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EP0530249A1 - Polyolefines amorphes - Google Patents

Polyolefines amorphes

Info

Publication number
EP0530249A1
EP0530249A1 EP19910909567 EP91909567A EP0530249A1 EP 0530249 A1 EP0530249 A1 EP 0530249A1 EP 19910909567 EP19910909567 EP 19910909567 EP 91909567 A EP91909567 A EP 91909567A EP 0530249 A1 EP0530249 A1 EP 0530249A1
Authority
EP
European Patent Office
Prior art keywords
groups
units derived
alkyl
olefin
amorphous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19910909567
Other languages
German (de)
English (en)
Inventor
Brian Wilson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Imperial Chemical Industries Ltd
Original Assignee
Imperial Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Publication of EP0530249A1 publication Critical patent/EP0530249A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene

Definitions

  • This invention relates to amorphous polyolefins and in particular to amorphous copolymers of low molecular weight acyclic, particularly alpha- aliphatic olefins such as ethylene and/or propylene with bridged ring olefinic monomers especially norbornene derivatives.
  • Polyethylene and (isotactic) polypropylene are crystalline polymers having good chemical, particularly solvent, resistance and are
  • T g glass transition temperatures
  • They are substantially unaffected by moisture. They have relatively low glass transition temperatures (T g ) and thus have low strength at elevated temperatures. Being crystalline, they are translucent rather than optically clear in the wavelength range of visible light. Their low strength and relatively poor optical properties mean that these polymers are not suitable for applications such as optical disks, optical fibres and other similar optical components. It has long been known that higher Tg amorphous polymers can be made by copolymerising ethylene with norbornene and certain derivatives, for example as described in British Patent Specification Nos. 777414, 951022, US Patent Specifications Nos. 2799668 and 2883372, West German Offenlegungsschrift No 2421838 and East German Patent Specifications Nos. 215087, 222317 and 246903.
  • the present invention is based on the finding that certain cyclic aromatic substituted derivatives of bridged cyclic olefinic monomers can give clear amorphous copolymers with acyclic olefins having a good combination of optical, mechanical and physico-chemical properties. This combination of properties makes these copolymers candidates for use in optical products such as optical discs, especially CD-ROM, WORM and erasable or re-writable optical discs, optical fibres and related devices and components.
  • the present invention provides an amorphous polymer containing units derived from an acyclic mono-olefin and units derived from a norbornene type olefin including units of the formula (I):
  • n 1 is 0, 1 or 2
  • n 2 is 0 or 1 and n 1 + n 2 > 0;
  • n 3 is 0 or from 1 to 4;
  • n 4 is 0 or from 1 to 4;
  • each R 1 , each R 2 and each R 3 is independently a hydrogen or halogen atom, or an alkyl, cycloalkyl, aralkyl, alkaryl or aryl group;
  • the ring group A 1 is 1,2-cyclohexylene or a 1,2-phenylene group which may be unsubstituted or substituted with one or more halogen atoms, alkyl or aryl groups and may have further 1,2-cyclohexylene or a 1,2-phenylene ring group(s) respectively fused to it.
  • the invention includes a method of making an amorphous copolymer as defined above which comprises, polymerising a mixture of at least one acyclic mono-olefin and at least one monomer of the formula (II):
  • n 1 , n 2 , n 3 , and n 4 are each, independently, as defined above for formula (I); each R 1 , each R 2 , each R 3 , is, independently, as defined above for formula (I) or is an alkenyl group or an alkynyl group; and
  • ring group A 2 is a 1,2-phenylene ring group which may be
  • halogen atoms are preferably chlorine atoms; alkyl groups are
  • alkyl groups particularly C 1 to C 4 alkyl, especially methyl or ethyl, groups; cyclo- alkyl groups are particularly cyclohexyl groups; alkenyl groups are particularly C 2 to C 5 alkenyl, especially ethenyl or propenyl, groups; alkynyl groups are particularly C 2 to C 5 alkynyl, especially ethynyl or propargyl, groups; aralkyl groups are particularly phenyl substituted c 1 to C 4 alkyl groups, especially benzyl or phenylethyl groups; alkaryl groups are particularly C 1 to C 4 alkyl substituted phenyl groups; and aryl groups are particularly phenyl groups.
  • Alkyl, cycloalkyl, aralkyl, alkaryl or aryl groups or substituents in formulae (I) and (II) can be further substituted with halogen atoms, alkyl, alkenyl, alkynyl, cycloalkyl, aralkyl, alkaryl or aryl groups, in particular as above specified.
  • the index n 1 is most desirably 0 or 1, but, as is described below, the synthesis of the corresponding monomers (II) can conveniently be carried out by a Diels-Alder reaction that can lead to a mixture of monomeric species of the formula (II) thus giving an average value of n 1 which is non-integral.
  • the indices n 3 and n 4 are most usually equal, and in particular they are both 1 (to give a cyclohexyl ring) or both 2 (to give a cyclooctyl ring). It is also possible for both to be zero to give a cyclobutyl ring or one to be 0 and the other 1 (to give a cyclopentyl ring).
  • n 1 , and n 2 give particular sub-classes of repeating units of the formulae (I) a to c and corresponding monomers (II) a to c: when n 1 is 0 and n 2 is 1:
  • each R 1 , each R 2 and each R 3 and the ring group A 1 are, independently, as defined above for formula (I) or formula (II) respectively.
  • a 3 is a label for the ring rather than defining a separate ring group.
  • the amorphous copolymer of the invention includes units derived from at least one acyclic mono-olefin especially ethylene, propylene or a mixture of the two.
  • Units derived from other mono-olefins particularly alpha-olefins, e.g. C 4 to C 5 alpha-olefins, or vinyl aromatic monomers e.g. styrene or vinyl toluene, can be used although these will not normally be used to the exclusion of ethylene or propylene.
  • Mixtures of acyclic mono-olefins, particularly alpha-olefins, and combinations of acyclic mono-olefins with relatively small proportions of other olefinic monomers can be used. In such mixtures it is desirable that the main part of units derived from the olefin [other than units derived from norbornene type monomers, including units of the formula (I)] are ethylene and/or propylene.
  • the copolymers of the invention preferably do not have significant ethylenic
  • copolymers will, typically according to the invention, be hydrogenated to remove this additional ethylenic unsaturation before forming of the polymers into end products.
  • the extent of hydrogenation can be
  • the amorphous copolymer includes units of the formula (I) above and can include units derived from other norbornene type monomers such as norbornene itself, alkyl substituted norbornenes, such as methyl norbornene (5-methylnorbornene) and MDMON. Units derived from
  • ethylenically unsaturated norbornene type monomers can be used with reduction of the copolymer is reduced to remove the ethylenic
  • Examples of such monomers include dicyclopentadiene and ethylidene norbornene.
  • the proportions of the norbornene type olefin and the acyclic mono- olefin in the amorphous copolymer have a strong influence on the properties of the copolymer. If the units derived from the norbornene type olefin represent less than about 10 mole %, the polymer product is likely to be crystalline to a significant extent and, in practice, products containing fractions greater than 602 of units derived from the norbornene type olefin are difficult to prepare.
  • the copolymers of this invention will more usually contain from 15 to 40 mole % of units derived from the norbornene type olefin(s).
  • the proportion of units of the formula (I) will usually be at least 25% and more usually at least 50%. Generally, within these limits, a higher proportion of units derived from the norbornene type olefin will give a copolymer having a higher Tg and higher rigidity.
  • the proportion of units derived from acyclic mono-olefin monomer(s) in the copolymer will, correspondingly, generally be from 90 to 40 particularly from 85 to 60 mole %. The bulk of this will most usually be units derived from ethylene. Thus, a typical copolymer will contain from 85 to 60 mole % of units derived from ethylene, although up to about 50 mole % of these units can be replaced by units derived from propylene.
  • the proportion of units derived from olefinic monomers, other than ethylene and propylene, will be less than the combined proportion of ethylene and propylene and will usually not be greater about than
  • the monomers of the formula (II) above can be made by Diels-Alder type reaction(s) between suitable precursors under typical Diels-Alder conditions.
  • Monomers of the formula (II)a can be made by reacting an anthracene (substituted as appropriate for the monomer desired) with a corresponding dieneophile.
  • an anthracene substituted as appropriate for the monomer desired
  • a corresponding dieneophile where the ring A 3 is a 5- or more membered ring, the dieneophile will typically be the corresponding cyclic diene,
  • cyclopentadiene behaving as a dienophile despite, itself, being a conjugated diene
  • 1,4-cyclohexadiene and 1,5-cyclooctadiene to give the 5-, 6- and 8-membered ring olefin monomers.
  • the dieneophile will usually be the corresponding 3,4-dihalocyclobutene (particularly a 3,4-dichlorocyclobutene).
  • the immediate product of this Diels-Alder reaction is a dihalo-monomer, which can be converted into a monomer of the formula (II) by dehalogenating it.
  • Monomers of the formula (II)b where n 1 is 1 can be made by reacting an anthracene (substituted as appropriate for the monomer desired) with a corresponding di-olefin bridged ring dieneophile such as a
  • 1,4-norbornadiene (substituted as appropriate for the monomer desired).
  • the corresponding monomers where n 1 is greater than 1 can be made by a further Diels-Alder reaction from monomers where n 1 is 1 acting as a dienophile with a cyclopentadiene (substituted as appropriate for the monomer desired) as the diene.
  • Monomers of the formula (II)c can be made by reacting a monomer of the formula (II)a acting as a dienophile with a cyclopentadiene
  • proportions of the cyclopentadiene will typically be a mixture of compounds of differing values of n 1 and the average value of n 1 will thus usually be non-integral.
  • the monomers of the formula (II)a can be somewhat less reactive in the copolymerisation reaction than other monomers of the formula (II). We believe that this is because the ring A 3 in the monomer is less strained than in other monomers of the formula (II). Accordingly, we generally prefer to convert such monomers into the corresponding monomers of the
  • the copolymers of the invention can be synthesised by polymerisation reactions which are generally known. Typically, the polymerisation will be carried out in the presence of a Ziegler-Natta type catalyst system.
  • a Ziegler-Natta type catalyst system One restriction on the polymerisation is that it should avoid formation of polymer by the so-called ring opening metathesis polymerisation (ROMP) mechanism, as this makes (co-)polymers which contain ethylenic double bonds.
  • ROMP ring opening metathesis polymerisation
  • co-catalyst in a molar ratio in the range 1:4 to 1:20, usually about 1:10.
  • the amount of the vanadium catalyst used will be chosen for best results, but will typically be from 1/200 to 1/1000 mole of catalyst per mole of the total monomer polymerised.
  • Typical concentrations in the polymerisation reaction mixture are about 0.1 to 5, particularly about 0.5, mmo1.1 - 1 for vanadium and labout 1 to 50,particularly about 5, mmo1.1 -1 for aluminium.
  • the polymerisation reaction is typically carried out with the monomers in solution e.g. in a hydrocarbon solvent such as toluene.
  • the acyclic olefin monomer(s), particularly ethylene and/or propylene, are introduced into the reaction mix by bubbling the gaseous acyclic olefin monomer into the solution.
  • the gaseous acyclic olefin monomer is introduced into the reaction mix by bubbling the gaseous acyclic olefin monomer into the solution.
  • an inert carrier gas such as dry nitrogen.
  • the reaction will typically be carried out at or somewhat below ambient temp- erature e.g.
  • reaction proceeds suitably fast, for laboratory synthesis, under atmospheric pressure although higher pressures can be used to increase the effective concen- tration of gaseous monomer(s), particularly ethylene and/or propylene.
  • the rate of adding the acyclic olefin monomer(s) will determine the relative proportions of the norbornene type monomer(s) to the acyclic olefin monomer(s).
  • the desired proportion will, thus, be used to decide the rate of addition of the acyclic olefin monomer(s) and the proportion of diluent gas used.
  • gaseous hydrogen can be added as a chain transfer agent to control the molecular weight of the polymer produced.
  • the polymerisation reaction can be carried out as a batch or as a continuous process.
  • the copolymers of the invention are amorphous polymers and are optically transparent (rather than translucent). As made the polymers including aromatic rings can be coloured, usually fairly pale yellow. We think it likely that this reflects absorption by the aromatic ring systems in the blue visible or near ultra violet region of the spectrum although it may merely be the result of small quantities of coloured impurities. Fully hydrogenated polymers of the formula (I) are
  • the respective units derived from different monomers are distributed randomly, both in terms of the chain sequence and the stereochemistry of the sidechains. They typically have T g values in the range 110 to 220°C, good stiffness properties and are substantially unaffected by water or atmospheric moisture. They can be fabricated into optical components such as optical discs, especially CD-ROM, WORM and erasable or re-writable optical discs, optical fibres and related devices and components. Accordingly the invention includes an optical component including an amorphous copolymer of or made by the method of the
  • DCDBTCT 1,8-DiChloro-9,10,11,12-DiBenzoTetraCyclo[6.2.2.1 3,6 .0 2 ' 7 ]- Trideca-4,9,11-triene
  • acac - acetylacetonate e.g. vanadium(III)acetylacetonate
  • Et - ethyl e.g. dichloroethoxyoxovanadium is abbreviated as
  • Proportions of respective monomers incorporated into polymers - these are derived by measuring the ratio of aromatic to aliphatic protons from the integration of 1 H nmr analysis of the copolymer. Spectra were taken on a GSX 400 MHz spectrometer using 1,1,2,2-deuterated tetrachloroethane as solvent. From knowledge of the structure of the monomers, the molar proportion, of the residues derived from the respective monomers was calculated. The result is expressed as mole 2, usually by quoting the ethylene content (EC) or propylene content (PrC).
  • EC ethylene content
  • PrC propylene content
  • Tg Glass Transition temperature
  • IV Intrinsic Viscosity
  • X-Ray Diffraction (XRD) wide angle X-ray diffraction was carried out on a Phillips PW1710 Diffractometer, using a 1730 generator with 0.1° step size and a 6 second count at temperatures from 4 to 40°C. The technique is used to assess the crystallinity of the polymers. The results are quoted as "A" for polymers that showed no significant crystallinity i.e. are substantially amorphous.
  • Birefringence (BR) - was measured on an Ehrinhaus Compensator taking measurements with both the 633 and 1302nm lasers. The results are quoted in nm.
  • a norbornene type monomer (DBTCT) was copolymerised with ethylene as follows: A 1 litre flanged glass reactor fitted with a mechanical stirrer, a gas inlet dispersion tube, a thermometer and a dropping funnel was used as the polymerisation vessel. The vessel was thoroughly purged and provided with an atmosphere of dry nitrogen, charged with dry toluene (250 ml), the DBTCT and DEAC as the aluminium alkyl co-catalyst, and the dropping funnel was charged with the vanadium(III)acetylacetonate
  • the vessel was cooled to the required temperature and a mixture of nitrogen, at a flow rate of 36 1.h -1 , and ethylene, at the flow rate set out in Table 1, were passed through the solution in the vessel for 10 min.
  • the polymerisation reaction was then initiated by starting to add the vanadium catalyst solution from the dropping funnel.
  • the catalyst solution was added gradually to the reaction mixture over the reaction period.
  • the nitrogen/ethylene gas flow rate was maintained for the reaction times and temperature as set out in Table la below. A few minutes after the completion of the catalyst solution addition, the reaction was then terminated by adding methanol (5 ml).
  • the copolymer was recovered by adding the reaction mix to a large excess of methanol (containing 0.52 by volume of 1M HC1 and a small quantity of 2-t.-butyl- 4-methylphenol as antioxidant) and separating the precipitated copolymer, which was washed sequentially with methanol then with acetone and then dried in vacuo (overnight).
  • methanol containing 0.52 by volume of 1M HC1 and a small quantity of 2-t.-butyl- 4-methylphenol as antioxidant
  • the intrinsic viscosity, ethylene content, Tg, water absorption, XRD Analysis and birefringence were determined as described above and the results are set out in Table 2 below.
  • Example 2 These Examples are repeats of Example 1 except that dichloroethoxy- oxovanadium [VO(OEt)Cl 2 ] was used as the vanadium catalyst and the amounts of vanadium catalyst and the DEAC aluminium alkyl co-catalyst used are as set out in Table 1. The results of testing the copolymer products are included in Table 2.
  • Example 2 was repeated except that 302 by weight of the DBTCT monomer was dissolved in the dry toluene with the DEAC aluminium alkyl
  • Example 5 Example 4 was repeated except that EASC was used as the aluminium alkyl co-catalyst. The results of testing the copolymer product are included in Table 2.
  • Example 4 was repeated except that 302 by weight of the DBTCT monomer was dissolved in the dry toluene with the vanadium catalyst in the reactor and the remaining 702 by weight was included with in the solution in the dropping funnel the aluminium alkyl co-catalyst. Polymerisation was initiated by starting to add the aluminium alkyl co-catalyst and DBTCT solution in the dropping funnel to the solution in the reactor. The results of testing the copolymer product are included in Table 2.
  • Example 6 was repeated but with the process variations set out in Table 1. The results of testing the copolymer products are included in Table 2. Examples 8
  • Example 6 was repeated but using EASC as the aluminium alkyl co-catalyst.
  • the results of testing the copolymer products are included in Table 2.
  • Example 2 was repeated but using a reactor equipped with two dropping funnels.
  • some of the DBTCT monomer and the vanadium catalyst (0.2 mmole) were put in the reactor and the EASC aluminium alkyl co-catalyst (0.1 mmole) dissolved in dry toluene (80 ml) was placed in one dropping funnel and the remainder of the DBTCT monomer dissolved in dry toluene (80 ml) was placed in the other dropping funnel, with amounts of DBTCT monomer in the reactor and the second dropping funnel set out in Table 3 below (the DBCTC is indicated as monomer I in the Table).
  • the reactor was cooled to a reaction temperature of 12°C purged using nitrogen (at 36 1.hr -1 ) and ethylene at a flow rate of 9.6 1.hr -1 .
  • the polymerisation was initiated by starting to add the EASC solution from the dropping funnel.
  • the DBTCT monomer from the second dropping funnel was added gradually over the reaction period of 30 minutes.
  • the results of testing the copolymer product are set out in Table 4 below.
  • Example 9 was repeated but using the amounts of monomer in the reactor and second dropping funnel set out in Table 3 and an ethylene flow rate of 10.8 1.hr -1 .
  • the results of testing the copolymer product are included in Table 4.
  • Example 9 was repeated but using MDBTCT as the norbornene type monomer and using the amounts of monomer in the reactor and second dropping funnel set out in Table 3. The results of testing the copolymer product are included in Table 4.
  • Example 9 was repeated but using a combination of DBTCT and
  • Example 12 was repeated but using DCDBTCT and norbornene as the norbornene type monomers and using the amounts of the monomers in the reactor and second dropping funnel set out in Table 3. The results of testing the copolymer product are included in Table 4.
  • Example 14 Example 12 was repeated but using DBTTT and norbornene as the norbornene type monomers and using the amounts of the monomers in the reactor and second dropping funnel set out in Table 3. The results of testing the copolymer product are included in Table 4.
  • Example 15 Example 15
  • Example 9 was repeated but using a combination of ethylene and propylene as the acyclic olefin monomers to produce a terpolymer product.
  • the amounts of the DBTCT monomer used in the reactor and second dropping funnel are set out in Table 3 and 40 ml dry toluene was used as the solvent for the EASC used as the aluminium alkyl co-catalyst in the first dropping funnel.
  • the results of testing the copolymer product are included in Table 4. Examples 16 and 17
  • Example 15 repeated Example 15 with the process variations set out in Table 3.
  • the results of testing the copolymer products are included in Table 4. :

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  • Chemical & Material Sciences (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)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Des polyoléfines amorphes comprenant des unités dérivées de mono-oléfines acycliques, en particulier l'éthylène, et des unités dérivées d'oléfines du type norbornène comprenant des unités de la formule (I), où n1 représente 0, 1 ou 2, n2 représente 0 ou 1 et n1 + n2 > 0; n3 représente 0 ou de 1 à 4; n4 représente 0 ou de 1 à 4; R1, R2 et R3 représentent chacun hydrogène, halogène, alkyle, cycloalkyle, aralkyle, alkaryle ou aryle; le groupe cyclique A1 représente 1,2-cyclohexylène ou un 1,2-phénylène qui peut être non substitué ou substitué par un halogène, alkyle ou aryle et peut en outre incorporer du 1,2-cyclohexylène ou du 1,2-phénylène. Les polymères peuvent être produits par la polymérisation des monomères sous catalyse Ziegler-Natta. Ils sont amorphes et transparents, présentent des températures de transformation élevées et sont utiles dans des composants optiques tels que des disques optiques.
EP19910909567 1990-05-21 1991-05-21 Polyolefines amorphes Withdrawn EP0530249A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9011346 1990-05-21
GB909011346A GB9011346D0 (en) 1990-05-21 1990-05-21 Amorphous polyolefins

Publications (1)

Publication Number Publication Date
EP0530249A1 true EP0530249A1 (fr) 1993-03-10

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EP19910909567 Withdrawn EP0530249A1 (fr) 1990-05-21 1991-05-21 Polyolefines amorphes

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EP (1) EP0530249A1 (fr)
AU (1) AU7874691A (fr)
GB (1) GB9011346D0 (fr)
WO (1) WO1991018029A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1113907C (zh) * 1995-05-08 2003-07-09 奥普塔技术公司 非晶态烯烃共聚/三元聚合物
US6885415B2 (en) 2001-05-10 2005-04-26 Sumitomo Chemical Company, Limited Optical member and optical product provided therewith

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100441335B1 (ko) * 1995-12-07 2004-10-25 엑손모빌 케미칼 패턴츠 인코포레이티드 점착부여제및점착부여제의제조방법

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2883372A (en) * 1957-03-14 1959-04-21 Du Pont Copolymers of ethylene and dihydrodicyclopentadiene
JPH0819189B2 (ja) * 1987-10-02 1996-02-28 三井石油化学工業株式会社 環状オレフイン系ランダム共重合体の製法
DE68923842T2 (de) * 1988-10-06 1996-04-25 Showa Denko Kk Copolymer von Ethylen und ein polycyclisches Monomer, Verfahren zu deren Herstellung und optischer Artikel.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9118029A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1113907C (zh) * 1995-05-08 2003-07-09 奥普塔技术公司 非晶态烯烃共聚/三元聚合物
US6885415B2 (en) 2001-05-10 2005-04-26 Sumitomo Chemical Company, Limited Optical member and optical product provided therewith

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Publication number Publication date
WO1991018029A1 (fr) 1991-11-28
GB9011346D0 (en) 1990-07-11
AU7874691A (en) 1991-12-10

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