CA1303626C - (meth)acrylate esters - Google Patents

(meth)acrylate esters

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Publication number
CA1303626C
CA1303626C CA000551842A CA551842A CA1303626C CA 1303626 C CA1303626 C CA 1303626C CA 000551842 A CA000551842 A CA 000551842A CA 551842 A CA551842 A CA 551842A CA 1303626 C CA1303626 C CA 1303626C
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Prior art keywords
compound
hept
formula
deuterated
meth
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Expired - Fee Related
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CA000551842A
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French (fr)
Inventor
Peter Wegener
Rudolf Heumuller
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Hoechst AG
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Hoechst AG
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Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54Acrylic acid esters; Methacrylic acid esters
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00Carboxylic acid nitriles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Abstract of the disclosure:

Esterification of wholly or partially deuterated (meth)-acrylic acid with alcohols which have only a little hy-drogen or none at all in the molecule gives monomers which, after polymerization give transparent polymeric materials with low attenuation of light waves and with a high glass temperature.

Description

13V362~

HOECHST A~TIENGESELLSCHAFT HO~ 86/F 281 Dr.~A/mu Descr;ption:

tMeth)acrylate esters The invention relates to esters of wholly or partially deuterated (meth)acrylic acid with alcohols, which have only a little hydrogen or none at all in the molecule, to processes for the preparation of these esters and to their use for the preparation of transparent polymeric materials for optical fibers. Various esters of perdeuterated meth-acryLic acid and their use for the preparation of trans-parent pclymers for optical fibers are known.

Thus, fluoroalkyl esters of deuterated methacrylic acid of the formula ~ CD3 CD2 = C~ / Rl wherein R1 and R2 COOCH
~ R2 are lower fluoroalkyl radicals or hydrogen atoms, but at Least one of the two radicals is required to be a lower fluoroalkyl radical, are known tcf. Japanese Published Application 61-20,906). 2,2,2-Trifluoroethyl, 2,2,3,3-tetrafluoro-1-propyl and 1,1,1,3,3,3-he~afluoro-2-prc,pyl are mentioned by name. On the other hand, these esters still contain a relatively large number of hydrogen atoms in the molecule, which have an attenuating effect on the light transmission of the polymers prepared from these esters.

Esters of wholly or partially deuterated methacrylic acid with borneol, isoborneol and fenchyl alcohol are also known (cf. EP-A 144,712; US Patent 4,575,188). However, the methyl groups in the alcohol components of these esters make a considerable contribution to the residual hydrogen 13~?362~;

content of the esters, since their hydrogen atoms are diff;cult to replace by deuterium.

As is known, one hydrogen atom per mole of monomer in-S creases the attenuat;on of the light transmission of the polymer in the wavelength region from 600 to 800 nm due to absorpt;on by about 11 d~/km. It was then desirable to find monomers which provide the polymeric transparent materials prepared from them by polymer;2at;0n with the lowest possible attenuation. At the same time, the trans-parent polymeric materials should have a glass point TG
~hich is higher than that of the hitherto mainly used polymethyl methacrylate (TG = 105C).

It has been found that the object can be achieved when uholly or partialLy deuterated (meth)acrylic acid is ester-ified with certain alcohols which contain only a little hydrogen or none at all in the molecule.

Thus, the invention relates to a compound of the formula t I ) Rl R3 C = C - COO - R4 ( I ) uherein R1 and R2 are identical or different and are a hydrogen atom or deuterium atom, R3 is H, D, -CH3, -CH2D, -CHD2 or -CD3 and R4 is one of the groups -C(CH3)2-CN, -C(CD3)z-CN, (bicyclo-2.2.1-hept-2-yl) or (tricyclo-2.2.12'6-hept-3-yl), 13~626 it being possible for the rings to be deuterated, and, if R3 ;s -CD3, R4 can also be -C~CF3)2-CF~CF3)2, -CF~CF3)2 or -CD~CF3)2-s The invention also relates to a process for their preparat-ion and to their use for the preparat;on of transparent polymeric materials.

In the formu~a (I), R1 and R2 are preferably a deuterium atom, R3 is preferably a deuterium atom or one of the groups -CH3, -CH2D, -CHD2 or -CD3, especially a deuter;um atom or a perdeuteromethyl group, and R4 is preferably ~ (bicyclo-2.2.1-hept-2-yl, norbornyl) or ~ (tricyclo-2.2.1.02'6-hept-3-yl), it be;ng possible for the rings to be deuterated, and in the case of R3 = -CD3 can also be -C(CF3)2-CF(CF3)2, -CF(CF3)2 or -CD(CF3)2.
; 25 The acid components of the esters according to the inven-tion are thus preferably deuterated acrylic acid and meth-acrylic acid. The preparation of the deuterated acids is known per se, and it can be carried out, for example, in the follo~ing manner.

Methyl (meth)acrylate, deuterium oxide, a noble metal salt and a polymerization inhibitor are stirred for several hours at a temperature of around 100C in a reactor.
It is also possible to obtain perdeuterated acrylic acid in accordance with the following reaction equation:

13~336~6 Lindlar Ca~011)23~ Catalyst>
H-C-C-COOR D-C-C-COOR D2C=CD-COOR
D20 D2 gas If required, the corresponding acids can be obtained from the esters.

For the further conversion (ester;fication), the acid of ~0 the formula II
Rl\ R3 / C=C-C~ -R~ (II) wherein R~, R2 and R3 are as defined above, is used as such ~R5 = OH or OD) or in the form of an acid halide (R5 =
Cl or 8r, preferably Cl). The acid halide is prepared by means of a conventional halogenating agent, for example oxalyl chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, benzoyl chloride, benzotrichloride, phosphorus tribromide and especially thionyl chloride. The halogenation with thionyl chloride is preferably carried out in the presence of a catalyst such as dimethylformamide. The reaction is carried out in an aromatic hydrocarbon, for example toluene, xylene or trimethylbenzene, as the solvent and the reaction temper-ature is in the range from 50 to 100C, preferably 70 to 90C.

The (meth)acrylic acid or the acid halide is then reacted with a compound of the formula ~III) HoR4 (III) wherein R4 is as defined above.

The acid halide is preferably used for the esterification of the alcohols HO-C(CH3)-CN, HO-CD(CF3)2, HO-CF(CF3)2 ~3~3~Z~

and Ho-c(cF3)2-cFtcF3)2-The ester;fication is preferably carried out in a sol-vent, and the reaction temperature is -10 to 50C, prefer-ably 0 to 25C. The solvent used is a polar organic sol-vent, especially a symmetrical, asymmetrical or cyclic ether, for example diethyl ether, dipropyl eeher, diiso-propyl ether, tert.-butyl methyl ether, tetrahydrofuran and dioxane, an aliphatic halogenohydrocarbon, preferably chlorohydrocarbon, for example dichloromethane, trichloro-methane, tetrachloromethane, 1,1-dichloroethane and 1,2-dichloroethane, an aromatic halogenohydrocarbon, prefer-ably chlorohydrocarbon, for example chlorobenzene and 1,2-or 1,3-dichlorobenzene, or an aliphatic or aromatic nit-rile, for example acetonitrile and benzonitrile. The sol-vent can also be a mixture of several polar solvents. It is e~pedient to carry out the esterification of the acid halide ~ith the alcohol in the presence of an organic base, especially a trialkylamine having 1 to 4 carbon atoms in each of the alkyl groups. The base is employed in a quan-tity from 0.5 to 2 mole, preferably 0.8 to 1.2 mole (rel-ative to 1 mole of acid halide). The ester obtained is isolated from the reaction mixture by distillation, prefer-ably under a pressure of 1,013 to 200 mbar, or - after removal of the solvent by distillation - by hot extraction of the solid residue ~ith a non-polar solvent, preferably ; an aliphatic hydrocarbon such as n-hexane, and subsequent crystallization. It is appropriate to carry out the dis-tillation in the presence of a conventional polymeri2ation inhibitor, for example hydroquinone or hydroquinone mono-methyl ether; the latter is used in a quantity from 100 to S00 ppm (relative to acid halide). The bottom temper-ature is in the range from 20 to 100C, preferably 30 to 85C. For further purification, the ester is distilled again, preferably under a reduced pressure, or recrystallized.
:
The alcohol is employed in a quantity of O.S mole, prefer-ably 0.8 to 1.2 mole (relative to 1 mole of (meth)acrylic acid).
,,~
, ~
. .

l;~V~2~

Operation in the presence of a dehydrating agent, for example oleum, represents a ~urther esterification method.

The (meth)acryl;c acid esters of bicycloheptyl (norbornyl) and tricycloheptyl alcohol can be prepared according to known methods by acid-catalysed addition of (meth)acrylic acid to bicycloheptene or b;cycloheptadiene respectively.

After known free-radical polymerization by themselves, with one another and/or with other comonomers, for example methacrylic acid esters of aliphatic or alicyclic alcohols, the esters according to the invention give transparent polymeric materials which show low attenuation of incident light and a high glass temperature TG. The alcohols used for the preparation of the esters according to the inven-tion contain either no hydrogen or only a littLe hydrogen in the molecule.

Compared with borneol and isoborneol, the methacrylates Z0 of which are known, the cyclic alcohols of the norbornene type (bicyclo-2.2.1-heptan-2-ol and tricyclo-2.2.1 o2 6-heptan-3-ol) have the advantage of a more favorable C/H
ratio and offer the possibility of replacing all the hydrogen atoms by deuterium by means of catalytic H/D exchange with D20, on the basis of a Wagner-Meerwein rearrangement.
Since a mixture of exo- and endo-norborn-2-yl alcohol or exo- and endo-tricyclohept-3-yl alcohol is formed in the addition reaction, the anisotropy of a polymer produced from the esters is reduced, whereby the transparence is increased.

The transparent polymeric materials obtained from the esters are used for the production of optical fibers, resist material, ienses, optical data storage media and other transparent articles.

The invention is explained in more detail by the examples which follow.

13~:~36Z~

Example 1 2-Cyano-isopropyl methacrylate 9 ml of 2-cyano-isopropyl alcohol ~0.098 M) were added to 10 ml of methacrylic acid chloride (0.103 M) in S0 ml of methyL tert.-butyl ether, 15 ml of triethylamine were then added dropwise with ice-cooling and the mixture was stirred for 1 hour. The triethylammonium hydrochloride was filtered off, and the filtrate was freed of solvent and distilled in vacuo. 7.9 9 of 2-cyano-isopropyl methacrylate were dis-tilled off at 49 - 50C/1.3 mbar, corresponding to 51.6 yield.
IR(CH2Cl2): C=0 at 1750 cm 1, C-N at 2290 cm 1 (weak) Molecular massO 15 Example 2 The perdeuterated compound was prepared analogously from methacrylic acid chloride-D5 and 2-cyano-isopropyl alcohol-D6. Yield 90 9, boiling point 53C/1.3 mbar.
Molecular mass: 164 Example 3 50 mg of di-lauroyl peroxide were in each case dissolved in 5 ml of the 2-cyano-isopropyl methacrylate according to each of Examples 1 and 2, and the solutions were kept for 20 hours at 50C and then for 2 hours at 90C. This gave glass-clear polymers of glass temperature 117C and a decomposition temperature 220C.

Example 4 Norbornyl methacrylate 165 9 of norbornene (= 1.75 M) were dissolved in 100 ml of methylene chloride, and 1 9 of tert.-butylpyrocatechol was added as a stabilizer. With stirring and cool;ng, a ;

13~362~

mixture of 150 ml of methacryl;c ac;d and 15 ml of ~f3 etherate was added dropw;se at 30 - 40C in the course of 2 hours.
The mixture was stirred for a further 2 hours, and the solution was washed with water untiL neutral, dried and concentrated by dist;llat;on. The v;scous res;due was distilled in an oil pump vacuum at bD;l;ng po;nt =52C/0.013 mbar. Th;s gave 210 9 of norbornyl methacryLate, corres-pond;ng to 66~ y;eld. lR(CH2Cl2) C=0 at 1710 cm 1 Molecular mass: 180 The H -NMR spectrum was cons;stent w;th the ind;cated structure Example 5 Starting from methacryl;c ac;d-D5 and partially deuterated norbornene, ;t was possible to prepare the deuterated ester (partially deuterated in the norbornyl radical) analogously to Example 4, the yield and boiling point corresponding to the undeuterated compound.

Example 6 5 ml of each of the pure compGunds from Example 4 and Example 5 were kept with 50 mg of d;lauroyl peroxide in each case for 20 hours at 50C and then for 2 hours at 90C.
This gave glass-clear, hard polymers. The d;fferent;al thermal analysis gave 2 TG values of 120.8C and 172C, decompos;tion temperature 225C.
Example 7 Perfluoro-dimethylbutyl perdeutero-methacrylate 40 9 of perfluorodimethyl-butan-2-ol were added to 10 ml of methacrylic acid chloride-D5, dissolved in 50 ml of methyl tert.-butyl ether. 17 ml of triethylam;ne were added dropwise with stirr;ng and cool;ng. The temperature was ma;ntained at Z0C. After 1 hour, the precipitated triethyl--13~36Z6 _ 9 _ ammonium hydrochlor;de was filtered off with suction and the filtrate was distilled. The perfluorodimethylbutyl perdeuteromethacryLate boiled at 45C/11 mbar. The yield was 14 9, corresponding to 28.5% of theory.

The ester was polymerizable with 1% of dilauroyl peroxide (20 hours at 50C, 1 hour at 90C) and gave a glass-clear polymer having a glass temperature of 111C.

E~ample 8 Tricyclo-2.2.1.02 6-hept-3-yl acrylate 30 ml of norbornadiene (= 0.32 M) were d;ssolved in 50 ml of CH2Cl2, and a mixture of 20 ml of acrylic acid (= 0.29 M), 0.5 9 of tert.-butylpyrocatechol and 3 ml of ~F3 etherate were added dropwise to the solut;on at 20C with stirring.

A slightly exothermic reaction was observed. After 6 hours, the batch was transferred into a separating funnel and washed therein with water, and then dried. In the distil-lation which followed, 12.6 9 of a substance passed over at 60C and 1.7 mbar. The substance had a molar mass of 164, and the H1- and C13-NMR spectrum showed the structure of a tricyclo-2.2.1.02 6-hept-3-yl acrylate. Yield 26.5%.

Example 9 Tricyclo-2.2.1.02 6-hept-3-yl methacrylate Analogously to Example 8, a mixture of 25 ml of methacrylic acid, 5 ml of BF3 etherate and 1 9 of tert.-butylpyro-catechol (as stabilizer) was added to 35 ml of norbornadiene dissolved in 50 ml of CH2Clz. After 6 hours of a slightly exothermic reaction, the batch was worked up as in Example 8.

Boiling point 75 - 85C at 1.7 mbar, yield 32 9 = 62%
of theory: molecular mass 178.

~3~33~

The H1- and C13-NMR specerum showed the structure of a tricyclo-2.2.1.02~6-hept-3-yl methacrylate.

Example 10 Deuterohexafluoroisopropyl perdeutero-methacrylate 30 ml of perdeuterated methacrylic acid and 45 ml of per-deuterated hexafluoroisopropanol (prepared by catalytic hydrogenation of hexafluoroacetone with D2 on a Pd/C
catalyst) were mixed with 75 ml of ~6X oleum. During the reaction, the temperature rose to 40C. After 15 minutes, the mixture was transferred into a thin-layer evaporator and distilled at a wall temperature of 130C under a vacuum of 44 mbar. At a top temperature of 50 to 60C, 60 9 of crude deuterohexafluoroisopropyl perdeuteromethacrylate passed over, and this was distilled once more. This gave 50 9 of end product, corresponding to a yield of 60Z of theory.
The ester was polymerizable by means of 0.1% by weight of dilauroyl peroxide and gave a polymer having a TG value of 74C and a decomposition temperature h;gher than 200C.

Example 11 Perfluoroisopropyl perdeutero-methacrylate 12.9 g (0.222 M) of potassium fluoride were suspended in 80 ml of diglyrol d;methyl ether. 33 9 (0.198 M) of hexa-fluoroacetone were passed ;nto this suspens;on at room temperature. The batch was then stirred for a further 2 hours and the und;ssolved potass;um fluoride was then sep-arated off. 22 9 (0.2 M) of methacryl;c ac;d chloride-Ds were added dropw;se to the filtrate at room temperature and the react;on m;xture was stirred for a further hour.
After the sol;d formed had been separated off, the fil-trate was distilled.

~3~362~i Colorless liquid, bo;ling point 45.2 - 45.4 C/80 mbar.
Yield 32 9 = 64X of theory.

The ester was polymerizable by means of 0.5% by weight of dilauroyl pero~ide for 24 hours at 50C, to give a gLass-clear polymer having a TG value of 76C.

Claims (6)

1. A compound of the formula (I) (I) wherein R1 and R2 are identical or different and are a hydrogen atom or deuterium atom, R3 is H, D, -CH3, -CH2D, -CHD2 or -CD3 and R4 is one of the groups -C(CH3)2-CN, -C(CD3)2-CN, (bicyclo-2.2.1-hept-2-yl) or (tricyclo-2.2.12.6-hept-3-yl), wherein the rings may be deuterated, and wherein at least one of R1 to R4 contains a deuterium atom, and, if R3 is -CD3, R4 can also be -C(CF3)2-CF(CF3)2, -CF(CF3)2 or -CD(CF3)2-
2. A compound as claimed in claim 1, wherein, in the formula (I), R3 is -D, -CH3, -CH2D, -CHD2 or -CD3 and R4 is (bicyclo-2.2.1-hept-2-yl) (tricyclo-2.2.1.02.6-hept-3-yl), wherein the rings may be deuterated, and, in the case of R3 = -CD3, can also be -CtCF3)2-CF(CF3)2, -CF(CF3)2 or -CD(CF3)2.
3. A process for preparing the compound as defined in claim 1 by reacting a compound of the formula (II) (II) wherein R1, R2 and R3 are as defined in claim 1 and R5 is a halogen atom, an OH group or an OD group, with a compound of the formula (III) HOR4 (III) wherein R4 is as defined in claim 1, at a temperature from -10 to 50°C in the presence of a catalyst.
4. The use of compound of the formula (I) as claimed in claim 1 for the production of transparent polymeric materials.
5. The compound of the formula (I) as claimed in claim 1 for use in the production of transparent polymeric materials.
6. The use of a compound of the formula (I) (I) wherein R1 and R2 are identical or different and are a hydrogen atom or deuterium atom, R3 is D, -CH2D, -CHD2 or -CDs and R4 is one of the groups -C(CH3)2-CN, -C(CD3)2-CN, (bicyclo-2.2. 1-hept-2-yl ) or (tricyclo-2.2.12'6-hept-3-yl), wherein the rings may be deuterated, and, if R3 is -CD3, R4 can also be -C(CF3)2-CF(CF3)2, -CF(CF3)2 or -CD(CF3)2, for the production of polymeric materials which show low attenuation of incident light and a high glass temperature (TG).
CA000551842A 1986-11-15 1987-11-13 (meth)acrylate esters Expired - Fee Related CA1303626C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19863639117 DE3639117A1 (en) 1986-11-15 1986-11-15 (METH) ACRYLIC ACID ESTER
DEP3639117.4 1986-11-15

Publications (1)

Publication Number Publication Date
CA1303626C true CA1303626C (en) 1992-06-16

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Family Applications (1)

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CA000551842A Expired - Fee Related CA1303626C (en) 1986-11-15 1987-11-13 (meth)acrylate esters

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EP (1) EP0268192B1 (en)
JP (1) JPS63130563A (en)
KR (1) KR880006162A (en)
CN (1) CN1030572A (en)
AT (1) ATE80146T1 (en)
AU (1) AU8118887A (en)
CA (1) CA1303626C (en)
DE (2) DE3639117A1 (en)
DK (1) DK596987A (en)
ES (1) ES2044892T3 (en)

Cited By (1)

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US7495122B2 (en) 2003-07-24 2009-02-24 Wako Pure Chemical Industries Heavy-hydrogenated norbornyl (meth)acrylates, process for producing them, polymers thereof and optical members

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DE3704915A1 (en) * 1987-02-17 1988-08-25 Hoechst Ag ELECTROCHEMICAL METHOD FOR REPLACING HALOGENATOMS IN AN ORGANIC COMPOUND
JPH02211401A (en) * 1989-02-13 1990-08-22 Hitachi Chem Co Ltd Optical parts and optical elements
DE3912151A1 (en) * 1989-04-13 1990-10-18 Hoechst Ag TRANSPARENT THERMOPLASTIC MOLDS FROM 2,3-DIFLUORACRYLIC ACID ESTERS
JP2636636B2 (en) * 1992-06-15 1997-07-30 株式会社日本触媒 Method for producing (meth) acrylate
DE4310866A1 (en) * 1993-04-02 1994-10-06 Kernforschungsz Karlsruhe Measuring arrangement having an optical measuring probe
WO2005010060A1 (en) * 2003-07-24 2005-02-03 Fuji Photo Film Co., Ltd. Heavy-hydrogenated (meth)acrylates, process for producing them, polymers thereof and optical members
US8175379B2 (en) 2008-08-22 2012-05-08 Adobe Systems Incorporated Automatic video image segmentation
US8358691B1 (en) 2009-10-30 2013-01-22 Adobe Systems Incorporated Methods and apparatus for chatter reduction in video object segmentation using a variable bandwidth search region
DE102011122745A1 (en) 2011-12-29 2013-07-04 Sebastian Oberwalder Combination material, used for preparing articles and coatings, comprises polyurethane material, metal particles such as e.g. lead and tungsten or their corresponding oxides, sulfides, fluorides and/or oxide sulfides, and boron or its salt
KR101874069B1 (en) 2013-11-29 2018-07-03 김노을 Plastic hot water boiler
CN105732384A (en) * 2014-12-11 2016-07-06 浙江蓝天环保高科技股份有限公司 Preparation method of metacrylic acid ester containing fluoro-alcohol

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US3681438A (en) * 1970-10-26 1972-08-01 Union Carbide Corp Preparation of bicyclo (2.2.1) hept-2-en-ylmethyl acrylate
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7495122B2 (en) 2003-07-24 2009-02-24 Wako Pure Chemical Industries Heavy-hydrogenated norbornyl (meth)acrylates, process for producing them, polymers thereof and optical members

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DK596987A (en) 1988-05-16
ES2044892T3 (en) 1994-01-16
DK596987D0 (en) 1987-11-13
JPS63130563A (en) 1988-06-02
CN1030572A (en) 1989-01-25
AU8118887A (en) 1988-05-19
DE3781514D1 (en) 1992-10-08
ATE80146T1 (en) 1992-09-15
EP0268192B1 (en) 1992-09-02
KR880006162A (en) 1988-07-21
EP0268192A3 (en) 1990-05-30
DE3639117A1 (en) 1988-05-19
EP0268192A2 (en) 1988-05-25

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