0.1114 Phenyl-SO 2 α-cumyl Uncle's octyl group
V 0.1955 Chlorine α-cumyl Uncle's octyl group
W 0.1668 Fluorine α-cumyl Uncle's octyl group
X 0.2220 Hydrogen Phenyl Uncle's octyl group
Data in these tables clearly illustrate that, by electron-withdrawing group, especially the benzotriazole that replaces of trifluoromethyl or phenyl-alkylsulfonyl is especially had a weather resistance on the benzo ring, and the low rate of loss absorbance after this exposes by actinic radiation is measured.Compound S, U, V and W are especially had a weather resistance, and are fit to above-mentioned pattern.Really, the especially competent prediction of compound U is by above data acknowledgement.The data of compound T and U show at R 1The position has effective macoradical such as α-cumyl is compared with the simple alkyl such as the tertiary butyl are arranged at this, has increased beneficial effect.

Claims (12)

1. a coating composition makes said composition stable with benzotriazole, after this benzotriazole adds said coating, embodies enhanced weather resistance and low rate of loss, and said composition contains:
(a) a kind of resin, this resin are selected from thermoset acrylics melamine resin or vinylformic acid urethane resin,
(b) structural formula that accounts for resin solid weight 0.01 to 5% is a kind of benzotriazole of A ',
Figure C9712242200021
In the formula
G 2Be fluorine, chlorine, cyano group, R 3SO 2-, CF 3-,-CO-G 3,-COO-G 3Or-CO-N (G 3) 2
G 3For the alkyl of 1 to 12 carbon atom is arranged,
R 1Be hydrogen, the alkyl of 1 to 12 carbon atom is arranged, phenyl has the benzene alkyl of 7 to 15 carbon atoms, or the said phenyl or the said benzene alkyl that are replaced by 1 or 2 alkyl that 1 to 4 carbon atom arranged on phenyl ring,
R 2Be the alkyl that 1 to 12 carbon atom is arranged, phenyl has the benzene alkyl of 7 to 15 carbon atoms, or-CH 2CH 2COOG 4, G wherein 4Be hydrogen, the alkyl of 1 to 24 carbon atom is arranged, or the said alkyl that is replaced by OH, the said alkyl by 1 to 6-O-atomic separation was perhaps both replaced by OH, again by the said alkyl of 1 to 6-O-atomic separation,
R 3Be the alkyl that 1 to 18 carbon atom is arranged, the aryl of 6 to 10 carbon atoms is arranged, or by 1 or 2 said aryl that the alkyl replacement of 1 to 4 carbon atom is arranged,
When coating is exposed under the actinic rays, this benzotriazole shows enhanced weather resistance and low rate of loss, promptly 1200 hours loss amounts of irradiation are lower than 0.22 absorbance unit under Xenon-Arc Weather-Ometer, shine 1500 hours loss amounts and be lower than 0.27 absorbance unit, shine 2500 hours loss amounts and be lower than 0.40 absorbance unit.
2. according to the composition of claim 1, wherein structural formula is in the compound of A ',
G 2Be fluorine, chlorine, cyano group, R 3SO 2-, CF 3-,-COO-G 3Or-CO-N (G 3) 2
G 3For the alkyl of 1 to 8 carbon atom is arranged,
R 1Be hydrogen, phenyl or α-cumyl,
R 2Be the alkyl or phenyl that 4 to 12 carbon atoms are arranged,
R 3Be phenyl or the alkyl that 8 to 12 carbon atoms are arranged.
3. according to the composition of claim 2, G wherein 2Be phenyl-SO 2-, octyl group-SO 2-, fluorine or CF 3-, R 1Be α-cumyl or phenyl, R 2Be the tertiary butyl or uncle's octyl group.
4. according to the composition of claim 1, it comprises the phenolic antioxidant of stable quantity in addition, is selected from:
3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid Octadecane ester, four (3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid) neopentane four esters, 3, the two Octadecane esters of 5-di-t-butyl-4-hydroxyl-benzylphosphonic acid, 1,3,5-three (3,5-di-t-butyl-4-hydroxyl-benzyl) isocyanuric acid ester, two (3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid) sulphur diethyl ester, 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl-benzyl) benzene, two (3-methyl-5-tertiary butyl-4-hydroxy phenylpropionic acid) (3,6-two oxa-s eight methylene radical) ester, 2,6-di-t-butyl-p-cresol, 2,2 '-ethylidene-two (4, the 6-di-tert-butylphenol), 1,3,5-three (2,6-dimethyl-4-the tertiary butyl-3-hydroxyl-benzyl) isocyanuric acid ester, 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-hydrocinnamamide oxygen) ethyl] isocyanuric acid ester, 3,5-two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) rice phenol, two (3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid) hexa-methylene ester, 1-(3,5-di-t-butyl-4-hydroxyl-anilino)-3,5-two hot sulfenyl-s-triazines, N, N '-hexa-methylene-two (3,5-di-t-butyl-4-hydroxyl-hydrocinnamamide), two (3,5-di-t-butyl-4-hydroxyl-benzylphosphonic acid ethyl ester) calcium, two [3,3-two (3-tert-butyl-hydroxy phenyl) butyric acid diethyl ester, 3,5-di-t-butyl-4-hydroxyl-dibenzylsulfide guanidine-acetic 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)-ethyl]-oxamide.
5. according to the composition of claim 4, wherein phenolic antioxidant is four (3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid) neopentane four esters, 3,5-di-t-butyl-4-hydroxyl-phenylpropionic acid Octadecane ester, 1,3,5-trimethylammonium-2,4,6-three (3,5-di-t-butyl-4-hydroxyl-benzyl) benzene, 1,3,5-three (3,5-di-t-butyl-4-hydroxyl-benzyl) isocyanuric acid ester, 2,6-di-t-butyl-p-cresol, 2,2 '-ethylidene-two (4, the 6-di-tert-butylphenol).
6. according to the composition of claim 1, it comprises the hindered amine of effective stable quantity in addition, is selected from: sebacic acid two (2; 2,6,6-tetramethyl piperidine-4-yl) ester; sebacic acid two (1,2,2; 6,6-pentamethyl-piperidin-4-yl) ester, (3; 5-di-t-butyl-4-hydroxyl-benzyl) butyl malonic acid two (1,2,2; 6,6-pentamethyl-piperidin-4-yl) ester, 4-benzoyl-2; 2,6, the 6-tetramethyl piperidine; 4-stearoyl-oxy-2,2,6; 6-tetramethyl--piperidines, 3-n-octyl-7,7; 9,9-tetramethyl--1,3; 8-three azepines-spiral shell [4.5] decane-2,4-diketone, nitrilotriacetic acid(NTA) three (2; 2,6,6-tetramethyl piperidine-4-yl) ester; 1,2-two (2,2; 6,6-tetramethyl--3-Oxypertine-4-yl) ethane, 2; 2,4,4-tetramethyl--7-oxa--3; 20-diaza-21-oxygen two spiral shells [5.1.11.2] heneicosane, 2, the hot amino of 4-two chloro-uncles 6--s-triazine and 4; 4 '-hexa-methylene two (amino-2,2,6; 6-tetramethyl--piperidines) polycondensation product, 1-(2-hydroxyethyl)-2,2; 6, the polycondensation product of 6-tetramethyl--4-hydroxy-piperdine and Succinic Acid, 4; 4 '-hexa-methylene two-(amino-2,2,6; the 6-tetramethyl piperidine) and the polycondensation product of glycol dibromide, 1; 2,3,4-butanetetra-carboxylic acid four (2; 2,6,6-tetramethyl piperidine-4-yl) ester; 1,2,3; 4-butanetetra-carboxylic acid four (1,2,2; 6,6-pentamethyl-piperidin-4-yl) ester, 2; 4-two chloro-6-morpholino-s-triazines and 4,4 '-hexa-methylene two-(amino-2,2; 6,6-tetramethyl piperidine) polycondensation product, N; N ', N ", N -four [(4; two (butyl-1,2,2; 6, the 6-pentamethyl-piperidin-4-yl)-amino-s-triazine-2-yls of 6-]-1,10-diamino-4; 7-diaza decane, blended 1,2; 3,4-butanetetra-carboxylic acid [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] ester; blended 1,2,3; 4-butanetetra-carboxylic acid [1; 2,2,6; 6-pentamethyl-piperidin-4-yl/β; β, β ', β '-tetramethyl--3; 9-(2; 4,8,10-four oxaspiros [5.5]-undecane) diethyl] ester; two (2; 2,6,6-tetramethyl piperidine-4-carboxylic acid) eight methylene radical esters; 4; 4 '-ethylene two (2,2,6; 6-tetramethyl-piperazine-3-ketone); N-2,2,6; 6-tetramethyl piperidine-4-base-dodecyl Succinic Acid imide; N-1,2,2; 6; 6-pentamethyl-piperidin-4-yl-dodecyl Succinic Acid imide, N-1-ethanoyl-2,2; 6; 6-tetramethyl piperidine-4-base-dodecyl-Succinic Acid imide, 1-ethanoyl-3-dodecyl-7,7; 9; 9-tetramethyl--1,3,8-thriazaspiro [4.5] decane-2; the 4-diketone; sebacic acid two (1-octyloxy-2,2,6; 6-tetramethyl piperidine-4-yl) ester; Succinic Acid two (1-cyclohexyloxy-2,2,6; 6-tetramethyl piperidine-4-yl) ester; 1-octyloxy-2,2,6; 6-tetramethyl--4-hydroxy-piperdine; poly-{ [the hot amino of uncle 6--s-triazine-2,4-two bases] [2-(1-cyclohexyloxy-2,2; 6; 6-tetramethyl piperidine-4-yl) imino--hexa-methylene-[4-(1-cyclohexyloxy-2,2,6; 6-tetramethyl piperidine-4-yl) imino-] }
With 2,4,6-three [N-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl)-normal-butyl amino]-s-triazine.
7. according to the composition of claim 6, wherein hindered amine compound is a sebacic acid two (2,2,6,6-tetramethyl piperidine-4-yl) ester, sebacic acid two (1,2,2,6,6-pentamethyl-piperidin-4-yl) ester, (3,5-di-t-butyl-4-hydroxyl-benzyl) butyl malonic acid two (1,2,2,6,6-pentamethyl-piperidin-4-yl) ester, 1-(2-hydroxyethyl)-2,2,6, the polycondensation product of 6-tetramethyl--4-hydroxy-piperdine and Succinic Acid, 2, the hot amino of 4-two chloro-uncles 6--s-triazine and 4,4 '-hexa-methylene two (amino-2,2,6,6-tetramethyl--piperidines) polycondensation product, N, N ', N ", N -four [(4; two (butyl-1,2,2; 6,6-pentamethyl-the piperidin-4-yl)-amino of 6-)-s-triazine-2-yl]-1,10-diamino-4; 7-diaza decane, sebacic acid two (1-hot amino-2,2; 6,6-tetramethyl piperidine-4-yl) ester, two (1-cyclohexyloxy-2; 2,6, the 6-tetramethyl piperidine-4-yl) esters of Succinic Acid, 1-octyloxy-2,2,6,6-tetramethyl--4-hydroxy-piperdine, poly-{ [the hot amino of uncle 6--s-triazine-2,4-two bases] [2-(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidine-4-yl) imino--hexa-methylene-[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)-normal-butyl amino]-the s-triazine.
8. according to the composition of claim 1, it contains another kind of UV absorption agent in addition, and it is selected from s-triazine, N, N '-oxalyl pentanoic, hydroxy benzophenone, benzoic ether and α-Qing Jibingxisuanzhi.
9. according to the composition of claim 10, wherein composition also has the s-triazine in addition, and it is 2, two (2,4-dimethyl-phenyl)-6-of 4-(the hot oxygen phenyl of 2-hydroxyl-4-)-s-triazine; 2,4-phenylbenzene-6-(the own oxygen phenyl of 2-hydroxyl-4-)-s-triazine; 2, two (2,4-dimethyl-phenyl)-6-[2-hydroxyl-4-(the 3-dodecane oxygen/tridecane oxygen-2-hydroxyl third oxygen) phenyl of 4-]-the s-triazine; Or 2-(2-hydroxyl ethylamino)-4, two [N-butyl-N-(1-hexamethylene oxygen-2,2,6,6-tetramethyl piperidine-4-yl) amino]-s-triazines of 6-.
10. compound that structural formula is I ' In the formula
G 2Be cyano group, E 3SO 2-, CF 3-,-COO-G 3-CO-NHG 3Or-CO-N (G 3) 2
G 3For the alkyl of 1 to 12 carbon atom is arranged,
E 1Be hydrogen, phenyl has the benzene alkyl of 7 to 15 carbon atoms, or the said phenyl or the said benzene alkyl that are replaced by 1 or 2 alkyl that 1 to 4 carbon atom arranged on phenyl ring,
E 2Be the alkyl that 1 to 12 carbon atom is arranged, phenyl has the benzene alkyl of 7 to 15 carbon atoms, or-CH 2CH 2COOG 4, G wherein 4Be hydrogen, the alkyl of 1 to 24 carbon atom is arranged, by the said alkyl that OH replaces, the said alkyl by 1 to 6-O-atomic separation was perhaps both replaced by OH, again by the said alkyl of 1 to 6-O-atomic separation,
E 3Be the alkyl that 8 to 18 carbon atoms are arranged, the aryl of 6 to 10 carbon atoms is arranged, or by 1 or 2 said aryl that the alkyl replacement of 1 to 4 carbon atom is arranged, condition is to work as G 2Be E 3SO-or E 3SO 2-time, E 1It or not the benzene alkyl.
11. according to the compound of claim 10, wherein G 2Be cyano group, E 3SO 2-, CF 3-,-CO-G 3Or-CO-N (G 3) 2,
G 3For the alkyl of 1 to 8 carbon atom is arranged,
E 1Be hydrogen, phenyl or α-cumyl,
E 2Be the alkyl that 4 to 12 carbon atoms are arranged,
E 3Be phenyl or octyl group, condition is to work as G 2Be E 3SO 2-time, E 1It or not α-cumyl.
12. according to the compound of claim 11, wherein G 2Be CF 3-, E 1Be α-cumyl, E 2Be the tertiary butyl or uncle's octyl group.
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