Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0098—Organic pigments exhibiting interference colours, e.g. nacrous pigments
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
  • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
  • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
  • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring

Definitions

• the present invention relates to a cholesteric polymer P1 obtainable by a ring-opening metathesis polymerization ("ROMP") of strained cyclic olefins.
• ROMP ring-opening metathesis polymerization
• the present invention relates to crosslinked cholesteric polymers, processes for the preparation of the inventive polymers and their use.
• US 5,362,315 claims a pigment whose color depends on the viewing angle.
• the pigment comprises oriented three-dimensionally support-free substances of liquid-crystalline structure having a chiral phase and, optionally dyes and pigments, wherein said optional dyes and pigments do not serve as a base for the oriented three-dimensionally crosslinked liquid- crystalline substances having a chiral phase.
• WO 95/32247 describes interference pigments based on a SCLCP comprising a nematic and a chiral component. These pigments are synthesized e.g. by a in-situ photopolymerization of a nematic liquid crystalline diacrylate and a cholesteric liquid crystalline diacrylate, or a mixture of corresponding diacrylates and monoacrylates.
• WO 96/02597 describes a process for printing substrates with a coating or printing agent, in which a mixture of mono- and/or diacrylates are polymerized, whereby at least one component is chiral.
• WO 96/17901 describes a liquid crystalline material in the form of a cholesteric polymer network, wherein the polymerized material is obtainable by copolymerization of a compound having at least two equal polymerizable functional groups and a chiral polymerizable compound, the latter being a terpenoid.
• the crosslinking is carried out in-situ.
• the object of this invention was to provide side-chain liquid crystalline polymers which are obtainable by a ring-opening metathesis polymerization of strained cyclic rings whereby the inventive compounds and the processes for its preparations should not show the abovementioned drawbacks.
• the inventive polymers should be cholesteric, crosslinkable, should show a narrow polydispersity, and the crosslinking of the cholesteric polymers should be carried out easily with regard to a technical and economical process.
• a cholesteric polymer P1 was found obtainable by a ring-opening metathesis polymerization ("ROMP") of
• Z stands for A t ⁇ -As-A ⁇ As-A ⁇ -A?-, if y is 1 , or, in case y is 2, for A ⁇ -(A 2 -A 3 -A -A 5 -A 6 -A 7 -) 2
• Bi stands for a chiral organic group
• B 2 stands for an organic crosslinkable group
• B 3 stands for an organic, non-chiral, non-crosslinkable group
• a T stands for a radical selected from the group consisting of X X
• Vlb including the exo- and the endo-isomers of the radicals IVa, IVb, and Via
• y is 1 in case A t is a monomer selected of IVa, IVb, Va, or Vb, or y is 2 in case A! is one of the biradicals Via or Vlb, and in which
• X is selected from the group consisting of -CH _-, -O- and -S-
• a 2 is -CH 2 - or -C(O)-
• a 3 is -O- or -NH-, or
• a A 2 -A 3 stands for a radical of the formula VII X
• a 4 is -(CH 2 ) ⁇ r or -[CH 2 -CH2-O-] X 2-CH 2 -CH 2 -, wherein Xi is an integer from
• x 2 is an integer from 1 to 6, is one of the following radicals
• a 7 is -CO-O-, -O-CO-, -NH-CO-, -CO-NH-.
• the cholesteric polymer P1 is obtainable by a ROMP- reaction of
• Z stands for A ⁇ -Aa-A VAe-A?-, if y is 1 , or, in case y is 2, for A 1 -(A 2 -A 3 -A 4 -A 5 -A 6 -A 7 -) 2
• Bi stands for a chiral organic group
• B 2 stands for an organic crosslinkable group
• B 3 stands for an organic, non-chiral, non-crosslinkable group
• Ai stands for a radical selected from the group consisting of - 5
• Vb, and y is 2 in case A T is one of the biradicals Via or Vlb, and in which
• X is selected from the group consisting of -CH 2 -, -O- and -S-, preferably,
• a 2 is -CH 2 - or -C(O)-
• a 3 is -O- or -NH-, preferably -O-, or
• a ⁇ -A 2 -A 3 stands for a radical of the formula VII
• X being preferably -CH _-, A is -(CH 2 )xr or -[C ⁇ -C ⁇ -O- ⁇ -C ⁇ -C ⁇ -, wherein is an integer from
• a 5 is one of the following radicals
• a 7 is -CO-O-, -O o-CO-, -NH-C-O-, or -CO-NH- 6 -
• chiral organic group B ⁇ usually any organic group exhibiting chirality, i.e. a molecule having at least a center of chirality or being intrinsically asymmetric, can be chosen.
• Such molecules and methods for the synthesis of chiral compounds are well-known in the art and examples can be found in every case-book dealing with organic chemistry.
• Preferred groups B are e.g. chiral hydrocarbons such as
• menthyl or camphor radicals such as menthyl or camphor radicals, alkaloid radicals such as quinine, groups which are derived from sugars, binaphthyl- or binaphthyl-derivatives, optically active glycoles, dialcohols or aminoacids.
• alkaloid radicals such as quinine
• groups which are derived from sugars, binaphthyl- or binaphthyl-derivatives such as optically active glycoles, dialcohols or aminoacids.
• organic chiral radicals are derivatives of e.g. cholesteryl radicals ("chol"), preferably
• terpenoid radicals such as methyl or camphor radicals
• alkaloid radicals such as quinine.
• organic crosslinkable group B 2 a radical of the formula
• B 2 ⁇ stands for an unsaturated group, preferably an unsaturated group having at least one carbon-carbon double bond, particularly preferred B 2 ⁇ comprises the vinyl group.
• organic, non-chiral, non-crosslinkable group B 3 preferably
• Ri stands for hydrogen, d-Cio-alkyl, CrCio-alkoxy, CrCio-alkylmercapto, -CN, - NO 2 or halogen, can be used.
• C ⁇ -C 10 alkyl stands for e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert.- butyl, n-amyl, tert.-amyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, preferably for d- C 4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert.-butyl;
• CrC 10 -alkoxy stands for e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, i-butoxy, tert.-butoxy, n-amyloxy, tert.-amyloxy, hexyloxy, heptyloxy, octyloxy, 2- ethylhexyloxy, nonyloxy, decyloxy, preferably for C r C 4 alkoxy such as methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, sec.-butoxy, i-butoxy, tert.-butoxy;
• CrCio-alkylmercapto stands for e.g. methylmercapto, ethylmercapto, n-propylmercapto, isopropylmercapto, n-butylmercapto, sec-butylmercapto, i-butylmercapto, tert.- butylmercapto, n-amylmercapto, tert.-amylmercapto, hexylmercapto, heptylmercapto, octylmercapto, 2-ethylhexylmercapto, nonylmercapto, decylmercapto, preferably for d- C alkyl such as methylmercapto, ethylmercapto, n-propylmercapto, isopropylmercapto, n- butylmercapto, sec-butylmercapto, i-butylmercapto, tert.-butyl
• Preferred non-crosslinkable, non-chiral organic groups B 3 are e.g.
• strained cyclic olefinic molecules are used as monomer III, whereby strained cyclic olefinic molecules has the meaning within the scope of this invention that all cycloolefines can be used, with the exception of cyclohexene and its derivatives which can not be polymerized by a ring opening metathesis reaction.
• E.g. strained cyclic olefinic molecules can be monocyclic or polycyclic, bridged or non- bridged ring systems, preferably with two to four rings, which can be unsubstituted or substituted, and which can contain one or more hetero atoms such as O, S, N or Si, in one or more rings, and which can contain condensed aromatic or heteroaromatic rings like o- phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene.
• the single cyclic rings contain 3 to 16, more preferably from 3 to 12, most preferred 3 to 8 carbon or hetero atoms.
• the strained cyclic olefinic molecules can contain further non-aromatic double bonds, depending on the size of the ring, preferably between two to four additional double bonds.
• the strained cyclic olefinic molecules do contain more than one double bond, e.g. 2 to 4 double bonds, then, usually depending on the chosen conditions of the reaction, the chosen monomer and the amount of the catalyst, three-dimensionally crosslinked polymers can be built.
• Preferred cycloolefinic molecules are Diels-Alder-adducts of cyclopentadiene such as e.g.
• Such strained cyclic olefinic molecules are commercially available or can be synthesized according to well-known methods.
• Preferred cholesteric polymers P1 are obtainable by the polymerization of e.g. -9
• cholesteric polymers P1 are obtainable by the polymerization of e.g.
• Z-B ⁇ Z-B 2 and Z-B 3 can be obtained via two routes, if A T is a radical of formula IV (a or b) or V (a or b), and depending on whether A 2 is -CH 2 - or -CO-, and A 3 stands for -O-.
• the first route, (I), in which A 2 is -CH 2 -, A 5 is -O- and A 7 is -COOH, comprises the following steps:
• Compound VIII, ArCH 2 -OH is known or can be prepared by well known methods.
• the first compound is known from Beilstein, ElV, Vol. 9, p.142-143, the second one has the CAS-registration number 13366-81-9.
• Reaction step (l)(1) e.g. can be carried out analogously to the method described in Macromolecules 26 (1993) 1393-1401.
• Reaction step (l)(2) is a simple nucleophilic displacement, well known in the art (see e.g. "Methoden der Organischen Chemie", Houben-Weyl, vol. 6/3, chapter “Methods for the preparation and conversion of ethers", 4 th edition, 1965, p.24-32. - 12 -
• Reaction step (l)(3) is a usual esterification and can be carried out according to known methods.
• compound XII is a carboxylic acid
• Such a reaction is well-known to the organic chemist, e.g. such a reaction is described in detail in Methoden der Organischen Chemie, Houben-Weyl, "Carbonsauren und Derivate", E5, 4 th Ed., esp. p. 695-700.
• DCC dicyclohexylcarbodiimide
• a second route, (II), to synthesize the starting monomers I, II and III, in which A 1 is a radical of formula IV or V, A 2 is -CO- and A 3 and A 5 stand for -O-, and A 7 stands for -C(O)-O-, comprises the following steps:
• Reaction step (H)(4) can be carried out in analogy to the method described in Macromolecules 28 (1995) 806. - 13 -
• bicyclo[2.2.1]hept-5-ene-2-carboxylic acid is commercially available from Aldrich or can be prepared starting from cyclopentadiene with acrylic acid methyl ester yielding the corresponding bicyclo[2.2.1]hept-5-ene-2-carboxylic acid methyl ester, which can be hydrolyzed into the carboxylic acid by known methods.
• a T stands for the norbornene radical and the bridging group X is -S- or -O-, then the norbornene derivative can be prepared via a Diels-Alder reaction followed by a hydrolysis step:
• Reaction step (H)(5) is a usual esterification and can be carried as described above (compound esterification of compound XII) via an acid chloride or via the DCC-method.
• Reaction step (H)(6) is a usual esterification and can be carried as described above (compound esterification of compound XII) via an acid chloride or via the DCC-method.
• Preferred monomers of formula VI, especially of formula Via are e.g.
• Monomers on the basis of compounds Via can be synthesized according to known methods, e.g. via the following route:
• the acid chloride can be prepared e.g. with thionyl chloride, and the esterification can be carried out e.g. in analogy to the abovementioned possibilities or in the presence of a base such as triethylamine in tetrahydrofurane.
• the ester can be prepared starting from a compound with the formula XV, which is converted into an ester e.g. with the known thionyl chloride route, whereby the alcohol group is preferably protected during esterification: -15-
• inventive monomers Z-B ⁇ Z- B and Z-B 3 relate to inventive monomers Z-B ⁇ Z- B and Z-B 3 .
• a further embodiment of the instant invention relates to a composition
• a composition comprising from (a) 10 to 50 mol-% of compound Z(B 1 ) y and (b) from 90 to 50 mol-% of a mixture of (b1 ) from 0 to 100 mol-% of compound Z(B 2 ) y and (b2) from 100 to 0 mol-% Z(B 3 ) y , wherein the mol- percentages of (a) and (b), and (b1) and (b2), resp., summing up to 100 mol-%.
• Another embodiment of the present invention relates to three-dimensionally crosslinked cholesteric polymers P2, whereby the inventive cholesteric polymers P1 , in which the amount of Z-B 2 , II, is not 0, are further treated by crosslinking the crosslinkable groups B 2 in a photo polymerization reaction or thermally induced, preferably by a photo polymerization.
• inventive polymers P1 are used, which have been prepared starting with amounts of Z-B T in the range of from 10 to 50, preferably from 20 to 50 mol-%, and 90 to 50, preferably 80 to 50 mol-% of a mixture of from 0 to 100, preferably 20 to 100 mol-% Z-B 2 and 100 to 0, preferably from 80 to 0 mol-% Z-B 3 , y being preferably 1.
• the polymer properties of the cholesteric polymers P1 usually depend on essentially the chosen educts (monomers), process parameters, and the desired properties.
• the molecular weight can be chosen in a range of from 5,000 to 100,000, preferably 10,000- 40,000 g/mol, the polydispersity is - as a rule - low, and preferably is in the range of from 1.0 to 2.0, particularly preferred from 1.1 to 1.5. It is further preferred to chose the T g in the range of 70 to 200, more prefereably from 70 to 150°C.
• Another embodiment of the present invention relates to a process for the preparation of the inventive polymers P1 , wherein the polymerized material is obtainable by copolymerization of - 16 - at least two kinds of monomers, wherein one monomer is a chiral compound, characterized in carrying out the copolymerization by a ring opening metathesis polymerization in the presence of a catalyst of
• reaction temperature is chosen in the range of from 0 to 10, preferably from 20 to 80°C.
• reaction pressure is chosen in the range of from 80 to 500, preferably from 90 to 200 kPa.
• reaction time is chosen in the range of from 1 to 24, preferably from 3 to 10 h.
• catalysts usually all known catalysts which are able to catalyze a ring opening metathesis reaction can be used.
• Such polymerization catalysts are well-known e.g. from US 4,426,502, EP-A 348,852, WO 96/20235, WO 93/20111 , WO 96/04289, WO 97/06185. - 17 -
• Hali and Hal 2 denote independently from each other halogen such as F, Cl, Br or I,
• Ti and T 2 denote independently from each other for a tertiary phosphine or phosphite, or both together stand for a bitertiary diphosphine or diphosphite,
• T 3 stands for an organic group such as aryl, alkyl, alkenyl, vinyl, benzyl, or a heteroatom bonded group such as alkoxy, aryloxy, alkenyloxy, alkylthio or arylthio.
• CI 2 [P(i-Pr) 3 ] 2 Ru CHPh
• the mol ratio of catalyst to the total amount of monomers is chosen in the range of from 0.0005 to 0.1 , preferably from 0.01 to 0.04.
• the above described processes can be carried out in the presence of a solvent such as - usually depending on the chosen catalyst - halogenated hydrocarbons like methylene chloride, 1 ,1 ,2-trichloroethane, and chloroform, aromatic hydrocarbons like toluene and xylenes.
• a solvent such as - usually depending on the chosen catalyst - halogenated hydrocarbons like methylene chloride, 1 ,1 ,2-trichloroethane, and chloroform, aromatic hydrocarbons like toluene and xylenes.
• the amount of solvent is chosen in the range of from 0.01 mol to 1 mol per 1 liter, preferred 0.08 to 0.12, particularly preferred 0.1 mol/l of the reaction mixture.
• Another preferred embodiment of this invention relates to the abovementioned processes, whereby at the end of the reaction a catalyst end-capping agent is added to remove the catalyst from the polymer chain. - 18 -
• Such a catalyst end-capping agent can be either a vinyl compound such as vinyl ethyl ether, vinyl trimethyl silane for the ruthenium based catalysts, or an aldehyde such as benzaldehyde for the molybdenum based catalysts.
• a vinyl compound such as vinyl ethyl ether, vinyl trimethyl silane for the ruthenium based catalysts, or an aldehyde such as benzaldehyde for the molybdenum based catalysts.
• aldehyde such as benzaldehyde for the molybdenum based catalysts.
• the mol ratio of the catalyst end capping agent to the amount of used catalyst is chosen in the range of from 1 :1 to 1 :1000, preferred from 1 :10 to 1 :100.
• the reaction mixture can be worked up in a known manner.
• the polymer is precipitated in a solvent, in which the polymer is not or only partially soluble, such as ethanol or methanol.
• chain transfer agents such as terminal alkenes can be added to the reaction mixture.
• chain transfer agents such as terminal alkenes
• Such agents are known, e.g. from Macromolecules 28 (1995) 500-511 , esp. for molybdenum based catalysts, and from Macromolecules 26 (1993) 4742-4747 for ruthenium based catalysts.
• Another embodiment of the instant invention relates to a process for the preparation of the crosslinked polymer P2, wherein the inventive cholesteric polymer P1 (wherein the preparation step the amount of component (b1) has been chosen to be greater than zero, is further treated by crosslinking the crosslinkable groups B 2 in a photo polymerization reaction or thermally induced, preferably by a photo polymerization.
• the polymeric material usually is crosslinked in such a manner that it is applied at a sufficient temperature, depending on the kind of used polymeric material, e.g. - in case of norborneethers and norborneesters are used - of from 0 to 180°C, preferably 20 to 120°C, to a substrate, e.g. made out of a polyester, then oriented by conventional methods, for example, by treating the melt with a doctor blade or by applying electrical or magnetic fields and, subsequently, exposing the whole composition to radiation from a UV lamp.
• a sufficient temperature depending on the kind of used polymeric material, e.g. - in case of norborneethers and norborneesters are used - of from 0 to 180°C, preferably 20 to 120°C, to a substrate, e.g. made out of a polyester, then oriented by conventional methods, for example, by treating the melt with a doctor blade or by applying electrical or magnetic fields and, subsequently, exposing the whole composition to radiation from a UV lamp.
• the polymeric material is crosslinked in the presence of a photoinitiator, a polymerization inhibitor, and, if desired, non-mesogenic monomers, and/or a reactive diluter, and/or a chiral dopant.
• a photoinitiator e.g., a photoinitiator, a polymerization inhibitor, and, if desired, non-mesogenic monomers, and/or a reactive diluter, and/or a chiral dopant.
• the layer thickness is chosen in the range of from 3 to 24, preferably of from 3 to 6 ⁇ m.
• a photoinitiator is added to the polymeric material (such as the known QUANTACURE ®, or IRGACURE® type photoinitiator types) in an effective amount.
• the polymeric material such as the known QUANTACURE ®, or IRGACURE® type photoinitiator types
• the use of such a photoinitiator is described in more detail for example in US 5,211 ,877.
• the crosslinking can also be carried out by known methods using heat, i.e. thermally induced.
• dihydroxy benzene which can be substituted with C C 6 -alkyl or in which one or both hydroxy groups are replaced with an ether group.
• ether group Such compounds are described e.g. in US 5,211 ,877.
• Preferred compounds are e.g. hydroquinone, hydroquinone mono methylether, 4-tert.-butyl catechol.
• a chiral dopant such as cholesteryl-4-methacryloyloxy-benzoate (see e.g. US 5,211 ,877) can be applied in amounts in the range of from 5 to 40% by weight, related to the amount of polymer P1.
• a reactive diluter such as a dimethacrylate, e.g. ethanedioldimethacrylate, diethyleneglycoldimethacrylate, triethyleneglycoldimethacrylate, or hexanedioldimethacrylate can be applied in amounts in the range from 0.1 to 20 % by weight, related to the amount of P1.
• the photoinitiator generally is chosen in an amount in the range of 0.1 to 3% b.w., based on the polymer P1
• the polymerization inhibitor generally is chosen in an amount in the range of from 0.01 to 0.05% b.w., based on the polymer P1
• the amount of diluter generally is chosen in the range of from 0.1 to 20% b.w., based on the polymer P1.
• the crosslinking is carried out with UV light having a wavelength in the range of from 200 to 240 nm for a time period generally in the range of from 10 to 60 seconds depending on the chosen power. - 20 -
• the obtained polymer P2 generally is removed mechanically by peeling off the support by known methods, e.g. by guiding the backing over a deflecting roller of small diameter, or using a ultrasonic bath.
• any other method by which the polymerized material can be removed from the backing is also suitable.
• the pigment material usually can be milled in a known manner, for example using a mill, such as an air-jet mill.
• crosslinked side-chain liquid crystalline polymers P2 are those comprising as repeating units the following structures
• Another embodiment of the present invention is related to the use of the inventive polymers P1 as precursor for the preparation of the inventive compounds P2, whereby P1 is crosslinked by the above described methods.
• Another embodiment of the present invention relates to the use of the inventive polymer P2 as pigments for coloring high molecular weight organic materials, e.g. biopolymers, plastic materials, including fibres, glasses, ceramic products, for formulations in decorative cosmetics, for the preparation of inks, printing inks, paint systems, in particular automotive paints and dispersion colors.
• organic materials e.g. biopolymers, plastic materials, including fibres, glasses, ceramic products
• decorative cosmetics for the preparation of inks, printing inks, paint systems, in particular automotive paints and dispersion colors.
• suitable organic materials of high molecular weight which can be colored with the inventive polymer P2 of this invention are vinyl polymers, for example polystyrene, poly- ⁇ -methylstyrene, poly-p-methylstyrene, poly-p-hydroxystyrene, poly-p-hydroxy- phenylstyrene, polymethyl methacrylate and polyacrylamide as well as the corresponding methacrylic compounds, polymethylmaleate, polyacrylonitrile, polymethacrylonitrile, polyvinyl chloride, polyvinyl fluoride, polyvinylidene chloride, polyvinylidene fluoride, polyvinyl acetate, polymethyl vinyl ether and polybutyl vinyl ether; polymers which are derived from maleinimide and/or maleic anhydride, such as copolymers of maleic anhydride with styrene; polyvinyl pyrrolidone; ABS; ASA; polyamides; polyimides; polya
• cellulose, cellulose ethers and esters such as ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate, starch, chitin, chitosan, gelatine, zein; natural resins; synthetic resins such as alkyd resins, acrylic resins, phenolic resins, epoxide resins, aminoformaldehyde resins - 22 - such as urea/formaldehyde resins and melamine/formaldehyde resin; vulcanized rubber; casein; silicone and silicone resins; rubber, chlorinated rubber; and also polymers which are used, for example, as binders in paint systems, such as novolaks which are derived from d- C 6 -aldehydes such as formaldehyde and acetaldehyde and a binucluear or mononuclear, preferably mononuclear, phenol which, if desired, is substituted by one or two CrC 9 alkyl
• Particularly preferred high molecular weight organic materials are, for example, cellulose ethers and esters, e.g. ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate, natural resins or synthetic resins (polymerization or condensation resins) such as aminoplasts, in particular urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyester, ABS, ASA, polyphenylene oxides, vulcanized rubber, casein, silicone and silicone resins as well as their possible mixtures with one another.
• cellulose ethers and esters e.g. ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate
• natural resins or synthetic resins polymerization or condensation resins
• aminoplasts in particular urea/formalde
• organic materials in dissolved form as film formers, for example boiled linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and urea/formaldehyde resins as well as acrylic resins.
• film formers for example boiled linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and urea/formaldehyde resins as well as acrylic resins.
• Said high molecular weight organic compounds may be obtained singly or in admixture, for example in the form of granules, plastic materials, melts or in the form of solutions, in particular for the preparation of spinning solutions, paint systems, coating materials, inks or printing inks.
• the novel inventive polymer P2 are used for the mass coloration of polyvinyl chloride, polyamides and, especially, polyolefins such as polyethylene and polypropylene as well as for the preparation of paint systems, including powder coatings, inks, printing inks and coating colors.
• preferred binders for paint systems are alkyd/melamine resin paints, acryl/melamine resin paints, cellulose acetate/cellulose butyrate paints and two-pack system lacquers based on acrylic resins which are crosslinkable with polyisocyanate.
• the novel inventive polymer P2 can be added in any desired amount to the material to be colored, depending on the end use requirements.
• the pigments composed according to this invention can be used in an amount in the range from 0.01 to 40, preferably from 0.1 to 20 % by weight, based on the total weight of the colored high molecular weight organic material.
• composition comprising
• customary additives such as fillers, paint auxiliaries, siccatives, plasticizers, UV-stabilizers, and/or additional pigments in effective amounts such as from 0.01 to 40, based on the total amount of (a) and (b).
• the pigmenting of the high molecular weight organic materials with the novel inventive polymer P2 is usually effected by incorporating said novel inventive polymer P2, if desired in the form of masterbatches, in the high molecular weight organic materials using customary apparatus suitable to this end, such as extruders, roll mills, mixing or milling apparatus.
• the material thus treated is then normally brought into the desired final form by methods which are known per se, such as calendering, molding, extrusion molding, coating, casting, extruding, or by injection molding.
• plasticizers can be added to the high molecular weight substances prior to molding.
• Plasticizers may be, for example, esters of phosphoric acid, phthalic acid and sebacic acid. Said plasticizers may be added before, during or after pigmenting the high molecular weight substances with the inventive polymer P2 of this invention. - 24 -
• novel inventive polymer P2 may advantageously be used in admixture with fillers, transparent and opaque white, colored and/or black pigments as well as customary luster pigments in the desired amount.
• the corresponding high molecular weight organic substances such as binders, synthetic resin dispersions etc. and the novel inventive polymer P2 are usually dispersed or dissolved together, if desired together with customary additives such as fillers, paint auxiliaries, siccatives, plasticizers and/or additional pigments, in a common solvent or mixture of solvents.
• customary additives such as fillers, paint auxiliaries, siccatives, plasticizers and/or additional pigments
• the inventive polymers P1 have the advantage that they exhibit a very narrow polydispersity.
• the starting material used are derivatives of norbornene with an endo-exo ratio of 9:1.
• the norbornenes are synthesized using usual synthetic methods starting from Bicyclo[2.2.1]hept- 5-ene-2 carboxylic acid methyl ester (obtained by Diels-Alder of cyclopentadiene with acrylic acid methyl ester).
• Polymers are characterized by their GPC (showing less than 3% of monomers) and by elemental analysis.
• Example 1 45.4 g (0.22 mol) of dicyclohexylcarbodiimide ("DCC") are added to a suspension of 30.4 g (0.22 mol) of bicyclo-[2.2.1]-hept-5-ene 2-carboxylic acid, 30.4g (0.22 mol) of 4-[6-(hydroxyhexyl)oxy] benzoic acid (as described in Macromolecules 1995, 28, - 25 -
• DCC dicyclohexylcarbodiimide
• Example 2 5.23 g (0.044 mol) of thionyl chloride is added dropwise to a suspension of 14.34 g (0.04 mol) of the product obtained in example 1 in 50 ml of dried tetrahydrofurane ('THF') at r. t. The mixture is then heated to 50°C for 2 hours, at which point gas evolution has ceased. This crude mixture is added to a solution of 7.08 g (0.04 mol) 4-methacryloyl- amino-Dhenol (obtained by reaction of 4-aminophenol with methacryloyl anhydride according to J. Org. Chem. USSR 4 (1968) p.
• Example 3 4.54 g (0.022 mol) of DCC are added to a suspension of 7.17 g (0.02 mol) of the product obtained in example 1 , 7.73 g (0.02 mol) of cholesterol and 0.27 g (0.0022 mol) DMAP in 100 ml CH 2 CI 2 . The mixture is stirred overnight at r. t. under an atmosphere of nitrogen. The precipitated urea is filtered off and the resulting clear solution is washed with a 5% b.w. aqueous solution of NaHCO 3 , then with 0.1 N HCI, followed by again a 5% b.w. aqueous solution of NaHCO 3 , and finally with a saturated aqueous solution of NaCI.
• Thermotropic behaviour (determined using DSC and microscope): 90°C (T g ), 110°C - 170°C cholesteric phase, 170°C isotropic
• Example 5 4.14 g (0.03 mol) of 4-hydroxy-benzoic acid are added to a solution of 3.7 g (0.066 mol) of KOH and 10 mg crystals of Kl in EtOH (60ml) and water (6ml). 9.41 g (0.033 mol) of bicyclo[2.2.1]hept-2-en-5-yl)methyl 6-bromohexyl ether (CA:151889-75-7) are added dropwise to this solution at r. t. and thereafter the mixture is heated at 75°C for 6 h. The mixture is poured on 500 ml of iced water. After acidification with 1 N HCI the precipitated product is filtered, washed with water and dried.
• bicyclo[2.2.1]hept-2-en-5-yl)methyl 6-bromohexyl ether CA:151889-75-7
• Example 6 2.27 g (0.011 mol) of DCC are added to a suspension of 3.44 g (0.01 mol) of the product obtained in example 5, 4.25 g (0.011 mol) of cholesterol and 0.13 g (0.0011 mol) of DMAP in 60 ml dried CH 2 CI 2 . The mixture is stirred overnight at r. t. under an atmosphere of - 27 - nitrogen. The precipitated urea is filtered off and the resulting clear solution is washed with an aqueous 5% b.w. solution of NaHCO 3 , then with 0.1 N HCI, and afterwards with an aqueous 5% b.w. solution of NaHCO 3 , and finally with a saturated aqueous solution of NaCI.
• Thermotropic behaviour (determined using DSC and a microscope): 90°C (T g ), 110 - 175°C cholesteric phase, 175°C isotropic. - 28 -
• Example 9 A mixture of 1g of the product obtained in example 4, 0.2 g of cholesterol 4- methacryloyloxy-benzoate, 0.1 g hexanediol dimethacrylate, 0.03 g of 2-methyl-1-(4- (methylthio)phenyl)-2-morpholino-propanone-1 (e.g. commercially available as IRGACURE®907, Ciba Specialty Chemicals Inc.), 0.005 g isopropenylthioxanthone (e.g.
• the material is removed mechanically by peeling off from the support using an ultrasonic bath. Milling of the material is then carried out in a air-jet mill.
• Example 10 Example 9 is repeated with the difference, that 1 g of the product obtained in example 8 is used.

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• 1999
  • 1999-01-19 AU AU28283/99A patent/AU2828399A/en not_active Abandoned
  • 1999-01-19 EP EP99908799A patent/EP1051438A1/de not_active Withdrawn
  • 1999-01-19 WO PCT/EP1999/000281 patent/WO1999037701A1/de active Search and Examination

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