GB2247021A - Mono-, bi- or tri-carbocyclic phosphinic or phosphonic acid compounds - Google Patents

Mono-, bi- or tri-carbocyclic phosphinic or phosphonic acid compounds Download PDF

Info

Publication number
GB2247021A
GB2247021A GB9116822A GB9116822A GB2247021A GB 2247021 A GB2247021 A GB 2247021A GB 9116822 A GB9116822 A GB 9116822A GB 9116822 A GB9116822 A GB 9116822A GB 2247021 A GB2247021 A GB 2247021A
Authority
GB
United Kingdom
Prior art keywords
groups
group
mono
compound according
4alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB9116822A
Other versions
GB2247021B (en
GB9116822D0 (en
Inventor
Bansi Lal Kaul
Angelos-Elie Vougioukas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sandoz AG
Original Assignee
Sandoz AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sandoz AG filed Critical Sandoz AG
Publication of GB9116822D0 publication Critical patent/GB9116822D0/en
Publication of GB2247021A publication Critical patent/GB2247021A/en
Application granted granted Critical
Publication of GB2247021B publication Critical patent/GB2247021B/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
    • C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D211/56—Nitrogen atoms
    • C07D211/58—Nitrogen atoms attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3834—Aromatic acids (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
    • C07F9/4808—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the acid moiety containing a substituent or structure which is considered as characteristic
    • C07F9/4841—Aromatic acids or derivatives (P-C aromatic linkage)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6521—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Hydrogenated Pyridines (AREA)

Abstract

A mono-, bi- or tri carbocyclic phosphinic or phosphonic acid compound containing i) at least one group that is reactive to hydroxy and amino and/or ii) at least one group containing a sterically hindered amino, are useful for improving the dyeability of plastics materials. The compounds may be salts of aryl phosphinic or phosphonic acids in which the groups i) and/or ii) are present in the counter cation or the compounds may be aryl phosphinic or phosphonic acids in which groups i) and/or ii) are present in substituents on the aryl moiety.

Description

1 MONO-, BI- OR TRI-CARBOCYCLIC PHOSPHINIC OR PHOSPHONIC ACID COMPOUNDS
According to the invention there is provided a mono-, bi- or tricarbocyclic phosphinic or phosphonic acid compound containing i) at least one group that is reactive to hydroxy and/or amino and/or ii) at least one group containing a sterically hindered amine.
Preferably the group reactive to hydroxy and amino and the sterically hindered amine are connected to each other through a nitrogen or an oxygen atom or by ester, amide or salt grouping.
Preferably the mono-, bi- or tri- carbocyclic phosphinic and phosphonic acids according to the invention are those containing i) one group reactive to hydroxy and/or amino and ii) at least one, preferably two, sterically hindered amine groups.
Preferred mono-, bi- or tri- carbocyclic groups are C5-7cycloalkyl, (preferably cyclohexyl), phenyl-, naphthyl-, tetrahydronaphthyl-, acenaphthene- or acenaphthylene- groups. More preferably the carbocyclic group is a monocyclic group unsubstituted or mono- or disubstituted by non-water solubilizing substituents selected from halogen (especially chloro or bromo), hydroxyl, C1-4alkyl (e.g. tertiary butyl), phenyl-, C14alkoxy and/or Cl-4alkoxycarbonyl groups. Preferably the mono-, bi- or tri carbocyclic groups are unsubstituted.
Multicyclic carbocyclic groups can contain more than one phosphinic or phosphonic acid group. Preferred compounds however, contain at least one sterically hindered group per phosphinic or phosphonic acid group.
Case 153-5446 Groups that are reactive to hydroxy and/or amino groups are well known in reactive dye chemistry. Preferably these are cyclic groups bearing at least one reactive group and having at least two nitrogen atoms (that may be separated by one or two carbon atoms), for example, triazinyl, pyrimidinyl, quinoxalinyl and quinazolinyl groups as well as phthalazinyl, benzoxazolyl and benzthiazolyl groups as well as the groups of the formula -CO-(Alkyl 0Af R 30 R 30 - -C12C32-14 -COClC32 COCE=CH 2 R 30 R 3 Go- R56c.
1 R 1 R 0 \1 ".4, 1 -R 30 R -CO 30 F2C-CF2. 1 1 -CO-CH=CH-CH-CH2 -NS02-CH=CH2 1 Alkyl -CO-CH2CH2-CO2-aryl i 1 i I I 1 (i) (ii) (iii) (iv) (v) (vi) (vii) 1 i 1 1 1 1 1 i i 1 1 I i i 1 -3 -CO-C=CH2 1 13 0 -COCH=CC121 -CO-CH2-R30 -S02-CH2CH2-0-SO0a -S02-NH-CH2CH24-SO3Na -CO-CH2-N+(C1-4Alkyl)3A- -CO-CH2CH2-R30 -CO-CH-CH-CO0C1-4Alkyl 1 1 R3oR30 Case 153-5446 (viii) (ix) (X) (xi) (Xii) (Xiii) (xiv) in which R30 is a halogen atom, (preferably chlorine) or a group -NI(Cl-4alkyl)3 or -N+ A(pyridinium) and A- is an anion, for 01-/ example halide.
[Such groups are described in the article from K.G. Kleb, IlUeber neue Reaktivfarbstoffe", Angew. Chem. 76 (1964) No. 10, p. 423+ff; E. Siegel, "Chemie der Reaktivfarbstoffe", Chemica, Supplement March 1968, 3. Farbensymposium Interlaken, p. 102+ff; E. Siegel in "The Chemistry of Synthetic Dyes", Vol. VI, Chapter 1, edited by K. Venkataraman, Academic Press (1972)]. The contents of these articles are incorporated herein by reference.
More preferred groups that are reactive to hydroxy and amino are monoand di-chlorotriazinyl, mono- and di-chloro-pyrimidinyl or mono- or di-chloroquinoxalinyl, most preferably mono-chlorotriazinyl.
More preferably according to the invention there is provided compound of formula I or II i 1 1 -4 Case 153-5446 / Ra 0 1 cRS 1 -U) p 1 I P 2..00--,-(0)n -RRz RS 1 R R 3 /S R C-R G - R tz-R "I /1.1C,13 2 Z4 5 R'2 -R4 NR C-R \ R R 0 2 "1 n P: 1 OH p in which R is a mono-, bi- or tricarbocyclic group (preferably a phenyl group) unsubstituted or substituted by one or two substituents selected from the group of halogen, C1-4alkyl or C1-4alkoxy; R, is a group reactive to hydroxy and amino; R2 is the group -NR3- or -0- where R3 is hydrogen or Cl-4alkyl; R4 together with the two carbons to which the groups RO are attached and the nitrogen to which R5 is attached form a 5,-, 6- or 7-membered cyclic group, that is optionally substituted with further non-water-solubilizing substituents and/or to which a further cyclic group is attached to form a spiro group; R5 is hydrogen, Cl-4alkyl or acyl; each R8 independently is a Cl-6alkyl group, preferably methyl or ethyl, more preferably methyl; I i i 1 1 I i. 1 I I 1 1 1 i i 1 i 1 i i i 1 n is 0 or 1; p is 1, 2 or 3; and p,, is 0, 1 or 2 in which the sum of p + p,, is 1, 2 or 3.
Case 153-5446 Preferred sterically hindered amine containing groups are of the formula IRS C --R // \ 8 -R4 \\" / J -- C-R 1 8 8 - where the symbols are as defined above.
More preferred sterically hindered amine groups are of formula a) to e) below R 5 R 3 R! R ' -N If- (b) j 5 11 R 8 R 8 R 8 R 8 0 R Rcl R R= 8 R 8 R 8 R N - RS R8 R;R8 R, 9 R3 -R XR 9 R 8 R (e) ' ' (c) ' and where R51 is hydrogen, Cl-4alkyl (preferably methyl) or acyl, each R9 independently is hydrogen, Cl-4alkyl or one R9 is phenyl and the other R9 group is hydrogen or Cl-4alkyl or both groups R9 together form a group - (CH2)11-and Y is -N-CO or -CON- Case 153-5446 Preferably the groups of formulae a) to e) are attached to the rest of the molecule by an -NH- or -0- bridging group.
Preferred acyl groups are of the formula R20-Al- or R21-A2- in which R20 is a hydrocarbon group that is unsubstituted or substituted and which may also contain a heteroatom; preferably however such a group is a phenyl group or a Cl-4alkyl group; A, is a bridging group -0-CO-, -S02- or O-SO2-; R21 is hydrogen or a group R20 independently of R20; A2 is the group -CO-NR22-CO- or -NR22-SO2- whereby R22 can only be attached to a nitrogen atom and R22 is hydrogen or a group R20 independently of R2o.
More preferably, any acyl group is a -CO-Cl-4 alkyl group.
Alternatively preferred compounds according to the invention are of formula III or IV / R3 0 R2-R4 R R R 8 c \_RS R - IN R.
Pa 1 R p R Ic (111) 10 4 R /3 8 r 0 n)' on 1 r 1 V) i 1 1 i i 1 i 1 i 1 A i 1 i 1 i i 1.i : 1 1 i j! 1 l! :i! i 'i i 1 i i 1 i 1 1 in which Case 153-5446 n is 0 or 1 r and r, are independently of each other, 1, 2, or 3 p, is 1, 2, 3 or 4 p.' is 0, 1, 2 or 3 provided that the sum of p, and p.' and of r and r' is 2, 3 or 4.
R101 is an amide or ester bound phenyl group and the other symbols are as defined above.
Preferred phosphinic and phosphonic acid groups are also those derived from compounds of formula V 0 H (0) P-- j R --_P- (0) H 0 10,' n 6H OH (V) in which R10,, is a direct bond, oxygen, Cl-4alkylene or -CH=CH- Compounds according to the invention can be prepared from known compounds by known methods, for example by: a) condensing an appropriate amount of a compound containing one or more groups capable of reacting with hydroxy and/or amino with an appropriate amount of a mono-, bi- or tricarbocyclic, amino or hydroxy group containing phosphinic or phosphonic acid or b) reacting an appropriate amount of a mono-, bi- or tri-carbocyclic phosphinic or phosphonic acid with an appropriate amount of a sterically hindered amine containing compound, which latter compound may contain one or more groups capable of reacting with hydroxy and/or amino groups.
Such appropriate amounts are clear to a person skilled in the art.
Case 153-5446 Preferably, in a process for the preparation of a compound of formula I one mole of a compound of formula I, fk, -R4 Wi p p a is reacted with p moles of a phosphinic or phosphonic acid of formula ill 0 11 HO-P-R 1 (0) n -R ts G") Preferably a compound of formula II is prepared by condensing one mole of a compound containing p + p. + optionally 1 (if the final compound should contain a group reactive to hydroxy and amino) reactive groups with p moles of a compound of formula M 0 H R2 and with p,, moles of a compound of formula W1 R. /3 C-R -, 8.
- II-R 11 R ', 5 11 R2- 8 - R a 1 i i 1 1 i i 1 1 1 i 1 i A -9- Case 153-5446 Condensation is carried out under known conditions, e.g. in aqueous medium at temperatures from 20-100'C under stirring, optionally increasing the pH by the addition of alkali.
Compounds of formula III can be prepared by forming a salt of one mole of a compound of the formula IIP / NH p R 19 / RS (11: / c - R,3 R 11R 5 Pa' where the symbols are as defined above, with pI moles of a mono-, bi- or tri- carbocyclic phosphinic or phosphonic acid.
Compounds of formula IV can be prepared by reacting one mole of a di-, tri- or tetracarboxylic acid (or a functional derivative thereof like the acid halide) with rI moles of a compound of formula III (111) Case 153-5446 and r moles of a compound of formula III' where the symbols are as defined above.
It has been found that the above-mentioned organic phosphinic and phosphonic acid compounds are extremely useful for improving the dyeability and, particularly when a sterically hindered amine group is present, the stability against light, especially UV light, oxidation, bleaching and heat when these products are applied to fully- or semisynthetic high molecular weight (especially hydrophobic) plastics and homogeneously mixed therein.
Preferred plastics materials are, for example, polyolefin (especially polyethelene and polypropylene), ethylene/propylene copolymers, polybutylene, polystyrol, chlorinated polyethylene, polyvinylchloride, polyester, polyamide, polycarbonate, polymethylmethacrylate, polyphenyleneoxide, polyurethane, polypropyleneoxide, polyacetate, phenylformaldehyde resins, epoxide resins, polyacrylnitrile and copolymers thereof, such as ABS-terpolymers. Preferably the compounds according to the invention are used to stabilize polypropylene, polyethylene (including high-molecular weight polyethylene),ethylene/ propylene copolymers, polyvinylchloride, polyester, polyamide, polyurethane, polyacrylnitrile, ABS-terpolymers of acrylic acid, styrol and acrylonitrile, copolymers of styrene and acrylonitrile or styrene and butadiene, most preferably polypropylene, polyethylene, ethylene/propylene copolymers or ABS.
The compounds according to the invention are particularly useful for improving the above-mentioned properties of synthetic polyamides, especially here for the improvement of dyeability, dye-intensity (dye yield) and the resulting dyeings have good light-fastness and washfastness properties as well as providing an improved stability of the substrate against damage due to light.
By synthetic polyamide is meant a variety of plastics materials, especially the polycondensate or polymerisate of dicarboxylic acid and diamines, for example adipic acid and hexamethylenediamine, lactams, such as c-caprolactam, aminocarbonic acids, for example i i 1 1 i i 1 i i r Case 153-5446 w-aminoundecane acid or from dicarboxylic acids (isophthalic or terephthalic acid) and from aromatic diamines, for example paraphenylenediamine.
Natural materials such as rubber can also be treated with the compounds according to the invention.
The compounds according to the invention can be worked into the material to be protected by known methods.
A particularly useful application process is the thorough mixing of a plastics material with the new compounds in the melt. Examples would be, in a kneader or through extruding, spray pouring, forming blown forms or spinning to produce required articles. Preferably polypropylene or polyethylene is used in granulate form, particulate form or powder form. Processes of working the compound into the polymer may be by extrusion, spray pouring, by rotation pouring or through blow-forming, for example to produce films, sheets, hoses, pipes, containers, flasks, profile parts, threads, fibres, bands or foam.
The plastics do not have to be completely polymerized or condensed before the mixture of the compounds according to the invention occurs with them. That is to say, monomers or prepolymers or precondensates can be added to the compounds according to the invention and then either at the same time as or after condensation or polymerisation of the plastics can be made into the final form.
Case 153-5446 In the following examples all parts and percentages are by weight. All temperatures are in 'C.
Example 1
423.5 parts 2-chloro-4,6-bis-(21,21,61,61-tetramethylpiperidyl-41amino)triazine (known from DE-PS 23 19 816) (Compound 1b) are suspended in 1500 parts water and the mixture is reacted with 142 parts phenyl phosphinic acid and heated to 50 and stirred at this temperature for 2 hours. The insoluble salt that results is filtered off, washed with water and dried under vacuum. The hygroscopic product melts at 218-220.
The product is of formula la cl 11 "L', N c H 3 CH 3 3 13 -u H. C11.1 H C 1 J 3 H 3 2 CH; 11 eO c 6 H 5 The elemental analysis is as follows:
C 56.6 (57.2)%, H 8.3 (8.0)%, Cl 6.3 (6.3)% N 17.1 (17.3)%, P 5.3 (5.5)%, 0 6.9 (5.7)% Example 2
184.5 parts of 2,4,6-trichlorotriazine and 314 parts 4-amino- phenyl phosphinic acid are added to 1300 parts water and the mixture is i i 1 1 i i 1 i 1 l 1 i 1 1 i 1 If Case 153-5446 stirred for 2 hours at 50'. The reaction product which is insoluble is filtered off, washed acid free with water and dried under vacuum. The resulting product is 2-chloro-4,6-bis-(41-phosphinic acid phenyl amino)- triazine with a melting point of over 3001.
Example 3
Example 1 is repeated using instead of the phosphinic acid, 158 parts of phenyl phosphonic acid.
Example 4
Example 2 is repeated using instead of the phosphinic acid, 346.0 parts of 4-amino-phenyl-phosphonic acid.
Examples 5-6
Example 1 is repeated using 284.0 parts of phenyl phosphinic acid [instead of 142.0 parts] (Ex. 5) or 316.0 parts phenyl phosphonic acid (Ex. 6).
The products of examples 1-6 enable hydrophobic plastics materials to have a noticabe improved dyeability and these plastics, (dyed or undyed) show excellent fastness against light and heat.
Examples 7-9
Example I is repeated except that instead of compound 1b, 544.0 parts of 2,4,5-tris-(2,,2,,6,,61- tetramethylpiperidyl-41-amino)-triazine is reacted with 284.0 parts (instead of 142.0 parts) of phenylphosphinic acid (Ex. 7) or 316.0 parts phenylphosphonic acid (Ex. 8).
Example 1 is repeated except that 556.0 parts of 2-(1',2',6', 6'pentamethylpiperidyl-41-amino)-4,6-bis-(211,211,611,611-tetram ethyl piperidyl-4-amino)-triazine is reacted with either 284.0 parts of phenyl phosphinic acid (Ex. 9) or 316 parts of phenyl phosphonic acid Case 153-5446 (Ex. 9a). The products have good fastness properties to light and heat and cause improved dyeability properties.
Example 10
2-(phenylphosphinic acid-41-amino)-4,6-bis-(211,211,611,611tetramethylpiperidyl-4"-amino)-triazine are prepared by the condensation of 423.5 parts 2chloro-4,6-bis-(2,,2,,6,,61-tetramethylpiperidyl-4amino)triazine with 157 parts 4 amino phosphinic acid in a 25% aqueous sodium hydroxide solution that is stirred for 58 hours at 801. The reaction mixture is then acidified with diluted hydrochloric acid bring the pH to about 2. The reaction product which is insoluble is then filtered, washed with water and dried. The resulting compound improves the dyeability of synthetic polymers in particular synthetic polyamide and improves the fastness of the plastic to the effects of light.
Examples 11-14 Example 1 is repeated except sing 442 parts of terephthalic acid bis-(2,2, 6,6tetramethylpiperidyl-4-)diamide is reacted with with 142 parts of phenyl phosphinic acid (Ex. 11) or 284 parts of phenylphosphinic acid (Ex. 12) or with 158 parts of phenyl phosphonic acid (Ex. 13) or 316 parts (Ex. 14) of phenyl phosphonic acid.
Examples 15-18 Example 1 is repeated except that 1,442 parts of isophthalic acid bis-(2, 2,6,6,-tetramethylpiperidyl-4-)-diamide is reacted with either 142. parts of phenyl phosphinic acid (Ex. 15) or 284 parts of phenyl phosphinic acid (Ex. 16) or with 158 parts phenyl phosphonic acid (Ex. 17) or 316 parts phenyl phosphonic acid (Ex. 18). The resulting product has good light and heat stability and has improved dyeability properties.
1 1.1 1 1:
I 1 Examples 19-30 Case 1535446 Example 1 is repeated except that 576 parts of trimesinic acid-tris(2,2,6, 6-tetramethylpiperidyl-4)-triamide (DE-PS 20 40 975) is reacted with either 142 parts of phenyl phosphonic acid (Ex. 19) or 284 parts of phenyl phosphinic acid (Ex. 20) or 426 parts phenyl phosphinic acid (Ex. 21) or 158 parts of phenyl phosphonic acid (Ex. 22) or 316 parts of phenyl phosphonic acid (Ex. 23) or 474 parts phenyl phosphonic acid (Ex. 24) to form a salt. The resulting products have good stability to light and heat and improve dyeability. Further products having the same effect can be produced by replacing the trimesinic acid with the same amounts of trimellitic acid-tris-(2,2,6,6-tetramethyl piperidyl-4)-triamide (Ex. 25- 30).
Examples 31-38 Example 1 is repeated except 710 parts pyromellitic acid tetrakis (2,2,6, 6,-tetramethylpiperidyl-4)-tetramide is treated with either 142 parts of phenyl phosphinic acid (Ex. 31) or 284 parts of phenyl phosphinic acid (Ex. 32) or 426 parts of phenyl phosphinic acid (Ex. 33) or 568 parts of phenyl phosphinic acid (Ex. 34).
Example 1 is repeated except that 710 parts pyromellitic acid tetrakis(2,2,6,6,-tetramethylpiperidyl-4)-tetramide is reacted with either 158 parts of phenyl phosphonic acid (Ex. 35) or 316 parts of phenyl phosphonic acid (Ex. 36) or 474 parts phenyl phosphonic acid (Ex. 37) or 632 phenyl phosphonic acid (Ex. 38).
Examples 39 and 40 Example 1 is repeated except that 423.5 parts of 2-chloro-4,6-bis(21,21, 61,61-tetramethylpiperidyl-41-amino)-triazine is reacted with either 282 parts of a diphenyl-diphosphinic acid mixture (Ex. 39) or 314 parts of a diphenyl-phosphonic acid mixture (Ex. 40) to form a salt. The resulting products have good fastness to light and heat and improve the dyeability of polymers.
16- Examples 41-46 Case 153-5446 Example 1 is repeated except that 442 parts of terephthalic-acid-bis(2,2, 6,6-tetramethylpiperidyl-4-)diamide is reacted with either 282 parts of a diphenyl- diphosphinic acid mixture (Ex. 41) or 314 parts of a diphenyl- diphosphonic acid mixture (Ex. 42). Instead of the terephthalic acid diamide of Examples 41 and 42, 442 parts of istophthalic-acid-bis-(2,2,6, 6-tetramethyl- piperidyl-4)-diamide may be used (Ex. 43 and 44) or 576 parts trimesinic-acid-tris-(2,2,6,6tetramethylpiperidyl-4-)-triamide (Ex. 45 and 46) or 576 parts of trimellitic acid-tris-(2,2,6,6-tetramethylpiperidyl-4)-triamide (Ex. 46a).
Examples 47-50 710 parts of pyromellitic-acid-tetrakis-(2,2,6,6-tetramethylpiperidyl4)- tetramide are reacted in a method analogous with Example 1 with either 282 parts of a diphenyl-diphosphinic acid mixture (Ex. 47), or 564 parts of diphenyl-diphosphinic acid mixture (Ex. 48) or 314 parts of a diphenyldiphosphonic acid mixture (Ex. 49) or 628 parts of a diphenyldiphosphonic acid mixture (Ex. 50).
Examples 51 and 52 Example I is repeated except that 423.5 parts of 2-chloro-4,6-bis(21,21, 61,61-tetramethylpiperidyl-41-amino)-triazine is reacted with either 132 parts of a naphthalene-phosphinic acid mixture (Ex. 51) or 148 parts of a naphthalene-phosphonic acid mixture (Ex. 52). After the product has been purified, a product is produced having very good dyeability properties and good fastness against light and heat on plastics materials.
Examples 53 and 54 Example 2 is repeated except that 184.5 parts of 2,4,6-trichlorotriazine is first reacted with 108 parts of 2,2,6,6- 1 1 i i i i 1 1 1 1 1 i 1 1 1 At 1; 17- Case 153-5446 tetramethyl-4-aminopiperidine followed by reacting with either 157 parts of 4-amino-phenyl-phosphonic acid (Ex. 53) or 173 parts of 4-amino-phenylphosphonic acid (Ex. 54).
Examples 55 and 56 Example 2 is repeated except that 218 parts of tetrachloro-pyrimidine is reacted with either 314 parts of 4-amino-phenyl-phosphinic acid (Ex. 55), or 346 parts of 4-amino-phenyl-phosphonic acid (Ex. 56). The resulting product is as effective as the product of Example 2.
Examples 5760
Examples 11 to 14 are repeated except that 444 parts of terephthalic acidbis-(2,2,6,6-tetramethylpiperidyl-4)-diester (the product of reacting terephthalic acid di-chloride and 2,2,6,6-tetramethyl-4hydroxypiperidine) are reacted with either 142 parts of phenyl phosphinic acid (Ex. 57) or 284 parts of phenyl phosphinic acid (Ex. 58) or 158 parts of phenyl phosphonic acid (Ex. 59) or 316 parts of phenyl phosphonic acid (Ex. 60). These products also show an excellent fastness to light and heat and improve the dyeability of plastics materials.
Examples 61 and 62 Example 1 is repeated except that instead of phenylphoshinic acid, 200 parts acenaphthenyl phosphinic acid (Ex. 61) or 216 parts of acenaphthenyl phosphonic acid (Ex. 62) are used.
Application Example 99 parts of poly-e-caprolactam in the form of powder is mixed with 1 part of the product of Example 1 in a mixer. The powder mixes homogenously in a very short period of time. After about 10 minutes the mixture is dried for 16 hours at 2200 brought to a melt-spin machine and after 8 minutes dwelling at 275-280 is spun into fibers under a nitrogen atmosphere. The resulting fiber material can 1 1 Case 153-5446 conventionally be dyed with acid dyestuffs in light to deep tones and the resulting dyes of a brilliant and show excellent light, wash, oxidation and rubbing fastness properties.
The application example can be repeated using instead of the 1 part of the product of Example 1, 1 part of any one of the Examples 2-60.
I I 1 i 1 i 1 1 1 1 Case 153-5446

Claims (19)

  1. CLAIMS:
    A mono-, bi- or tri carbocyclic phosphinic or phosphonic acid compound containing i) at least one group that is reactive to hydroxy and/or amino and/or ii) at least one group containing a sterically hindered amine.
  2. 2. A compound according to Claim 1 in which the mono-, bi- or tricarbocyclic groups are C5-7cycloalkyl, phenyl-, naphthyl-, tetrahydronaphthyl-, acenaphthene- or acenaphthylene- groups, unsubstituted or mono- or di- substituted by non-water solubilizing substituents selected from halogen, hydroxyl, C1-4alkyl, phenyl-, C14alkoxy and/or Cl-4alkoxycarbonyl groups.
  3. 3. A compound according to Claim 1 or Claim 2 in which the groups that are reactive to hydroxy and amino groups are selected from cyclic groups bearing at least one reactive group and having at least two nitrogen atoms (that may be separated by one or two carbon atoms).
  4. 4. A compound according to any one of the preceding claims in which the groups that are reactive to hydroxy and amino groups are selected from reactive group bearing triazinyl, pyrimidinyl, quinoxalinyl, quinazolinyl groups, phthalazinyl, benzoxazolyl, benzthiazolyl groups as well as groups of the formula -CO-(Alkyl R 30 0 R 30.
    -CH2CE2-N COCK=CH1) (i) (ii) 1 i i i R 30 R 3 1 co- 956C- I R 3 R 30 0 //--- m R 30 % - 1 _co & 30 1 1 0 F2 C- 2 1 -uu-(;ki=uh-(;H CH2 -NS02-CH=CM2 1 Alkyl -CO-CH2CH2-CO2-aryl -CO-C=CH2 1 R3 0 -COCH=CC12y -CO-CH2-R30 -S02-CH2CH2-0-SO3Na -S02-M-CH2CH2-0-SO3Na -CO-CH2-NI(C1-4Alkyl)3AG -COCH2CH2-R30 -CO-CH H-CO0C1-4Alkyl N 0 N 0 Case 1535446 (iii) (iv) (v) (vi) (vii) (viii) (ix) (X) (xi) (Xii) (Xiii) (xiv) 1 m 1 1 1.1 li 1 j 1 f 1 4, t Case 153-5446 in which R30 is a halogen atom or a group -W(C1-4alkyl)3 or -N' A- (pyridinium) and A- is an anion.
  5. 5. A compound according to any one of the preceding claims in which the groups that are reactive to hydroxy and amino groups are selected from mono and di-chlorotriazinyl, mono and di-chloropyrimidinyl and mono or dichloroquinoxalinyl.
  6. 6. A compound according to any one of the preceding claims of formula I or II R 1.
    /?Is 0 - /" C E3 1 Go-?- (0),H Rz-R ' KS R R, -R. NR p R in which I C-R C.R R a z _Y A 0 R is a mono-, bi- or tri- carbocyclic group unsubstituted or substituted by one or two substituents selected from the group of halogen, C1-4alkyl or C1-4alkoxy; R, is a group reactive to hydroxy and amino; R2 is the group -NR3- or -0- where R3 is hydrogen or Cl-4alkyl; Case 153-5446 R4 together with the two carbons to which the groups R8 are attached and the nitrogen to which R5 is attached form a 5,-, 6or 7-membered cyclic group, that is optionally substituted with further non-water-solubilizing substituents and/or to which a further cyclic group is attached to form a spiro group; R5 is hydrogen, Cl-4alkyl or acyl; each R8 independently is a Cl-6alkyl group, preferably methyl or ethyl, more preferably methyl; n is 0 or 1; p is 1, 2 or 3; and p,, is 0, 1 or 2 in which the sum of p + p. is 1, 2 or 3.
  7. 7. A compound according to any one of claims 1-5 of formula III or IV / RS 0 C R,3 p..
    IN R 5) Pa R in which R /8 8 -R 2 - P.
    RIO R 0 2 (0) r n is 0 or 1 r and r, are, independently of each other, 1, 2 or 3 p, is 1, 2, 3 or 4 p.' is 0, 1, 2 or 3 provided that the sum of p, and p,' and of r and r' is 2, 3 or 4, 1 1 i 1 i i 1 1 1 1 1 1 1 i c 1 1 1 1 1:I 1 k V) i 1 1 1 :I i 5:
    1 1 1 1 i 1 Case 153-5446 R10 is an amide or ester bound phenyl group and the other symbols are as defined in Claim 1.
  8. 8. A compound according to any one of the preceding claims in which the phosphinic and phosphonic acid groups are those derived from compounds of formula V 0 1 Y H- (0) -, R ' - 1 P- (0) -H n 6H - 1 0,,bii in which R10. is a direct bond, oxygen, Cl-4alkylene or -CH=CH,
  9. 9. A compound according to any one of the preceding claims in which the sterically hindered amine containing groups are of the formula R 1 C-1k /1/ \ 8 I, N-R- -' 4 \,-- C C-R 8 - 8 where the symbols are as defined in Claim 6.
  10. 10. A compound according to any one of the preceding claims in which the sterically hindered amine containing groups are of formula a) to e) below R 5 R 8 R! -
  11. 11 (a) ' 1 - D R a R 8 R 8 8 (d) R R- 8 R 8 R 8 R N N- (b) R R 0 (e) RS R 8 R. 5 R / R 8 1 9 R -W 1 X 5 \ YR 9 R 8 R 8 - 1 ' (c) ' Case 153-5446 where R51 is hydrogen, Cl-4alkyl or acyl, each R9 independently is hydrogen, Cl-4alkyl or one R9 is phenyl and the other R9 is hydrogen or Cl-4alkyl or both groups R9 together form a group -(CH2)11- and -Y- is -N-CO- or -CO-N- 11. A process for preparing a compound according to Claim 1 comprising a) condensing an appropriate amount of a compound containing one or more groups capable of reacting with hydroxy and/or amino with an appropriate amount of a mono-, bi- or tri-carbocyclic, amino or hydroxy group containing phosphinic or phosphonic acid or b) reacting an appropriate amount of a mono-, bi- or tri-carbocyclic phosphinic or phosphonic acid with an appropriate amount of a sterically hindered amine containing compound, which latter compound may contain one or more groups capable of reacting with hydroxy and/or amino groups.
  12. 12. A process for improving the dyeability of a plastics material comprising applying, to that plastics material, a compound according to Claim 1.
  13. 13. A plastics material to which a compound according to Claim 1 has been applied.
  14. 14. A plastics material according to Claim 13 in which the material is selected from polyolefin, ethylene/propylene copolymers, polybutylene, polystyrol, chlorinated polyethylene, polyvinyl chloride, polyester, polyamide, polycarbonate, polymethylmethacrylate, polyphenyleneoxide, polyurethane, polypropyleneoxide, polyacetate, phenyl-formaldehyde resins, epoxide resins, polyacryInitrile and copolymers thereof, such as ABSterpolymers.
    1 i i 1 i z 1 I i 1 i 1 I I i i i c 4 4 Case 153-5446
  15. 15. A plastics material according to Claim 13 in which the material is selected from polypropylene, polyethylene (including high-molecular weight polyethylene),ethylene/ propylene copolymers, polyvinylchloride, polyester, polyamide, polyurethane, polyacrylnitrile, ABS-terpolymers of acrylic acid, styrol and acrylonitrile, copolymers of styrene and acrylonitrile or styrene and butadien.
  16. 16. A compound substantially as herein defined with reference to any one of the examples.
  17. 17. A process preparing a compound according to Claim 1 with reference to any one of the examples
  18. 18. A plastics material substantially as herein defined with reference to the Application Example.
  19. 19. A process for improving the dyeability of a plastics material substantially as herein defined with reference to the Application Example.
    Published 1992 at The Patent Office Concept House- Cardiff Road- NewportGwent NP9 I RH Further copies may be obtained ir(iii Sales Branch- Unit 6. Nine Milt, Point- CA7nfelinfach. Cross KeYs. Newport. NP I 7HZ. Printed bi- Multiplex techniques ltd- Si 'vlan Crdi Ken,
GB9116822A 1990-08-09 1991-08-05 Mono-,bi- or tri-carbocyclic phosphinic or phosphonic acid compounds Expired - Fee Related GB2247021B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE4025228 1990-08-09

Publications (3)

Publication Number Publication Date
GB9116822D0 GB9116822D0 (en) 1991-09-18
GB2247021A true GB2247021A (en) 1992-02-19
GB2247021B GB2247021B (en) 1994-11-09

Family

ID=6411916

Family Applications (1)

Application Number Title Priority Date Filing Date
GB9116822A Expired - Fee Related GB2247021B (en) 1990-08-09 1991-08-05 Mono-,bi- or tri-carbocyclic phosphinic or phosphonic acid compounds

Country Status (6)

Country Link
JP (1) JPH04253988A (en)
CH (1) CH681542A5 (en)
DE (1) DE4125440A1 (en)
FR (1) FR2666091B1 (en)
GB (1) GB2247021B (en)
IT (1) IT1253878B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111875584A (en) * 2020-08-07 2020-11-03 宿迁市振兴化工有限公司 Preparation method of multifunctional light stabilizer

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19751857A1 (en) * 1997-11-22 1999-05-27 Kronos Titan Gmbh Inorganic particles for use in plastics, paints, etc.,

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1010743A (en) * 1960-12-27 1965-11-24 Du Pont Uracil derivatives
GB1312235A (en) * 1969-03-11 1973-04-04 Glaxo Lab Ltd Phosphonic acid salts
GB1347009A (en) * 1970-12-15 1974-02-13 Scottish Agricultural Ind Ltd Plant growth modification
GB1349165A (en) * 1970-06-19 1974-03-27 Huels Chemische Werke Ag Hydrocarbon motor fuels
GB1533461A (en) * 1975-02-03 1978-11-22 Nelson Res & Dev Phenyl-and benzylphosphonate esters having prostaglandin-blocking activity
GB1561001A (en) * 1976-01-24 1980-02-13 Hoechst Ag Piperidine hydroxyamides process for their preparation andtheir use as stabilizers for organic materials
EP0031054A1 (en) * 1979-11-29 1981-07-01 Sumitomo Chemical Company, Limited Soil disinfectant composition, a method for preventing and controlling diseases in soil and certain phenylphosphinic acid salts
EP0097534A2 (en) * 1982-06-23 1984-01-04 E.R. Squibb & Sons, Inc. Phosphonyl hydroxyacyl amino acid derivatives as antihypertensives
EP0115466A2 (en) * 1983-02-01 1984-08-08 Rhone-Poulenc Agrochimie Fungicidal salts of organophosphorus derivatives

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3684765A (en) * 1970-01-08 1972-08-15 Sankyo Co Stabilization of synthetic polymers
GB1372528A (en) * 1970-10-22 1974-10-30 Sandoz Ltd Benzene phosphonous acid compounds their production and use as stabilizers for organic materials
CH557693A (en) * 1971-06-23 1975-01-15 Ciba Geigy Ag PROCESS FOR PROTECTING ORGANIC MATERIALS AGAINST ULTRAVIOLET RADIATION.

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1010743A (en) * 1960-12-27 1965-11-24 Du Pont Uracil derivatives
GB1312235A (en) * 1969-03-11 1973-04-04 Glaxo Lab Ltd Phosphonic acid salts
GB1349165A (en) * 1970-06-19 1974-03-27 Huels Chemische Werke Ag Hydrocarbon motor fuels
GB1347009A (en) * 1970-12-15 1974-02-13 Scottish Agricultural Ind Ltd Plant growth modification
GB1533461A (en) * 1975-02-03 1978-11-22 Nelson Res & Dev Phenyl-and benzylphosphonate esters having prostaglandin-blocking activity
GB1561001A (en) * 1976-01-24 1980-02-13 Hoechst Ag Piperidine hydroxyamides process for their preparation andtheir use as stabilizers for organic materials
EP0031054A1 (en) * 1979-11-29 1981-07-01 Sumitomo Chemical Company, Limited Soil disinfectant composition, a method for preventing and controlling diseases in soil and certain phenylphosphinic acid salts
EP0097534A2 (en) * 1982-06-23 1984-01-04 E.R. Squibb & Sons, Inc. Phosphonyl hydroxyacyl amino acid derivatives as antihypertensives
EP0115466A2 (en) * 1983-02-01 1984-08-08 Rhone-Poulenc Agrochimie Fungicidal salts of organophosphorus derivatives

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111875584A (en) * 2020-08-07 2020-11-03 宿迁市振兴化工有限公司 Preparation method of multifunctional light stabilizer

Also Published As

Publication number Publication date
IT1253878B (en) 1995-08-31
JPH04253988A (en) 1992-09-09
ITRM910591A1 (en) 1993-02-02
ITRM910591A0 (en) 1991-08-02
FR2666091A1 (en) 1992-02-28
FR2666091B1 (en) 1994-01-14
GB2247021B (en) 1994-11-09
CH681542A5 (en) 1993-04-15
GB9116822D0 (en) 1991-09-18
DE4125440A1 (en) 1992-02-13

Similar Documents

Publication Publication Date Title
KR970002216B1 (en) Dyestuffs for dyeing plastics
US3282886A (en) Polycarbonamides of improved photostability and dye lightfastness
CA1198431A (en) Piperidyl derivatives of triazine copolymers, processes for their preparation and stabilised composition containing these derivatives
US3882090A (en) Water-soluble polyamides from alkyleneoxy bis(propyl-amine)
JP3041823B2 (en) Synthetic polyamides and their salts
KR20070004054A (en) Dyeable polyolefin fibers and fabrics
CN1198152A (en) Novel cinnamamides and their use as stabilizers
WO1999046323A1 (en) Light and thermally stable polyamide
MXPA98008878A (en) Polyamide stable to light and termicame
US3673158A (en) Sulfobetaine glycol modified poly(ethylene terephthalate)
GB2247021A (en) Mono-, bi- or tri-carbocyclic phosphinic or phosphonic acid compounds
SK282229B6 (en) Obtaining caprolactam by depolymerization of molten polycaprolactam and its use
KR100199220B1 (en) Improved dyeability of synthetic polyamide
US3787355A (en) Stabilizing of polyamides
US4888370A (en) Flame-resistant polyamides
US3867478A (en) Polyester composition
JPH06256650A (en) Stabilized polyamide composition
US3583941A (en) Linear polyester polymers containing alkali metal salts of sulfonated aliphatic compounds
WO2018190157A1 (en) Novel compound and resin composition
US3454670A (en) Polypropylene composition having improved dye receptivity containing epichlorohydrin/diamine/diphenol polycondensate
EP1409576A1 (en) Light-stabilized polymers comprising light-stabilizing moieties, articles therefrom and a method of making the same
JPH0625550A (en) Pigment compound and coloring material for resin
US4059653A (en) Antistatic dyeable polyamide composition
US3668278A (en) Blends of polyolefins and polyamides
US3538057A (en) Basic dyeable polyester polymers containing a metal salt of a cycloalkyl sulfonate

Legal Events

Date Code Title Description
PCNP Patent ceased through non-payment of renewal fee

Effective date: 19960805