CA1303786C - Transparent thermoplastic molding composition - Google Patents
Transparent thermoplastic molding compositionInfo
- Publication number
- CA1303786C CA1303786C CA000561196A CA561196A CA1303786C CA 1303786 C CA1303786 C CA 1303786C CA 000561196 A CA000561196 A CA 000561196A CA 561196 A CA561196 A CA 561196A CA 1303786 C CA1303786 C CA 1303786C
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- Canada
- Prior art keywords
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- deuterium
- denotes
- fluorine
- atoms
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Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
- G02B6/02—Optical fibres with cladding with or without a coating
- G02B6/02033—Core or cladding made from organic material, e.g. polymeric material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/22—Esters containing halogen
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
Abstract
Abstract of the disclosure A transparent thermoplastic molding composition which is essentially derived from an ester of a (meth)acrylic acid with a cyclic alcohol, can be produced in a simple and economical fashion. In this molding composition, acid and alcohol radicals can be deuterated and/or fluorinated.
The particularly preferred alcohol component is 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-en-2-ol. The molding composition can be processed into objects of high trans-parency and thermal distortion resistance.
The particularly preferred alcohol component is 1,4,5,6,7,7-hexachlorobicyclo[2.2.1]hept-5-en-2-ol. The molding composition can be processed into objects of high trans-parency and thermal distortion resistance.
Description
HOECHST AKTIENGESELLSCHAFT HOE 87/F 074 Dr.DA/je Description Transparent thermoplastic molding composition The invention relates to a transparent, thermoplastic mol-ding compos;tion which is suitable for the production of polymeric glasses, articles for the optical industry and optical fibers for transmission of light signals, and to a process for the production thereof. The molding compo-sition has a high thermal distortion resistance.
Optical fibers can comprise a core and a sheath, the corematerial always having a higher refractive index than the sheath material. The core material and the sheath mate-rial of such an optical fiber should absorb as littlelight as possible.
The polymeric materials employed the most frequently hitherto for optical fibers are homopolymers and copoly-mers of methyl methacrylate. Whereas halogen-containing polymers have also been employed for the core, exclusively - fluorine-containing polymers have hitherto been used for the sheath since they have a lower refractive index. In order to reduce light absorption, it has also already been proposed to replace the hydrogen atoms in the mono-mers and polymers by deuterium.
Copolymers of methyl methacrylate with a compound of the formula CH2=CR-(CO-O)n-Ararm (R=H or CH3; n = zero or 1, and m = 1 to 5) have been disclosed (cf. German Offenlegungsschrift 2,202,791). Acrylates and methacry-lates of mono-, di-, tri-, tetra- and pentabromophenol have been mentioned by name.
Furthermore, a molding composition is known which com-prises a polymeric ~-fluoroacrylate which can contain deuteriu0 atoms both on the B-carbon atom of the vinyl 1;~03786 group and in the alcohol component (European Application Publication 0,128,517). These polymers are used as core materials for optical fibers; they have a molecular weight of 200,000 to 5,000,000 (gel permeation), a re-fractive ;ndex of 1.45 to 1.60 and a softening point of 100 to 200C. The sheath material used for the optical fibers are polymers which have a lower refractive index;
su;table for this purpose are, inter alia, polymers of ~-fluoroacrylates whose alcohol component contains fluorine atoms, for example trifluoroethyl ~-fluoroacrylate and hexafluoroisobutyl ~-fluoroacrylate.
The preparation and properties of the abovementioned poly-(fluoroalkyl ~-fluoroacrylates) are likewise known (European Application Publication 0,128,516). The poly-mers are obtained by free-radical ;nitiated bulk, solu-tion or suspension polymerization of the monomers in the presence of a chain-transfer agent at a temperature of 0 to 100C. The polymers have a molecular weight of 200,000 to 5,000,000 (gel permeation), a refractive index of 1.36 to 1.44 and a softening point of 80 to 140C.
In add;tion, an opt;cal fiber has been described whose - core material is produced by block polymerization of, ;nter al;a, halogenated aryl methacrylates, for example pentafluorophenyl methacrylate (cf. Japanese Published Specificat;on 60-242,404).
Furthermore, polyhalogenated aryl(fluoro/meth)acrylate-conta;n;ng polymers have been proposed as materials for polymer;c opt;cal f;bers. Finally, polymers have been disclosed which were produced by polymerization of two allyl alcohol groups which have been ester;fied using the carboxylic acid groups of 1,4,5,6,7,7-hexachlorobicyclo-hept-5-ene-2,3-d;carboxylic acid (cf. Japanese Published Specification 61-51,901).
However, such polymers cannot be processed thermoplasti-cally since they crosslink during the polymerization.
Polymers which contain the 1,4,5,6,7,7-hexachloro[2.2.1]-bicyclohept-5-en-2-yl group in the alcohol part of acry-lates and methacrylates have also long been known (cf.
US Patent 3,022,277). ~owever, nothing has been disclosed on the optical properties, the thermal distortion resis-tance and the processing properties of these polymers, or on the properties of copolymers with other acrylates and methacrylates.
1û The object ~as to provide a polymer which can be prepared in a simple and economical fashion and which can be pro-cessed into objects of high transparency and thermal dis-tortion resistance.
It has been found that a transparent thermoplastic mold-ing composition which is essentially derived from an ester of a (meth)acrylic acid with a bicyclic alcohol, it being possibLe for the acid and alcohol radical to be deuterated and/or halogenated, is capable of achieving the object.
The invention thus relates to a transparent thermoplastic molding composition comprising 10 to 100% by weight of units which are derived from an ester of the formula (I) C
R~ R3 1 (R5)~ ¦ \ ( I ) 2,C = C - C - O - C ~C /
R
in wh;ch R6 R1 denotes a hydrogen, deuterium or fluorine atom, R2 denotes a hydrogen, deuterium or fluorine atom, R denotes a hydrogen, deuterium, fluorine, chlorine or bromine atom, a cyano group, or a methyL group in which all or some of the hydrogen atoms may be replaced by deuterium, fluorine or chlorine atoms, R4 denotes a hydrogen or deuterium atom or a C1- to Cs-alkyl group in which all or some of the hydrogen atoms may be replaced by deuterium or fluorine atoms, R5 denotes a -CHR9 or -CDR9 group in which R9 is a hydro-gen, deuter;um, fluorine, chlorine or bromine atom or a C1- to Cs-alkyl group in wh;~h all or some of the S hydrogen atoms may be replaced by deuterium or fluor-ine atoms, R6 denotes a fluorine, chlorine or bromine atom or a tri-fluoromethyl group, R7 denotes a -CH2 group in which all or some of the hydro-gen atoms may be replaced by deuterium, fluorine, chlor-ine or bromine atoms, by two CH30 groups or by one 1', 2' -ethanediyldioxy group, denotes a carbonyl group or an ethylene group ;n which all or some of the hydrogen atoms may be replaced by deuterium, chlorine or bromine atoms or by an oxo (0=) group, R8 denotes a -CR10=CR10 group in ~hich R10 is a fLuor-ine, chlorine or bromine atom or a trifluoromethyl group, or denotes a -C(R11)2-C(R11)2 group in which R11 is a fluorine atom or a trifluoromethyl group, and n is zero or 1, n not being zero when R7 is a -CH2- or carbonyl group, and 90 to 0% by weight of units which are derived from other - copolymerizable vinyl compounds.
In addition, the invention also relates to the process for the production of these molding compositions and to the transparent optical objects produced from the molding composition.
In formula (I), R1 is preferably a hydrogen, deuterium or fluorine atom, in particular a hydrogen or deuterium atom, R2 is preferably a hydrogen, deuterium or fluorine atom, in particular a hydrogen or deuterium atom, R3 ;s preferably a hydrogen, deuterium or fluorine atom, or a methyl group in which all or sone of the hydrogen atoms may be replaced by deuterium atoms, in particular is a deuterium or fluorine atom or a trideuteromethyl group, R4 is preferably a hydrogen or deuterium atom, R5 is preferably a methylene, deuteromethylene or chloromethylene group, in particular a methylene or deuteromethylene group, R6 is preferably a chlorine or bromine atom or a tri-fluoromethyl group, in particular a chlorine or bromine atom, R7 is preferably a methylene group in ~hich the hydro-gen atoms may be replaced by deuterium, chlorine or bromine atoms or by t~o methoxy groups, is a carbonyl group or an ethylene group in ~hich the hydrogen atoms may be replaced by chlorine atoms or by an oxo group, in particular is a -CH2-, -CD2-, -CCl2-, -C8r2-, -CHCl-, -C(=0)-, -C(=0)-CCl2- or -CH2-CH2- group, R8 is preferably a -CR10=CR10- group in which R10 may denote a chlorine or bromine atom or a trifluoromethyl group, in particular may denote a chlorine or bromine atom, or is a -C(R11)2-C(R11)2- group in ~hich R11 may denote a fluorine atom or a trifluoromethyl group, and n is preferably 1.
The acid component of the esters used according to the invention is thus preferably acrylic acid, methacrylic acid, rl-fluoroacrylic acid, ~,B-difluoroacrYlic acid or the corresponding fully or partly deuterated compounds, in particular perdeuteromethacrylic acid, perdeuteroacry-lic acid, ~-fluoroacrylic acid or perdeutero-~-fluoro-acrylic acid; the alcohol component is preferably 1,3,4,5,6,7,7-heptachlorobicycloC2.2.1]hept-5-en-2-ol, 1,4,5,6,7,7-hexachloro- or -hexabromobicycloC2.2.1]hept-5-en-2-ol, 1,4,5,6,7-pentachlorobicycloC2.2.1]hept-5-35 en-2-ol, 1,4,5,6-tetrachlorobicycloC2.2.1]hept-5-en-2-ol, 1,2,3,4-tetrachlorob;cycloC2.2.13hept-2-en-7-ol, 1,4,5,6-tetrakis(trifluoromethyl)-7-oxo- or -7-bis(methoxy)-bicycloC2.2.1]hept-5-en-2-ol, 1,2,3,4-tetrakis(tri-fluoromethyl)bicycloC2.2.1]hept-2-en-7-ol, 1,2,3,4-~03786 tetrabromo-5,6-dichlorobicyclot2.2.1]hept-2-en-7-ol, 1,2,3,4-tetrachloro-5,6-dibromobicyclo~2.2.1]hept-2-en-7-ol, 5,5,6,6-tetrakis(trifluoromethyl)bicycloC2.2.1]
heptan-2-ol, 5,5,6,6-tetrafluorobicyclo[2.2.1~heptan-2-ol, 1,4,5,5(or 6,6),7,8-hexachloro-6(or 5)-oxobicyclo C2~2.1]oct-7-en-2-ol or 1,4,5,5,6,6,7,8-octachloro-bicyclot2.2.1]oct-7-en-2-ol, in particular 1,4,5,6,7,7-hexachloro- or -hexabromobicyclot2.2.1]hept-5-en-2-ol, 1,4,5,6,7-pentachlorobicyclot2.2.1]hept-5-en-2-ol, 1,4,5,6-tetrachlorobicyclot2.2.1]hept-5-en-2-ol, 5,5,6,6-tetrak;s(trifluoromethyl)bicyclot2.2.1]heptan-2-ol, 5,5,6,6-tetrafluorobicyclot2.2.1]heptan-2-ol, 1,4,5,5(or 6,6),7,8-hexachloro-6(or 5)-oxobicyclo-t2.2.1]oct-7-en-2-ol.
According to the invention, those esters are preferabLy used in whose alcohol and ac;d component the hydrogen atoms have been substituted as fully as possible by deuterium, fluor;ne, chlorine and bromine atoms or by trifluoromethyl groups, in particular esters of perdeu_ teromethacrylic acid, perdeuteroacrylic acid, ~-fluoro-acrylic acid or perdeutero-~-fluoroacrylic acid with 1,4,5,6,7,7-hexachloro- or -hexabromobicyclo[2.201]
- hept-5-en-2-ol-2,2,3-d3,1,4,5,6,7-pentachlorobicyclo t2.2.1~hept-5-en-2-oL-2,2,3-d3, 1,4,5,6-tetrachloro-bicyclot2.2.1~hept-S-en-2-ol-2,2,3-d3, 5,5,6,6-tetrakis(trifluoromethyl)b;cyclot2.2.1~heptan-2-ol-1,2,3,4,7,7-d6, 5,5,6,6-tetrafluoro-bicyclot2.2.1]
heptan-2-ol-1,2,3,4,7,7-d6 or 1,4,5,5(or 6,6),7,8-hexachloro-6(or 5)-oxob;cyclot2.2.1]oct-7-en-2-ol-2,2,3-d3.
The molding composition according to the invention com-prises from 10 to 100, preferably 40 to 1ûO, in particu-lar S0 to 80, ~ by weight of units which are derived from an ester of the formula (I), and 90 to 0, preferably 60 to 0, in particular 50 to 20, % by weight of units ~hich are derived from other copolymeri~able vinyl compounds.
Su;table compounds are C1- to C6-alkyl esters of acryl;c i303786 acîd, C1- to C6-alkyl esters of methacrylic acid, C1- to C6-alkyl esters of ~-fluoroacrylic acid, styrene or sub-stituted styrene. The esters of acrylic acid, methacrylic ac;d and a-fluoroacrylic acid, and the deuterated deriva-tives thereof, are preferably used. In particular, methyl acrylate, methyl methacrylate and methyl ~-fluoroacrylate are employed, the corresponding deuterated compounds being particularly preferred.
The molding composition according to the invention is produced by free-radical block polymerization or suspen-sion, emulsion or solution polymerization, in particular by block polymerization, of a compound of the formula ~I) and, if appropriate, another copolymerizable vinyl compound.
Suitable free-radicaL active initiators are azo compounds, such as azo-bisisobutyronitrile, azo-bis(cyclohexylcarbo-nitrile), azo-bis(tert.-octane) and 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, and organ;c peroxides, such as tert.-butyl peroxide, tert.-butyl peroctoate, tert.-butyl peroxyisopropylcarbonate, tert.-butyl hydro-peroxide and tert.-butyl peroxyisobutyrate. The amount of initiator is in the range 0.001 to 3, preferably 0.035 to 0.3, mole per 100 moles of the monomer or monomers.
Polymerization is advantageously carried out in the pre-sence of a chain-transfer agent (regulator). Suitable for this purpose are, in part;cular, mercaptans, such as butyl mercaptan, tert.-butyl mercaptan, propyl mercaptan, phenyl mercaptan, tert.-hexyl mercaptan and butylene-1,4-dithiol, and esters of mercaptoacetic acid, for example ethyl mercaptoacetate and ethylene glycol bis(mercapto-acetate). The polymerization temperature is 60 to 180C, preferably 80 to 160C, particularly preferabLy 100 to 160C.
It is advisable to degas the reaction mixture before commencing the poLymerization For this purpose, the reaction mixture comprising monomers, initiator and, if 1~03786 appropriate regulator is initially cooled in a reactor to a temperature of at least -80C the reactor is then evacuated and ;n a sealed state warmed to a temperature of 0 to 25C; this procedure can be repeated several S times.
The molding composition according to the invention is produced in the form of a glass-clear thermoformable material. It is therefore sùitable above all as a material for the production of transparent objects for example resist materials lenses optical fibers and alone or mixed with another polymer which has a different refractive index as a material for optical data-storage media. The spectral transparency of the molding compo-sition is particularly h;gh in the wavelength range from 600 to 1 300 nm. The molding composition exhibits the characteristic properties belo~:
Mean molecular weight 8 000 to 5 00û 000 preferably 50 C00 to 200 000 (measured by the light-scattering method).
Glass-transition temperature 95 to 250C preferably 120 - to 200C particularly preferably 150 to 180C.
Decomposition temperature at least 230C preferably 250 to 300C.
The objects manufactured from the molding composition according to the invent;on have an excellent thermal dis-tortion res;stance and are nonflammable.
The follo~ing Examples serve to illustrate the invention in greater detail. Percentages in each case relate to the weight.
1~03786 _ 9 _ Exa-ple 1 1~ 1,2,3,4,7,7-Hexachlorob;cyclo[2.2.1]hept-2-en-5-yl acetate s 100 9 (0.366 mol) of hexachlorocyclopentadiene and 37 g (0.43 mol) of vinyl acetate were refluxed in a 250 ml three-neck flask equipped with magnetic st;rrer, thermometer and reflux condenser. During re-fluxing, the temperature cf the reaction mixture was initially 87C and towards the end, after 40 hours, 139C. The mixture was subjected to fractional dis-tillation, ~5 9 of the ester being obtained as the main fraction at 105-112C (0.05 mbar) (72% of theory).
2) 1,2,3,4,7,7-Hexachlorobicyclot2.2.1]hept-2-en-5-ol 1,760 ml of methanol and 17.6 ml of concentrated hydrochloric acid were added to 880 9 (2.45 mol) of compound 1 in a 4 l three-neck flask equipped with magnetic stirrer, thermometer and reflux condenser, and the mixture was refluxed for 4 hours. The solvent was then evaporated and the solid residue was recrys-- tallized from n-heptane, 704 g of the alcohol being obtained (~0% of theory).
Optical fibers can comprise a core and a sheath, the corematerial always having a higher refractive index than the sheath material. The core material and the sheath mate-rial of such an optical fiber should absorb as littlelight as possible.
The polymeric materials employed the most frequently hitherto for optical fibers are homopolymers and copoly-mers of methyl methacrylate. Whereas halogen-containing polymers have also been employed for the core, exclusively - fluorine-containing polymers have hitherto been used for the sheath since they have a lower refractive index. In order to reduce light absorption, it has also already been proposed to replace the hydrogen atoms in the mono-mers and polymers by deuterium.
Copolymers of methyl methacrylate with a compound of the formula CH2=CR-(CO-O)n-Ararm (R=H or CH3; n = zero or 1, and m = 1 to 5) have been disclosed (cf. German Offenlegungsschrift 2,202,791). Acrylates and methacry-lates of mono-, di-, tri-, tetra- and pentabromophenol have been mentioned by name.
Furthermore, a molding composition is known which com-prises a polymeric ~-fluoroacrylate which can contain deuteriu0 atoms both on the B-carbon atom of the vinyl 1;~03786 group and in the alcohol component (European Application Publication 0,128,517). These polymers are used as core materials for optical fibers; they have a molecular weight of 200,000 to 5,000,000 (gel permeation), a re-fractive ;ndex of 1.45 to 1.60 and a softening point of 100 to 200C. The sheath material used for the optical fibers are polymers which have a lower refractive index;
su;table for this purpose are, inter alia, polymers of ~-fluoroacrylates whose alcohol component contains fluorine atoms, for example trifluoroethyl ~-fluoroacrylate and hexafluoroisobutyl ~-fluoroacrylate.
The preparation and properties of the abovementioned poly-(fluoroalkyl ~-fluoroacrylates) are likewise known (European Application Publication 0,128,516). The poly-mers are obtained by free-radical ;nitiated bulk, solu-tion or suspension polymerization of the monomers in the presence of a chain-transfer agent at a temperature of 0 to 100C. The polymers have a molecular weight of 200,000 to 5,000,000 (gel permeation), a refractive index of 1.36 to 1.44 and a softening point of 80 to 140C.
In add;tion, an opt;cal fiber has been described whose - core material is produced by block polymerization of, ;nter al;a, halogenated aryl methacrylates, for example pentafluorophenyl methacrylate (cf. Japanese Published Specificat;on 60-242,404).
Furthermore, polyhalogenated aryl(fluoro/meth)acrylate-conta;n;ng polymers have been proposed as materials for polymer;c opt;cal f;bers. Finally, polymers have been disclosed which were produced by polymerization of two allyl alcohol groups which have been ester;fied using the carboxylic acid groups of 1,4,5,6,7,7-hexachlorobicyclo-hept-5-ene-2,3-d;carboxylic acid (cf. Japanese Published Specification 61-51,901).
However, such polymers cannot be processed thermoplasti-cally since they crosslink during the polymerization.
Polymers which contain the 1,4,5,6,7,7-hexachloro[2.2.1]-bicyclohept-5-en-2-yl group in the alcohol part of acry-lates and methacrylates have also long been known (cf.
US Patent 3,022,277). ~owever, nothing has been disclosed on the optical properties, the thermal distortion resis-tance and the processing properties of these polymers, or on the properties of copolymers with other acrylates and methacrylates.
1û The object ~as to provide a polymer which can be prepared in a simple and economical fashion and which can be pro-cessed into objects of high transparency and thermal dis-tortion resistance.
It has been found that a transparent thermoplastic mold-ing composition which is essentially derived from an ester of a (meth)acrylic acid with a bicyclic alcohol, it being possibLe for the acid and alcohol radical to be deuterated and/or halogenated, is capable of achieving the object.
The invention thus relates to a transparent thermoplastic molding composition comprising 10 to 100% by weight of units which are derived from an ester of the formula (I) C
R~ R3 1 (R5)~ ¦ \ ( I ) 2,C = C - C - O - C ~C /
R
in wh;ch R6 R1 denotes a hydrogen, deuterium or fluorine atom, R2 denotes a hydrogen, deuterium or fluorine atom, R denotes a hydrogen, deuterium, fluorine, chlorine or bromine atom, a cyano group, or a methyL group in which all or some of the hydrogen atoms may be replaced by deuterium, fluorine or chlorine atoms, R4 denotes a hydrogen or deuterium atom or a C1- to Cs-alkyl group in which all or some of the hydrogen atoms may be replaced by deuterium or fluorine atoms, R5 denotes a -CHR9 or -CDR9 group in which R9 is a hydro-gen, deuter;um, fluorine, chlorine or bromine atom or a C1- to Cs-alkyl group in wh;~h all or some of the S hydrogen atoms may be replaced by deuterium or fluor-ine atoms, R6 denotes a fluorine, chlorine or bromine atom or a tri-fluoromethyl group, R7 denotes a -CH2 group in which all or some of the hydro-gen atoms may be replaced by deuterium, fluorine, chlor-ine or bromine atoms, by two CH30 groups or by one 1', 2' -ethanediyldioxy group, denotes a carbonyl group or an ethylene group ;n which all or some of the hydrogen atoms may be replaced by deuterium, chlorine or bromine atoms or by an oxo (0=) group, R8 denotes a -CR10=CR10 group in ~hich R10 is a fLuor-ine, chlorine or bromine atom or a trifluoromethyl group, or denotes a -C(R11)2-C(R11)2 group in which R11 is a fluorine atom or a trifluoromethyl group, and n is zero or 1, n not being zero when R7 is a -CH2- or carbonyl group, and 90 to 0% by weight of units which are derived from other - copolymerizable vinyl compounds.
In addition, the invention also relates to the process for the production of these molding compositions and to the transparent optical objects produced from the molding composition.
In formula (I), R1 is preferably a hydrogen, deuterium or fluorine atom, in particular a hydrogen or deuterium atom, R2 is preferably a hydrogen, deuterium or fluorine atom, in particular a hydrogen or deuterium atom, R3 ;s preferably a hydrogen, deuterium or fluorine atom, or a methyl group in which all or sone of the hydrogen atoms may be replaced by deuterium atoms, in particular is a deuterium or fluorine atom or a trideuteromethyl group, R4 is preferably a hydrogen or deuterium atom, R5 is preferably a methylene, deuteromethylene or chloromethylene group, in particular a methylene or deuteromethylene group, R6 is preferably a chlorine or bromine atom or a tri-fluoromethyl group, in particular a chlorine or bromine atom, R7 is preferably a methylene group in ~hich the hydro-gen atoms may be replaced by deuterium, chlorine or bromine atoms or by t~o methoxy groups, is a carbonyl group or an ethylene group in ~hich the hydrogen atoms may be replaced by chlorine atoms or by an oxo group, in particular is a -CH2-, -CD2-, -CCl2-, -C8r2-, -CHCl-, -C(=0)-, -C(=0)-CCl2- or -CH2-CH2- group, R8 is preferably a -CR10=CR10- group in which R10 may denote a chlorine or bromine atom or a trifluoromethyl group, in particular may denote a chlorine or bromine atom, or is a -C(R11)2-C(R11)2- group in ~hich R11 may denote a fluorine atom or a trifluoromethyl group, and n is preferably 1.
The acid component of the esters used according to the invention is thus preferably acrylic acid, methacrylic acid, rl-fluoroacrylic acid, ~,B-difluoroacrYlic acid or the corresponding fully or partly deuterated compounds, in particular perdeuteromethacrylic acid, perdeuteroacry-lic acid, ~-fluoroacrylic acid or perdeutero-~-fluoro-acrylic acid; the alcohol component is preferably 1,3,4,5,6,7,7-heptachlorobicycloC2.2.1]hept-5-en-2-ol, 1,4,5,6,7,7-hexachloro- or -hexabromobicycloC2.2.1]hept-5-en-2-ol, 1,4,5,6,7-pentachlorobicycloC2.2.1]hept-5-35 en-2-ol, 1,4,5,6-tetrachlorobicycloC2.2.1]hept-5-en-2-ol, 1,2,3,4-tetrachlorob;cycloC2.2.13hept-2-en-7-ol, 1,4,5,6-tetrakis(trifluoromethyl)-7-oxo- or -7-bis(methoxy)-bicycloC2.2.1]hept-5-en-2-ol, 1,2,3,4-tetrakis(tri-fluoromethyl)bicycloC2.2.1]hept-2-en-7-ol, 1,2,3,4-~03786 tetrabromo-5,6-dichlorobicyclot2.2.1]hept-2-en-7-ol, 1,2,3,4-tetrachloro-5,6-dibromobicyclo~2.2.1]hept-2-en-7-ol, 5,5,6,6-tetrakis(trifluoromethyl)bicycloC2.2.1]
heptan-2-ol, 5,5,6,6-tetrafluorobicyclo[2.2.1~heptan-2-ol, 1,4,5,5(or 6,6),7,8-hexachloro-6(or 5)-oxobicyclo C2~2.1]oct-7-en-2-ol or 1,4,5,5,6,6,7,8-octachloro-bicyclot2.2.1]oct-7-en-2-ol, in particular 1,4,5,6,7,7-hexachloro- or -hexabromobicyclot2.2.1]hept-5-en-2-ol, 1,4,5,6,7-pentachlorobicyclot2.2.1]hept-5-en-2-ol, 1,4,5,6-tetrachlorobicyclot2.2.1]hept-5-en-2-ol, 5,5,6,6-tetrak;s(trifluoromethyl)bicyclot2.2.1]heptan-2-ol, 5,5,6,6-tetrafluorobicyclot2.2.1]heptan-2-ol, 1,4,5,5(or 6,6),7,8-hexachloro-6(or 5)-oxobicyclo-t2.2.1]oct-7-en-2-ol.
According to the invention, those esters are preferabLy used in whose alcohol and ac;d component the hydrogen atoms have been substituted as fully as possible by deuterium, fluor;ne, chlorine and bromine atoms or by trifluoromethyl groups, in particular esters of perdeu_ teromethacrylic acid, perdeuteroacrylic acid, ~-fluoro-acrylic acid or perdeutero-~-fluoroacrylic acid with 1,4,5,6,7,7-hexachloro- or -hexabromobicyclo[2.201]
- hept-5-en-2-ol-2,2,3-d3,1,4,5,6,7-pentachlorobicyclo t2.2.1~hept-5-en-2-oL-2,2,3-d3, 1,4,5,6-tetrachloro-bicyclot2.2.1~hept-S-en-2-ol-2,2,3-d3, 5,5,6,6-tetrakis(trifluoromethyl)b;cyclot2.2.1~heptan-2-ol-1,2,3,4,7,7-d6, 5,5,6,6-tetrafluoro-bicyclot2.2.1]
heptan-2-ol-1,2,3,4,7,7-d6 or 1,4,5,5(or 6,6),7,8-hexachloro-6(or 5)-oxob;cyclot2.2.1]oct-7-en-2-ol-2,2,3-d3.
The molding composition according to the invention com-prises from 10 to 100, preferably 40 to 1ûO, in particu-lar S0 to 80, ~ by weight of units which are derived from an ester of the formula (I), and 90 to 0, preferably 60 to 0, in particular 50 to 20, % by weight of units ~hich are derived from other copolymeri~able vinyl compounds.
Su;table compounds are C1- to C6-alkyl esters of acryl;c i303786 acîd, C1- to C6-alkyl esters of methacrylic acid, C1- to C6-alkyl esters of ~-fluoroacrylic acid, styrene or sub-stituted styrene. The esters of acrylic acid, methacrylic ac;d and a-fluoroacrylic acid, and the deuterated deriva-tives thereof, are preferably used. In particular, methyl acrylate, methyl methacrylate and methyl ~-fluoroacrylate are employed, the corresponding deuterated compounds being particularly preferred.
The molding composition according to the invention is produced by free-radical block polymerization or suspen-sion, emulsion or solution polymerization, in particular by block polymerization, of a compound of the formula ~I) and, if appropriate, another copolymerizable vinyl compound.
Suitable free-radicaL active initiators are azo compounds, such as azo-bisisobutyronitrile, azo-bis(cyclohexylcarbo-nitrile), azo-bis(tert.-octane) and 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, and organ;c peroxides, such as tert.-butyl peroxide, tert.-butyl peroctoate, tert.-butyl peroxyisopropylcarbonate, tert.-butyl hydro-peroxide and tert.-butyl peroxyisobutyrate. The amount of initiator is in the range 0.001 to 3, preferably 0.035 to 0.3, mole per 100 moles of the monomer or monomers.
Polymerization is advantageously carried out in the pre-sence of a chain-transfer agent (regulator). Suitable for this purpose are, in part;cular, mercaptans, such as butyl mercaptan, tert.-butyl mercaptan, propyl mercaptan, phenyl mercaptan, tert.-hexyl mercaptan and butylene-1,4-dithiol, and esters of mercaptoacetic acid, for example ethyl mercaptoacetate and ethylene glycol bis(mercapto-acetate). The polymerization temperature is 60 to 180C, preferably 80 to 160C, particularly preferabLy 100 to 160C.
It is advisable to degas the reaction mixture before commencing the poLymerization For this purpose, the reaction mixture comprising monomers, initiator and, if 1~03786 appropriate regulator is initially cooled in a reactor to a temperature of at least -80C the reactor is then evacuated and ;n a sealed state warmed to a temperature of 0 to 25C; this procedure can be repeated several S times.
The molding composition according to the invention is produced in the form of a glass-clear thermoformable material. It is therefore sùitable above all as a material for the production of transparent objects for example resist materials lenses optical fibers and alone or mixed with another polymer which has a different refractive index as a material for optical data-storage media. The spectral transparency of the molding compo-sition is particularly h;gh in the wavelength range from 600 to 1 300 nm. The molding composition exhibits the characteristic properties belo~:
Mean molecular weight 8 000 to 5 00û 000 preferably 50 C00 to 200 000 (measured by the light-scattering method).
Glass-transition temperature 95 to 250C preferably 120 - to 200C particularly preferably 150 to 180C.
Decomposition temperature at least 230C preferably 250 to 300C.
The objects manufactured from the molding composition according to the invent;on have an excellent thermal dis-tortion res;stance and are nonflammable.
The follo~ing Examples serve to illustrate the invention in greater detail. Percentages in each case relate to the weight.
1~03786 _ 9 _ Exa-ple 1 1~ 1,2,3,4,7,7-Hexachlorob;cyclo[2.2.1]hept-2-en-5-yl acetate s 100 9 (0.366 mol) of hexachlorocyclopentadiene and 37 g (0.43 mol) of vinyl acetate were refluxed in a 250 ml three-neck flask equipped with magnetic st;rrer, thermometer and reflux condenser. During re-fluxing, the temperature cf the reaction mixture was initially 87C and towards the end, after 40 hours, 139C. The mixture was subjected to fractional dis-tillation, ~5 9 of the ester being obtained as the main fraction at 105-112C (0.05 mbar) (72% of theory).
2) 1,2,3,4,7,7-Hexachlorobicyclot2.2.1]hept-2-en-5-ol 1,760 ml of methanol and 17.6 ml of concentrated hydrochloric acid were added to 880 9 (2.45 mol) of compound 1 in a 4 l three-neck flask equipped with magnetic stirrer, thermometer and reflux condenser, and the mixture was refluxed for 4 hours. The solvent was then evaporated and the solid residue was recrys-- tallized from n-heptane, 704 g of the alcohol being obtained (~0% of theory).
3) 1,2,3,4,7,7-Hexachlorobicyclo[2.2.1]hept-2-en-5-yl acrylate (AHC) 50 9 (0.158 mol) of compound 2 were dissolved in 150 ml of toluene in a 500 ml three-neck flask equipped with magnetic stirrer, thermometer and reflux condenser, and 21.5 9 (0.237 mol) of acryl chloride were added at 70C. The mixture was subsequently stirred at this temperature for a further 16 hours. The solvent was then evaporated and the res;due distilled. The fraction at around 118C ~60.6 9) was dissolved in diethyl ether and filtered through an Al203 column.
After evaporation of the diethyl ether from the ~103786 filtrate, 33.4 9 of the acrylate were obtained t57%
of theory).
After evaporation of the diethyl ether from the ~103786 filtrate, 33.4 9 of the acrylate were obtained t57%
of theory).
4) 1,2,3,4,7,7-Hexachlorobicyclo[2.2.1]hept-2-en-S-yl methacrylate (MA-HC) 200 9 (0.63 mol) of compound 2 were dissolved in S00 ml of toluene in a 1 L three-neck flask equipped with magnet;c stirrer, thermometer and reflux con-denser, and 99.2 9 (0.95 mol) of methacryl chloride were added. This mixture was then stirred under re-flux for 30 hours. The solvent was subsequently evaporated and the residue, dissolved in diethyl ether, filtered through an Al203 column. After evapora-tion of the diethyl ether, 189.4 9 of the methacrylate were obtained (78% of theory).
ExaopLe 2 A solution of 100 parts of hexachlorobicycloheptenyl acrylate (AHC), 0.05 part of dicumyl peroxide and 0.17 part of butyl mercaptan were filtered through a membrane ~ f;lter (pore s;ze 200 nm) into a glass vessel and care-fully degassed. For this purpose, the reaction mixture ~as firstly frozen using liquid nitrogen, and the glass vessel was then evacuated (0.001 mbar) and subsequently warmed to room temperature. This procedure was repeated three times. The reaction vessel was then sealed, and the degassed reaction mixture was initially warmed for 30 5 hours at a temperature of 123C, then at a temperature of 140C. After cooling to room temperature, a glass-clear polymeric material was obtained on which the follow-ing properties were measured.
35 Mean degree of polymerization Pw 2,050 Glass transition temperature159C
Decomposition temperature 270C
Melt flow index (250C; 3.8 kg)8 9/10 min 1303~86 Residual monomer content 0.5%
Refractive index n23 1.54 ExampLe 3 A solution of 50 parts of hexachLorobicycloheptenyl meth-acrylate ~MAHC), 0.03 part of a~oisobutyronitrile and 0.5 part of butyl mercaptan in 50 parts of chloroform were filtered and degassed analogously to Example 20 The de-gassed reaction mixture was then warmed at a temperatureof 60C for 20 hours. After the batch had been cooled to room temperature, 400 parts of acetone were added, and the resultant mixture was transferred ;nto 6,000 parts of hex-ane. The polymer which precipitates during this opera-tion was separated from the liquid, reprecipitated fromacetone/hexane and dried for 6 hours at a temperature of 100C in vacuo. 40 9 (80Z of theory) of a polymer were obtained on which the following properties were measured:
Mean degree of polymerization Pw 500 Glass transition temperature 220C
Decomposition temperature 300C
Exa~p~es 4 to 6 Solutions compr;sing various amounts of MAHC and methyl methacrylate (MMA) and containing 0.1 9 of a20isobutyro-nitrile and 0.15 g of butyl mercaptan in each case were filtered and degassed analogously to Example 2. The de-gassed reaction mixtures were each warmed to a tempera-ture of 60C for 30 minutes and, after cooling to room temperature, mixed with 300 ml of acetone. The mixtures obtained in each case were transferred into 5 l of hexane, and the precipitated copolymers were separated from the liquid and dried for 6 hours at a temperature of 70C.
The respective composition of the monomer mixture and the copolymer and the glass transition temperature (Tg) of the copolymer can be seen from Table 1.
Table 1 Example MMA:MAHC weight ratio Tg (C) l nD23 Monomer Copolymer mixture .
4 28:72 23:77 161 1.529 51:49 40:60 155 1.523 6 70:30 59:41 147 1.513 ~xaople 7 A mixture of 50 parts of MAHC and 50 parts of MMA, 0.05 part of tert.-butyl isopropylperoxycarbonate and 0.5 part of butanedithiol was saturated with nitrogen in a (press-ure-tight) reaction vessel equipped with stirrer and met-ering device. The reaction solution was warmed ~o 90Cwhile stirring.
It was possible to detect a slight increase in v;scosity, - and thus commencement of the reaction, from an increase in the power consumption of the stirrer. A sample was removed from the mixture 15 minutes after commencement of polymerization, and the MMA:MAHC concentration ratio was determined by gas chromatography. Corresponding to the increased consumption of MAHC, further parts of a mixture comprising 40 parts of MMA, 60 parts of MAHC, 0.05 par~ of butanedithiol and 0.4 part of tert.-butyl isopropylperoxycarbonate were metered in continuously, and the metering rate adjusted, in accordance with the re-sults of further (gas chromatographic) analyses so that a MMA:MAHC free monomer concentration ratio of 52:48 (9/9) was maintained in the reaction vessel.
~hen the subsequent metering ~as complete, the reaction mixture ~as heated to 160C over the course of 2 hours 1~03786 and kept at this temperature for 2 hours. The mixture was subsequently transferred into a two-stage degassing extruder where residual monomer was removed.
The glass transition point of the granulated material was Tg = 157C, and the mean degree of polymerization was Pw = 2,340.
Example 8 It was possible to mold the material from Example 2 in a mold at 250C under pressure to form lenses and similar optical objects. After the surface of a lens had been polished, a transmission of 91% of the incident light was achieved.
Transmission and image-formation properties of this lens remained unchanged even after storage for 24 hours at 100C and an atmospheric humidity of 100 0bar.
Comparison ExampLe A
A lens molded under the conditions of Example 8 from a polymeric glass element made from polymethyl methacrylate - (PMMA) exhib;ted, after polishing, a transmission of 89X
and comparable image-formation properties. After storage for only 2 hours at 120C, the surface of the lens was clearly cloudy and the shape of the lens had changed so substantially that a usable image was no longer produced.
Exa-ple 9 The polymerization by the method of Example 7 was repeated, and the polymer was processed directly, without granula-tion, to form an optical fiber. Of the light intensity which was shone into the front face of the optical fiber, it was possible to measure 45X after a length of three meters, and 7G% after a length of one meter.
After the fiber had been stored for 7 days at 120C and 130~786 an atmospheric humidity of 100 mbar, it was st;ll possible to detect 70% of the incident light intensity after a Length of one meter and 43% after three meters.
S Comparison Example ~:
A three-meter length of an optical fiber made from PMMA
exhibited a transmission of 70% at the beginning of the experiment. After storage at 110C for three hours, the length of the fiber had already shrunk by half and the transmission had dropped to 10% of the incident light intensity.
ExaopLe 2 A solution of 100 parts of hexachlorobicycloheptenyl acrylate (AHC), 0.05 part of dicumyl peroxide and 0.17 part of butyl mercaptan were filtered through a membrane ~ f;lter (pore s;ze 200 nm) into a glass vessel and care-fully degassed. For this purpose, the reaction mixture ~as firstly frozen using liquid nitrogen, and the glass vessel was then evacuated (0.001 mbar) and subsequently warmed to room temperature. This procedure was repeated three times. The reaction vessel was then sealed, and the degassed reaction mixture was initially warmed for 30 5 hours at a temperature of 123C, then at a temperature of 140C. After cooling to room temperature, a glass-clear polymeric material was obtained on which the follow-ing properties were measured.
35 Mean degree of polymerization Pw 2,050 Glass transition temperature159C
Decomposition temperature 270C
Melt flow index (250C; 3.8 kg)8 9/10 min 1303~86 Residual monomer content 0.5%
Refractive index n23 1.54 ExampLe 3 A solution of 50 parts of hexachLorobicycloheptenyl meth-acrylate ~MAHC), 0.03 part of a~oisobutyronitrile and 0.5 part of butyl mercaptan in 50 parts of chloroform were filtered and degassed analogously to Example 20 The de-gassed reaction mixture was then warmed at a temperatureof 60C for 20 hours. After the batch had been cooled to room temperature, 400 parts of acetone were added, and the resultant mixture was transferred ;nto 6,000 parts of hex-ane. The polymer which precipitates during this opera-tion was separated from the liquid, reprecipitated fromacetone/hexane and dried for 6 hours at a temperature of 100C in vacuo. 40 9 (80Z of theory) of a polymer were obtained on which the following properties were measured:
Mean degree of polymerization Pw 500 Glass transition temperature 220C
Decomposition temperature 300C
Exa~p~es 4 to 6 Solutions compr;sing various amounts of MAHC and methyl methacrylate (MMA) and containing 0.1 9 of a20isobutyro-nitrile and 0.15 g of butyl mercaptan in each case were filtered and degassed analogously to Example 2. The de-gassed reaction mixtures were each warmed to a tempera-ture of 60C for 30 minutes and, after cooling to room temperature, mixed with 300 ml of acetone. The mixtures obtained in each case were transferred into 5 l of hexane, and the precipitated copolymers were separated from the liquid and dried for 6 hours at a temperature of 70C.
The respective composition of the monomer mixture and the copolymer and the glass transition temperature (Tg) of the copolymer can be seen from Table 1.
Table 1 Example MMA:MAHC weight ratio Tg (C) l nD23 Monomer Copolymer mixture .
4 28:72 23:77 161 1.529 51:49 40:60 155 1.523 6 70:30 59:41 147 1.513 ~xaople 7 A mixture of 50 parts of MAHC and 50 parts of MMA, 0.05 part of tert.-butyl isopropylperoxycarbonate and 0.5 part of butanedithiol was saturated with nitrogen in a (press-ure-tight) reaction vessel equipped with stirrer and met-ering device. The reaction solution was warmed ~o 90Cwhile stirring.
It was possible to detect a slight increase in v;scosity, - and thus commencement of the reaction, from an increase in the power consumption of the stirrer. A sample was removed from the mixture 15 minutes after commencement of polymerization, and the MMA:MAHC concentration ratio was determined by gas chromatography. Corresponding to the increased consumption of MAHC, further parts of a mixture comprising 40 parts of MMA, 60 parts of MAHC, 0.05 par~ of butanedithiol and 0.4 part of tert.-butyl isopropylperoxycarbonate were metered in continuously, and the metering rate adjusted, in accordance with the re-sults of further (gas chromatographic) analyses so that a MMA:MAHC free monomer concentration ratio of 52:48 (9/9) was maintained in the reaction vessel.
~hen the subsequent metering ~as complete, the reaction mixture ~as heated to 160C over the course of 2 hours 1~03786 and kept at this temperature for 2 hours. The mixture was subsequently transferred into a two-stage degassing extruder where residual monomer was removed.
The glass transition point of the granulated material was Tg = 157C, and the mean degree of polymerization was Pw = 2,340.
Example 8 It was possible to mold the material from Example 2 in a mold at 250C under pressure to form lenses and similar optical objects. After the surface of a lens had been polished, a transmission of 91% of the incident light was achieved.
Transmission and image-formation properties of this lens remained unchanged even after storage for 24 hours at 100C and an atmospheric humidity of 100 0bar.
Comparison ExampLe A
A lens molded under the conditions of Example 8 from a polymeric glass element made from polymethyl methacrylate - (PMMA) exhib;ted, after polishing, a transmission of 89X
and comparable image-formation properties. After storage for only 2 hours at 120C, the surface of the lens was clearly cloudy and the shape of the lens had changed so substantially that a usable image was no longer produced.
Exa-ple 9 The polymerization by the method of Example 7 was repeated, and the polymer was processed directly, without granula-tion, to form an optical fiber. Of the light intensity which was shone into the front face of the optical fiber, it was possible to measure 45X after a length of three meters, and 7G% after a length of one meter.
After the fiber had been stored for 7 days at 120C and 130~786 an atmospheric humidity of 100 mbar, it was st;ll possible to detect 70% of the incident light intensity after a Length of one meter and 43% after three meters.
S Comparison Example ~:
A three-meter length of an optical fiber made from PMMA
exhibited a transmission of 70% at the beginning of the experiment. After storage at 110C for three hours, the length of the fiber had already shrunk by half and the transmission had dropped to 10% of the incident light intensity.
Claims (8)
1. A transparent thermoplastic molding compositio, compris-ing 10 to 100% by weight of units which are derived from an ester of the formula (I) (I) in which R1 denotes a hydrogen, deuterium or fluorine atom, R2 denotes a hydrogen, deuterium or fluorine atom, R3 denotes a hydrogen, deuterium, fluorine, chlorine or bromine atom, a cyano group, or a methyl group in which all or some of the hydrogen atoms may be replaced by deuterium, fluorine or chlorine atoms, R4 denotes a hydrogen or deuterium atom or a C1- to C5-alkyl group in which all or some of the hydrogen atoms may be replaced by deuterium or fluorine atoms, R5 denotes a -CHR9 or -CDR9 group in which R9 is a hydro-gen, deuterium, fluorine, chlorine or bromine atom or a C1- to C5-alkyl group in which all or some of the hydrogen atoms may be replaced by deuterium or fLuor-ine atoms, R6 denotes a fluorine, chlorine or bromine atom or a tri-fluoromethyl group, R7 denotes a -CH2- group in which all or some of the hydrogen atoms may be replaced by deuterium, fluorine, chlorine or bromine atoms, by tuo CH30 groups or by one 1',2'-ethanediyldioxy group, denotes a carbonyl group or an ethylene group in which all or some of the hydrogen atoms may be replaced by deuterium, chlorine or bromine atoms or by an oxo (O=) group, R8 denotes a -CR10=-CR10- group in which R10 is a fluor-ine, chlorine or bromine atom or a trifluoromethyl group, or denotes a -C(R11)2-C(R11)2- group in which R11 is a fluorine atom or a trifluoromethyl group, and n is zero or 1, n not being zero when R7 is a -CH2- or carbonyl group, and 90 to 0% by weight of units which are derived from other copolymerizable vinyl compounds.
2. A molding composition as claimed in claim 1, wherein the compound of the formula (I) is an ester of 1,4,5,6,7,7-hexachloro- or -hexabromobicyclo[2.2.1]hept-5-en-2-ol, 1,4,5,6,7-pentachlorobicyclo[2.2.1]hept-5-en-2-ol, 1,4,5,6-tetrachlorobicyclo[2.2.1]hept-5-en-2-ol, 5,5,6,6-tetrakis(trifluoromethyl)bicyclo[2.2.1]heptan-2-ol, 5,5,6,6-tetrafluorobicyclo[2.2.1]heptan-2-ol, or 1,4,5,5(or 6,6),7,8-hexachloro-6(or 5)-oxobicyclo[2.2.1]
oct-7-en-2-ol.
oct-7-en-2-ol.
3. A molding composition as claimed in claim 1, wherein the copolymerizable vinyl compounds are C1-C6-alkyl esters of acrylic acid, C1-C6-alkyl esters of methacrylic acid, C1- to C6-alkyl esters of .alpha.-fluoroacrylic acid, styrene or substituted styrene.
4. A process for the production of a transparent thermo-plastic molding composition by free-radical block poly -merization of the monomers, wherein 10 to 100% by weight of an ester of the formula (I) (I) in which R1, R2, R3, R4, R5, R6, R7, R8, R10 and R11 have the meanings mentioned in claim 1, and 90 to 0% by weight of another polymerizable vinyl compound are polymerized.
5. The process as claimed in claim 4, wherein 40 to 100% by weight of an ester of 1,4,5,6,7,7-hexachlorobicyclo-[2.2.1]-hept-5-en-2-ol and 60 to 0% by weight of another polymerizable vinyl compound are polymerized.
6. The use of a molding composition as claimed in claim 1 for the production of transparent optical objects.
7. The use as claimed in claim 6 for the production of opti-cal storage media.
8. The use as claimed in claim 6 for the production of opti-cal fibers.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873707923 DE3707923A1 (en) | 1987-03-12 | 1987-03-12 | TRANSPARENT THERMOPLASTIC MOLD |
| DEP3707923.9 | 1987-03-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1303786C true CA1303786C (en) | 1992-06-16 |
Family
ID=6322839
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000561196A Expired - Fee Related CA1303786C (en) | 1987-03-12 | 1988-03-11 | Transparent thermoplastic molding composition |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0282019A3 (en) |
| JP (1) | JPS63235311A (en) |
| CN (1) | CN1014792B (en) |
| AU (1) | AU606137B2 (en) |
| CA (1) | CA1303786C (en) |
| DE (1) | DE3707923A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU652220B2 (en) * | 1991-02-15 | 1994-08-18 | Toray Industries, Inc. | Plastic optical articles |
| GB9400016D0 (en) * | 1994-01-04 | 1994-03-02 | Minnesota Mining & Mfg | 2-Fluoroacrylate ester polymers and use thereof as optical materials |
| US6005137A (en) | 1997-06-10 | 1999-12-21 | 3M Innovative Properties Company | Halogenated acrylates and polymers derived therefrom |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3022277A (en) * | 1958-07-17 | 1962-02-20 | Hooker Chemical Corp | Polyhalogen containing bicyclic acrylate esters |
| US3143535A (en) * | 1962-12-31 | 1964-08-04 | Eastman Kodak Co | 2, 3-dibromohexahydro-4, 7-methanoindan-5-yl acrylate and methacrylate and polymers thereof |
-
1987
- 1987-03-12 DE DE19873707923 patent/DE3707923A1/en not_active Withdrawn
-
1988
- 1988-03-09 EP EP88103683A patent/EP0282019A3/en not_active Withdrawn
- 1988-03-10 CN CN 88101255 patent/CN1014792B/en not_active Expired
- 1988-03-11 CA CA000561196A patent/CA1303786C/en not_active Expired - Fee Related
- 1988-03-11 AU AU13035/88A patent/AU606137B2/en not_active Ceased
- 1988-03-11 JP JP63056447A patent/JPS63235311A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| AU1303588A (en) | 1988-09-15 |
| CN88101255A (en) | 1988-09-21 |
| AU606137B2 (en) | 1991-01-31 |
| DE3707923A1 (en) | 1988-09-22 |
| JPS63235311A (en) | 1988-09-30 |
| EP0282019A3 (en) | 1990-03-21 |
| EP0282019A2 (en) | 1988-09-14 |
| CN1014792B (en) | 1991-11-20 |
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