Thioxanthonecarboxylic acids, esters thioesters and amides with reactive functional groups and polymers prepared therefrom and having thioxanthone radicals as side chains

• US 4,594,400 A
• Filed: 09/19/1984
• Issued: 06/10/1986
• Est. Priority Date: 02/05/1980
• Status: Expired due to Fees

• Current Assignee: Ciba Specialty Chemicals Corp (BASF SE)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Zweifel, Hans, Kvita, Vratislav, Roth, Martin, Felder, Louis
• Primary Examiner(s): HENDERSON JR, CHRISTOPHER A
• Application Number:
  US06/652,683
• Time in Patent Office: 629 Days
• Field of Search: 525/327.5, 525/329.8, 525/348, 528/322, 526/256, 526/262
• US Class Current: 526/256
• CPC Class Codes: C07C 323/00 Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
• CPC Class Codes: C07D 209/48 with oxygen atoms in positions 1 and 3, e.g. phthalimide
• CPC Class Codes: C07D 335/16 Oxygen atoms, e.g. thioxanthones
• CPC Class Codes: C08F 2/50 with sensitising agents
• CPC Class Codes: C08F 20/38 Esters containing sulfur
• CPC Class Codes: C08G 63/688 containing sulfur
• CPC Class Codes: C08G 85/00 General processes for preparing compounds provided for in this subclass
• CPC Class Codes: C08G 85/004 Modification of polymers by chemical after-treatment
• CPC Class Codes: C08K 5/45 Heterocyclic compounds having sulfur in the ring
• CPC Class Codes: C08L 23/02 not modified by chemical after-treatment
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: G03F 7/031 Organic compounds not covered by group G03F7/029
• CPC Class Codes: G03F 7/032 with binders
• CPC Class Codes: G03F 7/0388 with ethylenic or acetylenic bands in the side chains of the photopolymer
• CPC Class Codes: Y10S 522/904 Monomer or polymer contains initiating group

Abstract

Thioxanthone carboxylic acid esters, thioesters and amides with reactive functional groups of the formula ##STR1## in which X, Y, Z, n and Q are as defined in the patent claim and Q is, for example, --OCH═CH₂, --OCH₂ CH═CH₂, --SCH₂ CH═CH₂ or --NHCH₂ CH═CH₂ (n=1), --OH, --SH, --NH₂, --COOH, --COCl or --OCO--C(R")═CH₂, in which R" is methyl or hydrogen (n=2), are suitable for the preparation of polymers with thioxanthone radicals in side chains. The compounds (I) and also the polymers which can be prepared therefrom can be employed as sensitizers for photocrosslinkable polymers or as initiators, if desired in a mixture with amines, for the photopolymerization of ethylenically unsaturated compounds or for the photochemical crosslinking of polyolefines.

Claims

1. A polymer which has a mean molecular weight of not less than 1000 and which contains, in side chains, thioxanthone groupings of the formula I'"'"' ##STR63## in which n is the number 1 or 2, X is hydrogen, halogen, --CN, --OH, --SH, --NH₂, --NO₂, phenylsulfonyl or alkylsulfonyl, alkyl, alkoxy, alkylthio, N,N-dialkylamino or --CO-alkyl having, in each case, 1-4C atoms in the alkyl moieties, Z is hydrogen, halogen, --OH, --SH or alkyl, alkoxy, alkylthio or N,N-dialkylamino having, in each case, 1-4C atoms in the alkyl moieties, Y is --OR₁ --, --SR₁ -- or --N(R₂)R₁ --, R₁ is straight-chain or branched alkylene having a total of 2-23C atoms and 2-13C atoms in the main chain, cyclopentylene, cyclohexylene, phenylene ##STR64## or --(CH₂ CH₂ O)_x --CH₂ CH₂ --, R₂ is hydrogen or straight-chain or branched alkyl having a total of 1-23C atoms and 1-13C atoms in the main chain, G is --CH₂ --, --CH₂ CH₂ --, --C(CH₃)₂ --, --O--, --SO₂ -- or --NH-- and x is an integer from 1 to 5, the proportion of groupings of the formula I'"'"' being not less than 2 percent, based on the number of recurring structural elements in the polymer.

2. A polymer according to claim 1, in which the proportion of groupings of the formula I'"'"' is 2-100 and preferably 20-100 percent, based on the number of recurring structural elements in the polymer.

3. A polymer according to claim 1, which has a mean molecular weight of about 1,000 to 100,000 and contains recurring structural elements of the formulae XI to XX ##STR65## in which "Th" is a radical of the formula I" ##STR66## and "Th₁ " is a radical of the formula I'"'"'" ##STR67## X, Y, Z and n are as defined under formula I'"'"', X'"'"' is hydrogen, halogen, --CN, --NO₂, phenylsulfonyl or alkylsulfonyl, alkyl, alkoxy, alkylthio, N,N-dialkylamino or --CO-alkyl having, in each case, 1-4C atoms in the alkyl moieties, Z₁ is hydrogen, halogen or alkyl, alkoxy, alkylthio or N,N-dialkylamino having, in each case, 1-4C atoms in the alkyl moieties, Q₁ is --O--, --S-- or --NH--, Q₂ is --O--, --S--, --NH-- or --NR'"'"'--, Q₃ is --OCO--, --O--, --S--, --NH-- or --NR'"'"'--, R'"'"' is alkyl having 1-5C atoms, R" is hydrogen or methyl, p is the number 1 or 2, Y₁ is --OR₁ --, --SR_1-- or --NH--R₁ -- and R₁ is straight-chain or branched alkylene having a total of 2-23C atoms and 2-13C atoms in the main chain, or phenylene.

4. A polymer according to claim 3, which consists of recurring structural elements of the formulae XI to XX and of identical or different recurring structural elements of the formula XXI ##STR68## in which X₅ is hydrogen, X₄ is hydrogen, chlorine or methyl and X₆ is hydrogen, methyl, chlorine, CN, --COOH, --CONH₂, phenyl, methylphenyl, methoxyphenyl, cyclohexyl, pyridyl, imidazolyl, pyrrolidyl, --COO-alkyl having 1-12C atoms in the alkyl moiety, --COO-phenyl, ##STR69## --COO-alkyl-OH having 1-3C atoms in the alkyl moiety, --OCO-alkyl having 1-4C atoms in the alkyl moiety, --OCO-phenyl, --CO-alkyl having 1-3C atoms in the alkyl, alkoxy having 1-20C atoms or phenoxy, or X₄ is hydrogen and X₅ and X₆ together are the grouping --CO--O--CO--, or are each --COOH or --COO-alkyl having 1-6C atoms in the alkyl.

5. A polymer according to claim 3 or 4, which contains recurring structural elements of the formulae XI, XIII to XV or XVII to XX and in particular recurring structural elements of the formulae XI, XIV or XVII, and also, if desired, identical or different recurring structural elements of the formula XXI, in which formulae R" is hydrogen or methyl, Q₁ is --O--, Q₂ and Q₃ independently of one another are --O-- or --NH--, p is the number 1, n is the number 1 or 2, Y is --OR₁ -- or --NHR₁ --, R₁ is alkylene having 2-6C atoms or, if Q₂ is --O--, also --CH₂ CH₂ OCH₂ CH₂ -- or ##STR70## X and X'"'"' are hydrogen, Z and Z₁ are hydrogen or methyl or methoxy bonded in the 7-position, X₅ is hydrogen, X₄ is hydrogen or methyl and X₆ is hydrogen, --OCOCH₃, --COOH or --COO-alkyl having 1-8C atoms in the alkyl, or X₄ and X₅ are each hydrogen and X₆ is --CN, chlorine, phenyl or alkoxy having 1-6C atoms or, if X₄ is hydrogen, X₅ and X₆ together are also --CO--O--CO--, and the groupings ##STR71## are bonded in the 1-position or 3-position to the benzene ring of the radical "Th" or "Th₁ ".