CN1018954B - Use of transparent thermoplastic composition for producing transparent optical product - Google Patents
Use of transparent thermoplastic composition for producing transparent optical productInfo
- Publication number
- CN1018954B CN1018954B CN 91103434 CN91103434A CN1018954B CN 1018954 B CN1018954 B CN 1018954B CN 91103434 CN91103434 CN 91103434 CN 91103434 A CN91103434 A CN 91103434A CN 1018954 B CN1018954 B CN 1018954B
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- atom
- deuterium
- alcohol
- fluorine
- expression
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Abstract
A transparent thermoplastic moulding compound essentially derived from an ester of a (meth)acrylic acid with a cyclic alcohol can be prepared in a simple and economical manner. In this moulding compound, acid and alcohol radicals may be deuterated and/or fluorinated. A particularly preferred alcohol component is 1,4,5,6,7,7-hexachloro- bicyclo[2.2.1]hept-5-en-2-ol. The moulding composition can be converted into articles of high transparency and heat resistance.
Description
The present invention relates to a kind of preparation polymer glass, optics industry article and fibre-optic transparent thermoplastic composition of propagating optical signal of being applicable to, and preparation method thereof.This moulding compound has high resistance to heat distorsion.
Optical fiber can be made of fuse and cover, and core is always than the refraction index height that overlaps material.This fibre-optic core and cover material should absorb luminous energy as few as possible.
Being most commonly used to so far make fibre-optic polymeric material, is the homopolymer and the multipolymer of methyl methacrylate.Although halogen-containing polymkeric substance also is used as core, have only fluorine-containing polymkeric substance to be used as the cover material so far, reason is that its refraction index is lower.In order to reduce light absorption, once the someone proposed with the hydrogen atom in deuterium substituted monomer and the polymkeric substance.
The patent disclosure that has methyl methacrylate and chemical formula be CH
2=CR-(CO-O)
n-ArBr
m(R=H or CH
3, n=0 or 1, m=1～5) the multipolymer (referring to No. the 2nd, 202,791, Deutsche Bundespatent communique) of compound enumerated the acrylate or the methacrylate of called after one, two, three, four and pentabromo-phenol.
In addition, known have a kind of moulding compound, is made up of poly-alpha-fluoro acrylic ester, all may contain D atom (european patent application discloses 0,128,517) on the beta carbon of vinyl wherein He in the alkoxide component.This base polymer is used as fibre-optic core.The gel infiltration method molecular weight of this base polymer is 200,000～5,000,000, refraction index be 1.45～1.60 and softening point be 100～200 ℃.As optical fiber cover material, it is the lower polymkeric substance of refraction index, the material of particularly suitable is the alpha-fluoro acrylic ester polymer that its alkoxide component contains fluorine atom, for example the polymkeric substance of the polymkeric substance of alpha-fluoro acrylic acid three fluoro ethyl esters and alpha-fluoro acrylic acid hexafluoro isobutyl ester.
The preparation and the character of above-mentioned poly-(alpha-fluoro fluoroalkyl acrylate) all are known (disclosing 0,128 referring to european patent application, 516).Have chain-transferring agent to exist and 0～100 ℃ of temperature under, bulk polymerization, solution polymerization or the suspension polymerization of all monomers by the free radical initiation can obtain this base polymer.Its gel infiltration method molecular weight is 200,000～5,000,000, and refraction index is 1.36～1.44, and softening point is 80～140 ℃.
In addition, the patent that has also discloses a kind of optical fiber, and its core is (referring to day present disclosure specification 60-242,404) that produce by the block polymerization of methacrylic acid halogenated aryl ester (for example methacrylic acid phenyl-pentafluoride base ester) especially.
In addition, the somebody proposes to do with the polymkeric substance of fluorine-containing (methyl) acrylic acid polyhalogenated aryl ester the material of polymer optical fibre.At last, patent disclosure has been arranged by 1,4,5,6,7, in 7-hexachloro two rings heptan-5-alkene-2, the polymkeric substance of the polymerization gained of 3-dicarboxylic acid two allyl alcohol esters makes to make fibre-optic material (referring to day present disclosure specification 61-51,901).
But this base polymer can not be with thermoplastic method processing, and reason is that this polymkeric substance takes place in polymerization process crosslinked.In the alcohol moiety of acrylate and methacrylate, contain 1,4,5,6,7, the polymkeric substance known for many years (referring to United States Patent (USP) the 3rd, 022, No. 277) of 7-hexachloro two ring [2,2,1] heptan-5-alkene-2-base.But the optical property of unexposed this base polymer of mistake, resistance to heat distorsion and working properties, or the character of the multipolymer of itself and other acrylate and methacrylate.
The object of the present invention is to provide a kind of available simple economy method polymkeric substance preparation, that can be processed into the material of the high grade of transparency and resistance to heat distorsion.
Have been found that a kind of mainly is the transparent thermoplastic composition that the ester by (methyl) acrylic acid and bicyclic alcohol obtains.Because its acidic group and alcohol radical can by deuterate and (or) halogenation, so can reach this purpose.
Therefore, the present invention relates to a kind of by 10～100%(weight) the ester shown in chemical formula (I) unit and the 90～0%(weight that produce) but the unit group that produces of other copolymerization of ethylene based compound
In the formula (I): R
1Expression hydrogen, deuterium or fluorine atom;
R
2Expression hydrogen, deuterium or fluorine atom;
R
3Expression hydrogen, deuterium, fluorine, chlorine or bromine atom, cyano group, or all or part of methyl that can be replaced by deuterium, fluorine or chlorine atom of hydrogen atom;
R
4Expression hydrogen or D atom, hydrogen atom is all or part of can be by the C that deuterium or fluorine atom replaced
1-C
5Alkyl;
R
5Expression-CHR
9Or-CDR
9Base, wherein R
9Be hydrogen, deuterium, fluorine, chlorine or bromine atom, or all or part of hydrogen atom can be by the C that deuterium or fluorine atom replaced
1-C
5Alkyl;
R
6Expression fluorine, chlorine or bromine atom or three fluoro methyl;
R
7Represent that all or part of hydrogen atom can be replaced-CH by deuterium, fluorine, chlorine or bromine atom
2-Ji is by two CH
3O base or one 1 ', 2 '-dioxoethyl (ethanediyldioxy) replaces-CH
2-Ji, ethylidene that expression carbonyl or all or part of hydrogen atom may be replaced by deuterium, chlorine or bromine atom or that replaced by the oxygen base;
R
8Expression-CH
10=CR
10-Ji, wherein R
10Be fluorine, chlorine or bromine atom, or three fluoro methyl, or expression-C(R
11)
2-C(R
11)
2-Ji, wherein R
11Be fluorine atom or three fluoro methyl.
N is 0 or 1, R
7For-CH
2N is not 0 when-Ji or carbonyl.
In addition, the invention still further relates to the method for this class moulding compound of preparation and the transparent optical article of making by this class moulding compound.
In the formula (I):
R
1Preferably hydrogen, deuterium or fluorine atom, good especially is hydrogen or D atom;
R
2Preferably hydrogen, deuterium or fluorine atom, good especially is hydrogen or D atom;
R
3Preferably hydrogen, deuterium or fluorine atom, or all or part of hydrogen atom methyl that may be replaced by deuterium, good especially is deuterium or fluorine atom, or three deuteriums are for methyl;
R
4Preferably hydrogen or D atom;
R
5Preferably methylene, deuterium be for methylene or chloro methylene, and good especially is that methylene or deuterium are for methylene;
R
6Preferably chlorine or bromine atom, or three fluoro methyl, good especially is the chlorine or bromine atom;
R
7Preferably hydrogen atom may be by deuterium, chlorine or bromine atom, or the methylene that replaces of dimethoxy, be carbonyl or hydrogen atom may by chlorine atom or oxygen base (0 two) replace 1, the 2-ethylidene,, be-CH well especially
2-,-CD
2-,-CCI
2-,-CBr
2,-CHCl-,-C(=0)-,-C(=0)-CCl
2-or-CH
2-CH
2-.
R
8Preferably-CR
10=CR
10-Ji, wherein R
10Expression chlorine or bromine atom, or three fluoro methyl may represent it is the chlorine or bromine atom especially, or-C(R
11)
2-C(R
11)
2-Ji, wherein R
11Can be fluorine atom or three fluoro methyl;
N is preferably 1.
Therefore, the acid constituents of the used ester of the present invention preferably acrylic acid, methacrylic acid, alpha-fluoro is acrylic acid, α, β-two fluoro acrylic acid, or the corresponding compounds in all or part of deuterium generation, thing be not full deuterium for methacrylic acid, full deuterium for acrylic acid, alpha-fluoro acrylic acid or full deuterium for alpha-fluoro acrylic acid.Alkoxide component preferably 1,3,4,5,6,7,7-seven or seven chloros two rings [2,2,1] heptan-5-alkene-2-alcohol, 1,4,5,6,7,7-hexachloro (or hexabromo) two ring [2,2,1] heptan-5-alkene-2-alcohol, 1,4,5,6,7-pentachloro-two rings [2,2,1] heptan-5-alkene-2-alcohol, 1,4,5,6-tetrachloro generations two ring [2,2,1] heptan-5-alkene-2-alcohol, 1,2,3,4-tetrachloro generations two ring [2,2,1] hept-2-ene"-7-alcohol, 1,4,5,6-four (three fluoro methyl)-7-oxygen (=0)-or-7-two (methoxy) two ring [2,2,1] heptan-5-alkene-2-alcohol, 1,2,3,4-four (three fluoro methyl) two rings [2,2,1] hept-2-ene"-7-alcohol, 1,2,3, the 4-tetrabromo is for-5,6-dichloro-two ring [2,2,1] hept-2-ene"-7-alcohol, 1,2,3, the 4-tetrachloro is for-5, and 6-two bromos two encircle [2,2,1] hept-2-ene"-7-alcohol, 5,5,6,6-four (three fluoro methyl) two rings [2,2,1] heptan-2-alcohol, 5,5,6, ring [2,2,1] heptan in 6-tetrafluoro generations two-2-alcohol, 1,4,5,5-(or 6,6), 7,8-hexachloro-6(or 5)-oxygen (C=0) two ring [2,2,1] suffering-7-alkene-2-alcohol or 1,4,5,5,6,6,7,8-eight chloros two ring [2,2,1] suffering-7-alkene-2-alcohol; Good especially is 1,4,5,6,7,7-hexachloro (or hexabromo) two rings [2,2,1] heptan-5-alkene-2-alcohol, 1,4,5,6,7-pentachloro-two ring [2,2,1] heptan-5-alkene-2-alcohol, 1,4,5, ring [2,2,1] heptan in 6-tetrachloro generations two-5-alkene-2-alcohol, 5,5,6,6-four (three fluoro methyl) two ring [2,2,1] heptan-2-alcohol, 5,5,6, ring [2,2,1] heptan in 6-tetrafluoro generations two-2-alcohol, 1,4,5,5(or 6,6), 7,8-hexachloro-6(or 5)-oxygen (C=0) two ring [2,2,1] suffering-7-alkene-2 alcohol.
Be used for ester of the present invention preferably the hydrogen of its alkoxide component and acid constituents as far as possible fully by deuterium, fluorine, chlorine and bromine atoms, or by the methyl substituted ester of three fluoro.Good especially ester is that full deuterium is for methacrylic acid, full deuterium is for acrylic acid, acid of α fluoropropenes or full deuterium generation-alpha-fluoro acrylic acid and 2,2,3-three deuteriums are for-1,4,5,6,7,7-hexachloro (or hexabromo) two ring [2,2,1] heptan-5-alkene-2-alcohol, 2,2,3-three deuteriums are for-1,4,5,6,7-pentachloro-two ring [2,2,1] heptan-5-alkene-2-alcohol, 2,2,3-three deuteriums are for-1,4,5, ring [2,2,1] heptan in 6-tetrachloro generations two-5-alkene-2-alcohol, 1,2,3,4,7,7-six deuteriums are for-5,5,6,6-four (three fluoro methyl) two ring [2,2,1] heptan-2-alcohol, 1,2,3,4,7,7-six deuteriums are for-5,5,6, and the 6-tetrafluoro is for two rings [2,2,1] heptan-2-alcohol or 2,2,3-three deuteriums generation-1,4,5,5(or 6,6), 7,8-hexachloro-6(or 5)-ester of oxygen (0=) two ring [2,2,1] suffering-7-alkene-2-alcohol.
Moulding compound of the present invention is by 10-100%(40-100% preferably, good especially is 50-80%) unit that produces by chemical formula (I) ester of (weight) and 90-0%(60-0% preferably, the good especially 50-20% of being) (weight) but the unit that produces of the vinyl compound by other copolymerization form.Suitable compounds is acrylic acid C
1-C
6Alkyl acid, methacrylic acid C
1-C
6Arrcostab, alpha-fluoro acrylic acid C
1-C
6Alkyl acid, styrene or substituted phenylethylene.Preferably use the acrylic acid ester of acrylic acid, methacrylic acid and alpha-fluoro, with and the derivant of deuterium.Particularly methyl acrylate, methyl methacrylate and alpha-fluoro methyl acrylate.Good especially is that corresponding deuterium is for compound.
Moulding compound of the present invention is by the compound shown in chemical formula (I) and another (if being fit to) but the free radical block polymerization or the suspension polymerization of the vinyl compound of copolymerization, emulsion polymerization or solution polymerization make, and especially preferably make by block polymerization.
The free radical activity initiating agent that is suitable for has: azo-compound, for example azoisobutyronitrile, azo two (cyclohexyl nitrile), azo two (uncle's octane) and 2-phenylazo-2,4-dimethyl-4-methoxy valeronitrile; And organic peroxide, for example tert-butyl peroxide, the sad tertiary butyl ester of mistake, peroxy isopropyl base carbonic acid tertiary butyl ester, tert-butyl peroxide and peroxide isobutyric acid tertiary butyl ester.The amount ranges of initiating agent is 0.001～3 mole of per 100 mole of monomer or all monomer, preferably 0.035～0.3 mole.Polyreaction is carried out under the situation that chain-transferring agent (correctives) arranged, and is more favourable.The chain-transferring agent that is specially adapted to this polyreaction has: thio-alcohol, for example butanethiol, tert-butyl mercaptan, the pure and mild phenyl mercaptan of propylthio; With the ester class of mercaptoacetic acid, ethyl thioglycolate, two (mercaptoacetic acid) glycol ester for example.Polymerization temperature is 60～180 ℃, and preferably 80～160 ℃, good especially is 100～160 ℃.
More favourable way is before beginning to carry out polyreaction, to make the reaction mixture degassing.Always earlier the temperature that contains the reaction mixture of each monomer, initiating agent and correctives is cooled at least-80 ℃ for this reason, then reactor is evacuated, and under the state of sealing, be heated to 0～25 ℃.Can repeat this step for several times.
The moulding compound that the present invention produces is a kind of thermoformable transparent material.Therefore be suitable for producing the material of transparent articles especially, for example as protective material, lens and fibre-optic material.Separately or the polymer mixed different, the material that can be used as the optical data storage medium with another refraction index.
The spectral transmittance of this moulding compound is high especially in the scope of 600～1300 millimicrons of wavelength.The characteristic of moulding compound is as follows:
The light scattering method mean molecular weight is 8,000～5,000,000, is preferably 50,000～200,000;
Glass temperature is 95～250 ℃, be preferably 120～200 ℃ good especially be 150～180 ℃;
Decomposition temperature is at least 230 ℃, is preferably 250～300 ℃.
Nonflammable by the article that moulding compound of the present invention is made, have good resistance to heat distorsion.
Hereinafter all embodiment of Jie Shaoing are intended to more detailed explanation is done in invention.All percentages are percent by weight.
Embodiment 1
1) acetate 1,2,3,4,7,7-hexachloro two ring [2,2,1] hept-2-ene"s-5-base ester
In 250 milliliters of three-neck flasks of magnetic stirrer, thermometer and reflux condenser are housed, 100 gram (0.366 mole) hexachlorocyclopentadienes and 37 gram (0.43 mole) vinyl-acetic esters are refluxed heat.In backflow heating process, the initial temperature of reaction mixture is 87 ℃, and the finishing temperature that is reached after 40 hours is 139 ℃.With this potpourri fractionation, can obtain 95 gram esters (main fractions that under 105～112 ℃ and 0.05 millibar, distillates) (theoretical amount 72%).
2) 1,2,3,4,7,7-hexachloro two ring [2,2,1] hept-2-ene"-5-alcohol
In 4 liters of three-neck flasks of magnetic stirrer, thermometer and reflux condenser are housed, 1,760 ml methanol and 17.6 milliliters of concentrated hydrochloric acids are added in the compound 1 of 880 grams (2.45 moles), stir out potpourri, heating 4 hours refluxes.Boil off solvent then and in normal heptane again crystallization go out solid residue, can obtain 704 gram alcohol (theoretical amount 90%)
3) acrylic acid 1,2,3,4,7,7-hexachloro two ring [2,2,1] hept-2-ene"s-5-base ester (AHC)
In 500 milliliters of three-neck flasks of magnetic stirrer, thermometer and reflux condenser are housed, 50 gram (0.158 mole) compounds 2 are dissolved in 150 milliliters of toluene, and add 21.5 gram (0.237 mole) acryloyl group chlorine down at 70 ℃.Under this temperature, stirred this potpourri again 16 hours then.Then, boil off solvent and distillation residue.Will be about 118 ℃ down cut (60.6 gram) be dissolved in the diethyl ether, pass through Al then
2O
3Post filters.Behind the diethyl ether in boiling off filtrate, obtain 33.4 gram acrylate (theoretical amount 57%).
4) methacrylic acid 1,2,3,4,7,7-hexachloro two ring [2,2,1] hept-2-ene"s-5-base ester (MA-HC)
In 1 liter of three-neck flask of magnetic stirrer, thermometer and reflux condenser is housed, 200 gram (0.63 mole) compounds 2 is dissolved in 500 milliliters of toluene, and adds 99.2 gram (0.95 mole) methacryl chlorine.Under situation about refluxing, stirred this potpourri 30 hours then.Then boil off solvent and residue is dissolved in the diethyl ether, pass through Al
2O
3Post filters.After boiling off diethyl ether, obtain 189.4 gram methacrylates (theoretical amount 78%).
Embodiment 2
Making the solution be made up of 100 parts of acrylic acid hexachloro bicycloheptene base esters (AHC), 0.05 part of dicumyl peroxide and 0.17 part of butanethiol is 200 millimicrons membrane filter by membrane aperture, and the glass container and the careful degassing are gone in filter.In order to outgas, at first use the liquid nitrogen frozen reaction mixture, then glass container is evacuated (0.001 millibar) then is heated to room temperature.Repeat above-mentioned steps three times.The good seal reaction vessel is followed the heat de-airing reaction mixture then, heats under 123 ℃ 5 hours earlier, reaches 140 ℃ then.Behind cool to room temperature, obtain transparent polymer material.The character that records is as follows:
Average degree of polymerization PW 2,050
159 ℃ of glass temperatures
270 ℃ of decomposition temperatures
Melt flow index (250 ℃, 3.8 kilograms) 8 grams/10 minutes
Residual monomer content 0.5%
Refraction index n
D1.54
Embodiment 3
With the method that is similar to embodiment 2, filter and outgas form solution by 50 parts of methacrylic acid hexachloro bicycloheptene base esters (MAHC), 0.03 part of diazonium isobutyronotrile, 0.5 part of butanethiol and 50 parts of chloroforms.Then, the reaction mixture that will outgas was heated under 60 ℃ 20 hours.Behind this potpourri cool to room temperature, add 400 parts of acetone, and the potpourri of gained is transferred in 6000 parts of hexanes.The polymkeric substance that is settled out in this operating process is told from liquid, from acetone/hexane, be settled out again and 100 ℃ and vacuum under dry 6 hours.Obtain 40 gram polymkeric substance (theoretical amount 80%).The character that records is as follows:
Average degree of polymerization PW 500
220 ℃ of glass temperatures
300 ℃ of decomposition temperatures
Embodiment 4-6
With the method that is similar to embodiment 2, the MAHC that contain different amounts and solution methyl methacrylate and that all contain 0.1 grammes per square metre nitrogen isobutyronotrile and 0.15 gram butanethiol are filtered and outgases.Each reaction mixture that outgases all is heated 30 minutes, reaches 60 ℃.Then, cool to room temperature mixes with 300 milliliters of acetone.Each potpourri of gained is transferred to respectively in 5 liters of hexanes.The multipolymer that is settled out is told from liquid, and following dry 6 hours 70 ℃ of temperature.
The glass temperature (Tg) of the composition of each monomer mixture, the composition of multipolymer and multipolymer is as shown in table 1.(seeing Table 1)
Embodiment 7
In the enclosure-type reaction vessel of stirrer and measuring instrument is housed, with the potpourri of the saturated 50 parts of MAHC of nitrogen, 50 parts of MMA, 0.05 part of isopropyl peroxide carbonic acid tertiary butyl ester and 0.5 part of dibutyl disulfide phenol.While stirring reaction solution is heated to 90 ℃.
The increase of stirrer power consumption can be measured the small increase of viscosity, and the beginning that hence one can see that reacts.A sample is taken out in after polyreaction begins 15 minutes from potpourri, and measures the concentration ratio of MMA and MAHC with gas chromatogram.Increase according to the MAHC consumption, according to the continuous later on result who analyzes of gas chromatogram, constantly add according to quantity by 40 parts of MMA, 60 parts of MAHC, 0.05 part of dibutyl disulfide phenol and 0.4 part of another kind of potpourri that isopropyl peroxide carbonic acid tertiary butyl ester is formed, and regulate the speed that adds according to quantity, the concentration ratio of MMA and MAHC free monomer is 52 in the reaction vessel thereby keep: 48(gram/gram).
After reinforced according to quantity finishing subsequently, in 2 hours, reaction mixture is heated to 160 ℃, and remained on this temperature following 2 hours.Then this potpourri is transferred in the secondary degassing extruding machine, to remove residual monomers.
The glass temperature Tg of pellet is 157 ℃.Average degree of polymerization Pw=2,340.
Embodiment 8
Depress with adding at 250 ℃, the material that available mould makes embodiment 2 is molded as lens and similar optical goods.After lens surface is polished, can reach the transmissivity of 91% incident light.
The transmissivity of this lens and imaging property are even store 24 hours under 100 ℃ and 100 millibars of atmospheric humiditys after, also remain unchanged.
Comparative Example A An
Use the polymer glass material that makes by polymethylmethacrylate (PMMA), under the condition of embodiment 8 usefulness, be molded as lens, after polishing, have 89% transmissivity and comparable imaging property.Storage is after firm 2 hours down at 120 ℃, and lens surface presents obvious muddiness, the lens shape significant change, so that no longer can form available image.
Embodiment 9
Method according to embodiment 7 is carried out polymerization, directly is processed into optical fiber without granulating.The light intensity of being shone on the optical fiber front end face after 3 meters of length, can measure 45%, after 1 meter of length, can measure 70%.
This fiber stores 7 days under 100 millibars of 120 ℃ and atmospheric humiditys after, the light intensity of injecting after 3 meters of length, can measure 43%, after 1 meter of length, can measure 70%.
Comparative Examples B
One 3 meters long optical fibers of PMMA system, when on-test, transmissivity is 70%.110 ℃ down store 3 hours after, the contraction in length of this fiber is to half of raw footage, transmissivity drops to injects 10% of light intensity.
Table 1
MMA: the MAHC(weight ratio)
Embodiment Tg(℃) n
23 D
The monomer mixture multipolymer
4 28∶72 23∶77 161 1.529
5 51∶49 40∶60 155 1.523
6 70∶30 59∶41 147 1.513
Claims (5)
1, transparent thermoplastic composition is used to make the purposes of transparent optical article, wherein said composition by the ester shown in chemical formula (I) of 10-100% (weight) and 90-0% (weight) but the unit that produces of other copolymerizable vinyl groups compound polymerization reaction formed:
In the formula (I):
R
1Expression hydrogen, deuterium or fluorine atom,
R
2Expression hydrogen, deuterium or fluorine atom,
R
3Expression hydrogen, deuterium, fluorine, chlorine or bromine atom, cyano group, or all or part of methyl that can be replaced by deuterium, fluorine or chlorine atom of hydrogen atom,
R
4Expression hydrogen or D atom, or all or part of C that can be replaced by deuterium or fluorine atom of hydrogen atom
1～C
5Alkyl,
R
5Expression-CHR
9Or-CDR
9Base, wherein R
9Be hydrogen, deuterium, fluorine, chlorine or bromine atom, or all or part of C that can be replaced by deuterium or fluorine atom of hydrogen atom
1-C
5Alkyl,
R
6Expression fluorine, chlorine or bromine atom, or three fluoro methyl,
R
7The expression hydrogen atom is all or part of can be replaced-CH by deuterium, fluorine, chlorine or bromine atom
2-Ji is by two CH
3O base or one 1 ', 2 '-dioxoethyl (ethanediyldioxy) replaces-CH
2-Ji, all or part of ethylidene that can be replaced by deuterium, chlorine or bromine atom or that replaced by the oxygen base of expression carbonyl or hydrogen atom,
R
8Expression-CH
10=CH
10-Ji, wherein R
10Be fluorine, chlorine or bromine atom, or three fluoro methyl, or expression-C (R
11)
2-C (R
11)
2-Ji, wherein R
11Be fluorine atom or three fluoro methyl,
N is 0 or 1, R
7For-CH
2When-Ji or carbonyl, n is not 0.
2, purposes according to claim 1, wherein the compound of chemical formula (I) is a kind of 1,4,5 in the moulding compound, 6,7,7-hexachloro (or hexabromo) two rings [2,2,1] heptan-5-alkene-2-alcohol, 1,4,5,6,7-pentachloro-two ring [2,2,1] heptan-5-alkene-2-alcohol, 1,4,5, ring [2,2,1] heptan in 6-tetrachloro generations two-5-alkene-2-alcohol, 5,5,6,6-four (three fluoro methyl) two rings [2,2,1] heptan-2-alcohol, 5,5,6,6-tetrafluoro generations two ring [2,2,1] heptan-2-alcohol or 1,4,5,5(or 6,6), 7,8-hexachloro-6(or 5) ester of an oxo two ring [2,2,1] suffering-7-alkene-2-alcohol; And but copolymerization of ethylene based compound wherein is acrylic acid C
1-C
6Arrcostab, methacrylic acid C
1-C
6Arrcostab, alpha-fluoro acrylic acid C
1-C
6Arrcostab, styrene or substituted phenylethylene.
3, purposes according to claim 1, wherein 40-100%(weight) 1,4,5,6,7, the ester and the 60-0%(weight of 7-hexachloro two ring [2,2,1] heptan-5-alkene-2 alcohol) another polymerizable vinyl compound be aggregated.
4, the purposes of the moulding compound described in the claim 1,2 or 3, this purposes is for being used to make optical storage medium.
5, the purposes of the moulding compound described in the claim 4, described purposes is for being used to make optical fiber.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873707923 DE3707923A1 (en) | 1987-03-12 | 1987-03-12 | TRANSPARENT THERMOPLASTIC MOLD |
| DEP3707923.9 | 1987-03-12 | ||
| DE3707923.9 | 1987-03-12 | ||
| CN 88101255 CN1014792B (en) | 1987-03-12 | 1988-03-10 | Transparent thermoplastic forming composition |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88101255 Division CN1014792B (en) | 1987-03-12 | 1988-03-10 | Transparent thermoplastic forming composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1057062A CN1057062A (en) | 1991-12-18 |
| CN1018954B true CN1018954B (en) | 1992-11-04 |
Family
ID=25742424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91103434 Expired CN1018954B (en) | 1987-03-12 | 1991-05-23 | Use of transparent thermoplastic composition for producing transparent optical product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1018954B (en) |
-
1991
- 1991-05-23 CN CN 91103434 patent/CN1018954B/en not_active Expired
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