US2367660A - Process of photopolymerization - Google Patents
Process of photopolymerization Download PDFInfo
- Publication number
- US2367660A US2367660A US425201A US42520141A US2367660A US 2367660 A US2367660 A US 2367660A US 425201 A US425201 A US 425201A US 42520141 A US42520141 A US 42520141A US 2367660 A US2367660 A US 2367660A
- Authority
- US
- United States
- Prior art keywords
- polymerization
- light
- photopolymerization
- compound
- methyl methacrylate
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 19
- 238000006116 polymerization reaction Methods 0.000 description 59
- 150000001875 compounds Chemical class 0.000 description 50
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 31
- 229920000642 polymer Polymers 0.000 description 29
- 229940102838 methylmethacrylate Drugs 0.000 description 28
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- 239000004215 Carbon black (E152) Substances 0.000 description 18
- 229930195733 hydrocarbon Natural products 0.000 description 18
- 239000011521 glass Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 16
- -1 hydrocarbon radicals Chemical class 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 230000001678 irradiating effect Effects 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 11
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 239000000178 monomer Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- 150000002367 halogens Chemical group 0.000 description 9
- 150000002431 hydrogen Chemical group 0.000 description 8
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 150000002978 peroxides Chemical class 0.000 description 7
- 239000005297 pyrex Substances 0.000 description 7
- 230000001419 dependent effect Effects 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 125000002560 nitrile group Chemical group 0.000 description 6
- 238000005266 casting Methods 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000006188 syrup Substances 0.000 description 4
- 235000020357 syrup Nutrition 0.000 description 4
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000003979 granulating agent Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229940032147 starch Drugs 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000005521 carbonamide group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229940055577 oleyl alcohol Drugs 0.000 description 2
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- OJUGVDODNPJEEC-UHFFFAOYSA-N phenylglyoxal Chemical compound O=CC(=O)C1=CC=CC=C1 OJUGVDODNPJEEC-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RXVBJUZEFSAYPW-UHFFFAOYSA-N 1,3-diphenylpropane-1,2,3-trione Chemical compound C=1C=CC=CC=1C(=O)C(=O)C(=O)C1=CC=CC=C1 RXVBJUZEFSAYPW-UHFFFAOYSA-N 0.000 description 1
- DMYOHQBLOZMDLP-UHFFFAOYSA-N 1-[2-(2-hydroxy-3-piperidin-1-ylpropoxy)phenyl]-3-phenylpropan-1-one Chemical compound C1CCCCN1CC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 DMYOHQBLOZMDLP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical class OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 241001303142 Lysobacter agri Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920001079 Thiokol (polymer) Polymers 0.000 description 1
- PDAVOLCVHOKLEO-UHFFFAOYSA-N acetyl benzenecarboperoxoate Chemical compound CC(=O)OOC(=O)C1=CC=CC=C1 PDAVOLCVHOKLEO-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- AWJZTPWDQYFQPQ-UHFFFAOYSA-N methyl 2-chloroprop-2-enoate Chemical compound COC(=O)C(Cl)=C AWJZTPWDQYFQPQ-UHFFFAOYSA-N 0.000 description 1
- SMUVTFSHWISULV-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile Chemical compound C=CC#N.COC(=O)C(C)=C SMUVTFSHWISULV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940079832 sodium starch glycolate Drugs 0.000 description 1
- 229920003109 sodium starch glycolate Polymers 0.000 description 1
- 239000008109 sodium starch glycolate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- 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
- C08F4/00—Polymerisation catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31913—Monoolefin polymer
- Y10T428/3192—Next to vinyl or vinylidene chloride polymer
Definitions
- This invention relates to the photopolymerization of polymerizable ethylenically unsaturated organic compounds, 1. e., the polymerization thereof under the influence of light.
- This invention has as an object an improvement in the photopolymerization of a photopolymerizable ethylenically unsaturated organic compound having a methylene (CH2) group attached by a double bond to a carbon which is in turn attached to a carbon all of the remaining valences of which are satisfied through polyvalent electronegative inorganic elements of the first full period of the periodic system, which comprises eiiectin the photopolymerization of said compound in the presence of, i. e., admixed with a vicinal ketaldonyl compound, i. e., a compound having a plurality of vicinal carbonyl groups wherein the terminal valences are satisfied by hydrogen or monovalent hydrocarbon radicals and :c is two or three, and preferably two.
- the photopolymerizable ethylenically unsaturated compounds of this invention have a methylene (CH2) group attached by a double bond to a carbon which is in turn attached to a carbon all of the remaining valences of which are satisfied through polyvalent electronegative inorganic elements of the first full period of the periodic system.
- They include the acids, esters, amides, and nitriles of acrylic, alpha-halogen substituted acrylic and alpha hydrocarbon substituted acrylic acids, i. e., compounds having the structure where X is hydrogen, halogen, or hydrocarbon and Y is COOR, CONHz, or CN, and R is hydrogen or hydrocarbon.
- the photopolymerization may be according to any of the modes known to the art, e. g., bulk,
- the vessel can be constructed or glass so that the light can enter the system through the sides of the vessel, or there can be a source of light within the vessel.
- the source of light may be sunlight, a mercury vapor lamp, a tungsten bulb, or some similar arrangement to give light either in the range of the ultraviolet rays plus visible light, or in the range of visible light alone. Polymerization occurs fairly rapidly under relatively mild conditions of temperature; and the rate is dependent on the temperature in the system and the intensity of the light. In order to obtain sheets and castings free from defects, it is desirable to control the temperature so that local over-heating does not occur.
- the extent of polymerization can be determined by measuring the refractive indexwhich changes with the degree of polymerization or by gravlmetric methods involving the separation of the polymeric product. By application of this process, bulk castings free from surface defects can be obtained in a relatively short period of time.
- emulsion polymerization the readily polymerizable ethylenic compounds and photopolymerization catalysts (vicinal polyketaldonyl compounds) are held in emulsion in water by an emulsifying agent.
- the emulsion is'then irradiated through the side of the vessel or by some other suitable method until polymerization has proceeded to the desired extent.
- Still more rapid polymerization occurs if a peroxide (such as hydrogen peroxide) is present in the emulsion together with the vicinal polyketaldonyl compound.
- the polymer is then precipitated from the emulsion, after the removal of residual monomer, by the addition of a small amount of an electrolyte or by freezing.
- the product is then thoroughly washed and dried in the usual manner.
- a material to be polymerized containing a.small amount of the vicinal polyketaldonyl compound as the photopolymerization catalyst is rapidly agitated in an aqueous system containing a small percentage (up to about 3%) of a protective colloid, which acts as the granulating agent, in a vessel equipped with a reflux condenser at such a temperature that moderate reflux is maintained.
- a protective colloid which acts as the granulating agent
- the material undergoing polymerization is dispersed in the form of small droplets which solidify as polymerization proceeds to give a polymer in the form of small granules.
- the granules are readily filtered from the mixture, washed free from occluded colloid-and dried.
- the ethylenic compound and the polyketaldonyl compound are dissolvediin a solvent and light is directed upon the solution until the desired extent of polymerization is achieved.
- Example I This example illustrates the bulk photopolymerization of methyl methacrylate in the presence of vicinal polyketaldonyl compounds.
- Methyl methacrylate specimens containing one per cent of their weight of the polyketaldonyl compound indicated in the table below were placed in glass vessels and were exposed at 40 C. to the light from a mercury vapor light (a Westinghouse H-3 lamp modified by mounting the bulb in a 20 mm. quartz tube) operating at 85 watts and mounted at a distance of 6 inches from the specimens.
- the indicated time represents the period required for the liquid monomer to be converted into a solid (about 30%) polymer. For example, the sample which contained diacetyl solidified in 2 hours, whereas a control specimen containing no photopolymerization catalyst solidified in 12 hours.
- the following table lists the observed data.
- the present example illustrates the eflect of diacetyl on the photopolymerization ofvarious monomers.
- the time element as noted in the table below represents the period in hours required for polymerization of the listed monomer to a solid and in each instance is compared with'the period necessary for similar polymerization of a control having no photopolymerization catalyst present.
- the material to be polymerized was placed in a glass vessel (capable of transmitting light of greater than 2850 A.) and 0.1% of diacetyl was samples were then irradiated with light from a 6 inch mercury vapor are operating at about 150 volts, and 4.5 amperes mounted at a distance of lO-l2 inches and the extent of polymerization measured by means of the refractive indices as polymerization proceeded.
- the following table indicates the time required to effect 5% polymerization of methyl methacrylate monomer in the presence of the designated amount of photopolymerization catalyst.
- Example III Time for 5% t Example III The previous examples illustrate the photopolymerization of methyl methacrylate in the added. The solution was then exposed at 40 C.
- Example II to the light from a mercury vapor are as in Example II at a distance of 10-12 inches until the material had become solid. In each instance a control without diacetyl was irradiated simultaneously.
- Example IV This example illustrates the preparation of a sheet Casting'by the process 01 this invention.
- Example V This example illustrates the Preparation of a large hulk casting by the practice of this invention.
- a solution of methyl methacrylate containing about 0.1% of 2,2-dimethyli-phenylbutanedione-3,4 was placed in a suitable glass container which was mounted in a fluid to provide a means for controlling the temperature of polymerization.
- Light from a mercury lamp as described in Example I was directed through the bottom of the container at a distance of 6-8 inches until polymerization appeared to be practically complete.
- the bulk casting was then baked several hours at about 75 C. to insure complete polymerization.
- the product thus obtained was practically colorless and is free from defects such as bubbles, striations, and the liige.
- Example VI 140 parts of methyl methacrylate, 260 parts of distilled water and 8 parts of an emulsifying agent (the sodium salt of the sulfate of oleyl alcohol) was added to each of three Pyrex glass vessels. of diacetyl was added. Two of these tubes were exposed at C. to the irradiation of a mercury vapor lamp, as described in Example I, at a distance of 6-8 inches, while the other was kept in the dark at the same temperature. At the end of 80 minutes all the emulsions were broken by the addition of an electrolyte (aluminum sulfate) and the polymers were isolated.
- the following table contains the data thus obtained, and shows the beneficial efiect of the presence of diacetyl in the photopolymerization of methyl -methacrylate.
- Example VII This example illustrates the emulsion photopolymerization of methyl methacrylate under the influence of a peroxide and a vicinal polyketaldonyl compound with only a very short initial irradiation, the polymerization continuing even in the dark.
- Example VIII The following example illustrates the simultaneous photopolymerization of methyl methacrylate and other unsaturated polymerizable materials by the emulsion process-in the presence of a peroxide and of a polyketaldonyl compound.
- the following table represents-data obtained from polymers prepared in the same way from vinyl chloride or vinylidene chloride with the designated monomer A.
- the polymers were formed under conditions analogous to those of the above description.
- Example IX The following example illustrates the beneficial effect of the presence of. a polyketaldonyl compound on the photopolymerization of methyl methacrylate in solution.
- Example X This example illustrates the application of this invention to the granular photopolymerization of methyl methacrylate.
- a mixture of 200 parts of water, 1 part ,of methyl starch (granulating agent), 100 parts of methyl methacrylate, and 0.5 part of diacetyl was placed in a vessel or such construction that its contents could be irradiated by means of a mercury vapor are, as described in Example II, at a distance of 6-7 inches.
- the mixture was stirred vigorously and was heated under reflux. In 55 minute polymerization was practically complete.
- the granular product was washed well and dried, giving an almost quantitative yield of. polymer.
- the material was molded into a chip which softened at about 123 C.
- Example XI This example illustrates the use of sunlight in the photopolymerization of methyl methacrylate with the aid of a photopolymerization catalyst.
- Example XII This example illustrates the use of a tungsten light in the catalysed photopolymerization of meth l methacrylate.
- Illustrative polyketaldonyl compounds include diacetyl, pentandione-2,3, octandione-2,3, l-phenylbutandione-LZ, benzil, 2,2-dimethyl-i-phenylbutandione-3,4, glyoxal, phenylglyoxal, diphenyltriketone, and cyclohexanedione.
- the invention is generic to the use of any such vicinal polyketaldonyl compounds in the photopolymerization, including photointerpolymerization, of an ethylenically unsaturated compound having a methylene (CI-I2) group attached by a double bond to a carbon which is in turn attached to a carbon all of the remaining valences of which are satisfied through polyvalent electronegative inorganic elements of the first full period of the periodic system, which compound may be photopolymerized either alone or at least in combination with another such compound.
- Illustrative compounds include acrylic, chloroacrylic, and methacrylic esters, amides, nitriles, e.
- methyl acrylate, methyl chloroacrylate, methyl methacrylate, methacrylamide, methacrylonitrile, and acrylonitrile are particularly preferred because of the rapidity, convenience and satisfactory nature of their photoolymerization.
- the acrylates and methacrylates are esters of aliphatic monocarboxylic acids of from 3 to 4 carbons having the carboxyl attached to a monovalent hydrocarbon radical having an ethylenic double bond between the carbon attached to the carboxyl and a carbon once'removed therefrom.
- Th invention is also applicable to mixtures which photopolymerize.
- certain unsaturated compounds which do not polymerize readily alone under the influence 01 light will polymerize simultaneously with other readily polymerizable materialsj these' unsaturated compounds also are included in this invention.
- An example is the simultaneous polymerization of diethyl iumarate, which does not polymerize readily, and methyl methacrylate which polymerizes easily.
- Unsaturated materials which do not polymerize under the action of light alone or at least in mixture with other photopolymenzable ethylenically unsaturated compounds are excluded from this invention.
- the present invention is an improvement in photopolymerization, i. e., in polymerization inii-uenced by radiant energy in the form of light rays, both visible and invisible.
- the term light as herein used includes wavelengths both in the infrared and in the ultraviolet and, of course, wavelengths of all light in the intermediate visible spectrum.
- Light waves in the infrared are operable in eilecting photopolymerization of the compounds herein described in the presence of the designated photopolymerization catalysts but the rate of photopolymerization is slower than in visible or in ultraviolet light.
- Light in the ultraviolet region having wavelengths shorter than 3200 Angstroms and, for example, down to 1800 Angstroms which is the limit of transmission of quartz is operable in this process.
- the most useful and effective light is that having wavelengths between 3200 Angstroms and 7000 Angstroms. Although as pointed out above, wavelengths below 3200 Angstroms are effective, no difference in the rate of polymerization is noted when wavelengths of light of equal intensity and lower than 3200 Angstroms are prevented from reaching the photopolymerizable compound. Thirty-two hundred Angstroms is the lower limit of transmission of ordinary glass and since light passing through this material is frequently used in this process, this figure represents a lower preferred limit. The upper limit of 7000 Angstroms represents the beginnin of the infrared band having the less effective wavelengths.
- the wavelengths of light actually utilized in the photopolymerization process depend frequently on the opacity or transparency of the walls of the container holding the photopolymerizable compound. In general, light which contains wavelengths higher than those to which the transparent material is partially or completely opaque is necessary. For example. when ordinary glass is used as a container for the photopolymerizable material, and light is transmitted through the walls of the container, the light reaching the photopolymerization reaction mixture is largely that containing wavelengths greater than 3200 Angstroms. When tubes or vessels of Pyrex glass are employed to hold the photopolymerization reaction mixture, the lower limit. of the light available is approximately 2850 angstroms.
- the limit of actinic rays for methyl methacrylate itself is about 3500 Angstrom, so that in photopolymerizations using methyl methacrylate monomer, light havinga wavelength greater than 3500 Angstroms should, in general, be available for the photopolymerization.
- the walls of the container are not always a limiting factor since it has been shown that X-rays of wavelengths of 0.7 Angstrom are also effective for causing polymerization.
- the rate of the photopolymerization varies directly with the intensity of the light and can usually be increased or diminished b increasing or diminishing the intensity of the light that reaches the reaction mixture.
- a convenient source of light of proper intensity is the mercury vapor are which emits light in the ultraviolet as well as in the visible range.
- Another convenient source of light is a tungsten bulb of suitable intensity, for example, a General Electric Mazda PS-52, 1500 watt, 110 volts, will function effectively.
- Sunlight is another source of effective light for carrying out the photopolymerization in the presence of the photopolymerization catalysts.
- Difiused daylight contains wavelengths of light which are active for the catalyzed photopolymerization but the reaction is considerably slower than with other more intense sources of light.
- the type of container used for the polymerization depends upon the results desired. For instance, in the bulk polymerization of a monomer to form sheeting, it is desirable to have smooth surfaces; and, consequently, glass plates ordinarily are used. In small scale granulation and emulsion polymerization Pyrex glass containers may be employed. However, in industrial applications such containers would not be available in sumciently large size and it is necessary to use metallic containers with the light above or within the material to be polymerized.
- the temperature of polymerization is dependent on the monomer being polymerized and the type of process employed. The usual range is from room temperature to about 100 C. In the bulk polymerization of a material such as methyl methacrylate it is necessary to keep the temperature fairly constant at some value within the range of 25 to 85 C. in order to control the polymerization and avoid the development of defacts.
- the molecular weight is somewhat dependent upon the temperature of polymerization as well as on other factors, and this consideration therefore enters into the determination of operating conditions.
- Granualr polymerization ordinarily is carried out at reflux temperature; emulsion polymerization at about 25-85 C. Temperatures above 100 C. can frequently'be advantageously employed in apparatus designed to withstand the operating pressure.
- the concentration of polyketaldonyl compound in the solution is of importance because-it appreciably affects the rate of polymerization, as shown in Example 2.
- the photopolymerization catalyst need not; be employed alone in the photopolymerization iof the readily polymerizable materials, but can be used in conjunction with a peroxide.
- the molecular weight of the polymer also is appreciably dependent on the concentration of the photopolymerization catalyst in the system.
- Emulsifying or dispersing agents selected must be suitable for use in the system employed.
- Dispersing agents which perform acceptably in acid media include salts of sulfonic acid and sulfuric acid esters of long chain compounds, such as the sodium salt of acetoxyoctadecanesulfate.
- This invention is not limited to the application of any specific emulsifying agents.
- the protective colloids used as granulating agents can be any type of soluble starch, methylated starch, partially hydrolyzed polyvinyl acetate, the sodium salts of polymers or interpolymers containing acrylic or methacrylic acids, polymethacrylamide,
- ketaldonyl has been applied to designate the 0 group as it appears in aldehydes and ketones in contradistinction to the 0:0 group as it appears in acids or esters.
- the CO group as it appears in acids R-CO-OH or esters R-COOR is very different in its properties from the carbonyl group in aldehydes and ketones and the expression ketaldonyl group is employed to distinguish th aldehydic and ketonic carbonyl group from the acidic CO group, i. e., to distinguish the CO-- group whose remaining valences are satisfied by hydrogen or carbon from the acidic -CO- group at least one of the valences of which is satisfied by hydroxyl, halogen, amido or like negative group.
- ketaldone is used as a ge neric designation for aldehydes and ketones.
- Process for preparing polymers which comprises irradiating, with light of wavelengths in the range of 1800 to 7000 Angstroms of such intensity and for a time sufficient to produce a substantial amount of polymerization, a composition comprising a photopolymerizable compound of the formula wherein X is selected from the class consisting of hydrogen, halogen, and hydrocarbon and Y is selected from the class consisting of the esterified x on -o wherein X is selected from the class consisting of hydrogen, halogen, and hydrocarbon and Y is selected from the class consisting of the esterified carboxyl group, the carbon-amido group,
- X is selected from the class consisting oi hydrogen, halogen, and hydrocarbon and Y is selected from the class consisting of the esterified carboxyl group, the carbon-amido group, and the nitrile group and, as a photopolymerization as accelerator therefor, acompound of the formula nF-co-co-a' wherein R and R. are selected from the class consisting of hydrogen and monovalent hydrogg carbon radicals.
- Process for preparin polymers which comprises irradiating, with light of wavelengths in the range of 1800 to 7000 Angstroms of such intensity and for a time sufiicient to produce a substantial amount of polymerization, a composition comprising a photopolymerizable compound of the formula CHFC ⁇ wherein X is selected from the class consisting of hydrogen, halogen, and hydrocarbon and Y is selected from the class consisting of the esterifled carboxyl group, the carbon-amide group,
- X is selected from the class consisting of hydrogen, halogen, and hydrocarbon and Y is selected from the class consisting of the esterified carboxyl group, the carbon-amido group, and the nitrile group and, as a photopolymerization accelerator therefor, diacetyl.
- Process for preparing polymers which comprises irradiating, with light of wavelengths in the range of 1800 to 7000 Angstroms of such intensity and for a time sufllcient to produce a substantial amount of polymerization, a composition comprising methyl methacrylate and, as a photopolymerization catalyst therefor, a vicinal polyketaldonyl compound.
- Process for preparing polymers which comprises irradiating, with light of wavelengths in the rangeof 1800 to 7000 Angstroms of such intensity and for a time sufficient to produce a substantial amount of polymerization, a composition comprising an alkyl ester of an acyclic monocarboxylic acid wherein the carboxyl is attached to a hydrocarbon radical of from two to three carbon atoms wherein the carbon attached to the carboxyl group is attached-by an ethylenic double bond to a methylene (CH2) group and, as a photopolymerization catalyst therefor, a vicinal polyketaldonyl compound.
- a composition comprising an alkyl ester of an acyclic monocarboxylic acid wherein the carboxyl is attached to a hydrocarbon radical of from two to three carbon atoms wherein the carbon attached to the carboxyl group is attached-by an ethylenic double bond to a methylene (CH2) group and, as a photopolymerization catalyst therefor,
- Process for preparing polymers which comprises irradiating, with light of wavelengths in the range of 1800 to '7000 Angstrom of such intensity and for a time sufilcient to produce a substantial amount of polymerization, a composition comprising methyl methacrylate and, as a photopolymerization catalyst therefor, diacetyl.
- Process for preparing polymers which comprises irradiating, with light of wavelengths in the range of 1800 to 7000 Angstroms of such intensity and for a time sufficient to produce a substantial amount of polymerization, a composition comprising an alkyl ester of an acyclic monocarboxylic acid wherein the carboxyl is attached to a hydrocarbon radical of from two to three carbon atoms wherein the carbon attached to the carboxyl group is attached by an ethylenic double bond to a methylene (CH2) group and, as a photopolymerization catalyst therefor, diacetyl.
- a composition comprising an alkyl ester of an acyclic monocarboxylic acid wherein the carboxyl is attached to a hydrocarbon radical of from two to three carbon atoms wherein the carbon attached to the carboxyl group is attached by an ethylenic double bond to a methylene (CH2) group and, as a photopolymerization catalyst therefor, diacetyl.
- Process for preparing polymers which comprises irradiating, with the light generated by a mercury vapor lamp having wavelengths in the range of 3200 to'7000 Angstroms of such intensity and for a time sufilcient to produce a substantial amount of polymerization, a composition comprising a photopolymerizablecompound of the formula wherein X is selected from the class consisting of hydrogen, halogen, and hydrocarbon and Y is selected from the class consisting of the esterifled carboxyl group, the carbon-amido group, and the nitrile group and, as a photopolymerization accelerator therefor, a vicinal polyketaldonyl compound.
- Process for preparing polymers which comprises irradiating, with the light generated by a mercury vapor lamp having wavelengths in the range of 3200 to 7000 Angstroms of such intensity and for a time sufficient to produce a substantial amount of polymerization, a composition comprising methyl methacrylate and diacetyl.
- Process for preparing polymers which comprises irradiating, with light of wavelengths in the range of 1800 to 7000 Angstroms of such intensity and for a time sumcient to produce a substantial amount of polymerization.
- a composition comprising a photopolymerizable compound of the formula wherein K is selected from the class consisting of hydrogen, halogen, and hydrocarbon and Y is selected from the class consisting of the esterifled carboxyl group, the carbonamide group, and the nitrile group and, as'a photopolymerization accelerator therefor, a compound of the formula wherein R and R are hydrocarbon radicals.
- Process for preparing polymers which comprises irradiating, with light of wavelengths in the range of 1800 to 7000 Angstroms or such in-- wherein R and R are hydrocarbon radicals.
- Process for preparing polymers which comprises irradlating, with light of wavelengths in the range of 1000 to 7000 Angstroms of such intensity and for a time sufliclent to produce a substantial' amount of polymerization, a composition comprising methyl methacrylate and, as a photopolymerization catalyst therefor, a compound of the formula R-CO-CO-R' wherein R and R' are hydrocarbon radicals.
- Process for preparing polymers which comprises irradiating, with light or wavelengths in the range of 1000 to 7000 Angstroms of such intensity and for a time sufllclent to produce a substantial amount of polymerization, a composition comprising acrylonitrile and, as a photopolymerization catalyst therefor, diacetyl.
- a composition comprising an alkyl ester of an acyclic monocarboxyllo acid wherem the carboxyl is attached to a hydrocarbon radical of from two to three carbon atoms wherein the carbon attached to the carboxyl group is attached by an ethylenlc double bond to a methylene (CH2) group and, as a photopolymerization catalyst therefor, behlil.
- Process for preparing polymers which oomprises irradiating, with light of wavelengths in the range of 1800 to 7000 Angstrom of such intensity and for a time sufficient to prod a substantlal amount of polymerisation, a composition comprising methyl methacrylate and, as e photopolymerization catalyst therefor benlil;
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE465271D BE465271A (fr) | 1941-12-31 | ||
US425201A US2367660A (en) | 1941-12-31 | 1941-12-31 | Process of photopolymerization |
US462824A US2413973A (en) | 1941-12-31 | 1942-10-21 | Photopolymerization of vinyl and vinylidene compounds |
GB17107/42A GB567778A (en) | 1941-12-31 | 1942-12-01 | Improvements in or relating to the photo-polymerisation of ethenoid compounds |
FR926637D FR926637A (fr) | 1941-12-31 | 1946-03-26 | Procédé de photopolymérisation et produits en résultant |
DEP1246A DE900275C (de) | 1941-12-31 | 1950-04-14 | Verfahren zur Polymerisation einer ungesaettigten photopolymerisierfaehigen Verbindung |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US425201A US2367660A (en) | 1941-12-31 | 1941-12-31 | Process of photopolymerization |
Publications (1)
Publication Number | Publication Date |
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US2367660A true US2367660A (en) | 1945-01-23 |
Family
ID=23685589
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
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US425201A Expired - Lifetime US2367660A (en) | 1941-12-31 | 1941-12-31 | Process of photopolymerization |
US462824A Expired - Lifetime US2413973A (en) | 1941-12-31 | 1942-10-21 | Photopolymerization of vinyl and vinylidene compounds |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US462824A Expired - Lifetime US2413973A (en) | 1941-12-31 | 1942-10-21 | Photopolymerization of vinyl and vinylidene compounds |
Country Status (5)
Country | Link |
---|---|
US (2) | US2367660A (fr) |
BE (1) | BE465271A (fr) |
DE (1) | DE900275C (fr) |
FR (1) | FR926637A (fr) |
GB (1) | GB567778A (fr) |
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US3153022A (en) * | 1958-10-03 | 1964-10-13 | Du Pont | Monomer-polymer acrylic sirups |
DK98917C (da) * | 1958-11-13 | 1964-06-01 | Du Pont | Polymer-i-monomer-sirup til anvendelse ved fremstilling af plast-produkter og fremgangsmåde til dens fremstilling. |
US3136638A (en) * | 1959-06-26 | 1964-06-09 | Gen Aniline & Film Corp | Photosensitive stencil and process of making the same |
BE609582A (fr) * | 1960-10-26 | 1900-01-01 | ||
US3133828A (en) * | 1961-12-13 | 1964-05-19 | Alfred D Slatkin | Process and apparatus for polymerized surface coating |
BE636522A (fr) * | 1962-08-24 | |||
NL297274A (fr) * | 1962-09-07 | |||
US3134684A (en) * | 1963-01-10 | 1964-05-26 | Grace W R & Co | Method of adhering vinylidene chloride polymer to polyethylene |
US3291600A (en) * | 1963-01-14 | 1966-12-13 | Rca Corp | Electrophotographic recording element and method of making |
US3214494A (en) * | 1963-01-18 | 1965-10-26 | Monsanto Co | Process for preparing polymers using a catalyst system comprising arylethylene oxide, aryl dicarbonyl and monocarboxylic acid |
DE1219224B (de) * | 1963-02-25 | 1966-06-16 | Bayer Ag | Polyesterformmassen |
US3317450A (en) * | 1963-03-14 | 1967-05-02 | Dow Chemical Co | Interpolymers of vinylidene chloride and diacrylate esters of a glycol |
US3265527A (en) * | 1963-05-27 | 1966-08-09 | Du Pont | Process of preparing non-woven polymer bonded fabric and article |
GB1062338A (en) * | 1963-11-19 | 1967-03-22 | Dunlop Rubber Co | Improvements in or relating to acrylic polymer emulsions |
US3361696A (en) * | 1964-05-13 | 1968-01-02 | Armstrong Cork Co | Water-based addition polymer |
US3359129A (en) * | 1964-05-15 | 1967-12-19 | Gen Motors Corp | Method of photopolymerizing acrylic monomer coatings |
US3351603A (en) * | 1965-02-19 | 1967-11-07 | American Cyanamid Co | Acrylate colorless transparent photoactivatable cementing compositions |
US3528844A (en) * | 1965-08-13 | 1970-09-15 | Ford Motor Co | Radiation-curable-vinyl resin paints and coated article |
US3421501A (en) * | 1965-09-22 | 1969-01-14 | Leroy E Beightol | Method and application of orthopedic appliances with an ultraviolet curable plastic impregnated bandage |
US3372672A (en) * | 1966-03-21 | 1968-03-12 | Gen Electric | Photopolymerization means in a vapor deposition coating apparatus |
GB1180846A (en) * | 1967-08-08 | 1970-02-11 | Agfa Gevaert Nv | Photopolymerisation of Ethylenically Unsaturated Organic Compounds |
JPS4818563B1 (fr) * | 1969-03-07 | 1973-06-07 | ||
US3565039A (en) * | 1969-06-25 | 1971-02-23 | Inca Inks | Printing and coating apparatus |
US3857768A (en) * | 1969-10-28 | 1974-12-31 | Ube Industries | Process for radiation cross-linking polymethyl acrylate-methyl acrylate compositions |
US3726710A (en) * | 1970-09-02 | 1973-04-10 | Union Carbide Corp | Silicon paper release compositions |
US3968305A (en) * | 1970-12-28 | 1976-07-06 | Mitsubishi Rayon Co., Ltd. | Mar-resistant synthetic resin shaped article |
US3715211A (en) * | 1971-02-01 | 1973-02-06 | Horizons Inc | Process and product of cold sealing an anodized aluminum article by a photo-polymerization process |
BE793646A (fr) * | 1972-01-03 | 1973-05-02 | Gaf Corp | Dalles de recouvrement de dimensions stables |
FR2290458A1 (fr) * | 1974-11-08 | 1976-06-04 | Thomson Csf | Resine sensible aux electrons et son application a la realisation de masques de haute resolution pour la fabrication de composants electroniques |
US3996394A (en) * | 1975-03-24 | 1976-12-07 | Union Carbide Corporation | Method of improving adhesion to plastic substrates |
US4358519A (en) * | 1977-12-05 | 1982-11-09 | Honeywell Inc. | Technique of introducing an interface layer in a thermoplastic photoconductor medium |
DE2937081A1 (de) * | 1978-09-11 | 1980-03-20 | Unisearch Ltd | Verfahren zum verleihen von permanentbuegeleigenschaften |
US6730244B1 (en) | 1986-01-28 | 2004-05-04 | Q2100, Inc. | Plastic lens and method for the production thereof |
US6201037B1 (en) | 1986-01-28 | 2001-03-13 | Ophthalmic Research Group International, Inc. | Plastic lens composition and method for the production thereof |
US5415816A (en) | 1986-01-28 | 1995-05-16 | Q2100, Inc. | Method for the production of plastic lenses |
US5185385A (en) * | 1987-01-13 | 1993-02-09 | Texaco Chemical Company | Polymerization process |
DE4432648A1 (de) | 1994-09-14 | 1996-03-21 | Bayer Ag | Tertiäre Amine, ein Verfahren zu ihrer Herstellung und ihre Verwendung als Härtungsbeschleuniger |
US6022498A (en) | 1996-04-19 | 2000-02-08 | Q2100, Inc. | Methods for eyeglass lens curing using ultraviolet light |
US6280171B1 (en) | 1996-06-14 | 2001-08-28 | Q2100, Inc. | El apparatus for eyeglass lens curing using ultraviolet light |
-
0
- BE BE465271D patent/BE465271A/xx unknown
-
1941
- 1941-12-31 US US425201A patent/US2367660A/en not_active Expired - Lifetime
-
1942
- 1942-10-21 US US462824A patent/US2413973A/en not_active Expired - Lifetime
- 1942-12-01 GB GB17107/42A patent/GB567778A/en not_active Expired
-
1946
- 1946-03-26 FR FR926637D patent/FR926637A/fr not_active Expired
-
1950
- 1950-04-14 DE DEP1246A patent/DE900275C/de not_active Expired
Cited By (76)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2484529A (en) * | 1944-09-27 | 1949-10-11 | Du Pont | Process for altering the properties of solid polymers of ethylene |
US2524862A (en) * | 1946-07-16 | 1950-10-10 | Ici Ltd | Method and apparatus for producing cast synthetic resin structures by photopolymerization of monomeric material |
US2552329A (en) * | 1947-07-25 | 1951-05-08 | American Cyanamid Co | Poly-enolic organic compounds used to modify physical properties of thermoplastic polymers |
US2525664A (en) * | 1947-12-10 | 1950-10-10 | Ici Ltd | Casting of photopolymerizable compositions |
US2555518A (en) * | 1948-01-31 | 1951-06-05 | Universal Oil Prod Co | Photochemical preparation of polyphenylalkanes |
US2641576A (en) * | 1948-11-06 | 1953-06-09 | Alexander H Kerr And Company I | Photopolymerization process and compositions |
US2666025A (en) * | 1949-05-02 | 1954-01-12 | Shell Dev | Process for polymerizing vinyl-type compounds by irradiation |
US3041172A (en) * | 1958-12-30 | 1962-06-26 | Gen Aniline & Film Corp | Photopolymerization of vinyl monomers with metal oxides as catalysts |
US3118767A (en) * | 1958-12-30 | 1964-01-21 | Gen Aniline & Film Corp | Photopolymerization of vinyl monomers with metal oxides as catalysts |
US3036086A (en) * | 1959-05-05 | 1962-05-22 | Adicoff Arnold | Method for the polymerization of vinyltetrazoles monomers |
US3147119A (en) * | 1962-05-18 | 1964-09-01 | Gen Aniline & Film Corp | Photopolymerization of vinyl monomers with metal oxides as catalysts |
US3557783A (en) * | 1967-04-12 | 1971-01-26 | Charles S Castner | Method of killing microprobes with microbicidal compounds and ultraviolet light |
US3770490A (en) * | 1971-01-05 | 1973-11-06 | Ppg Industries Inc | Method of making and coating with high solids cured acrylic syrups |
US3723120A (en) * | 1971-08-30 | 1973-03-27 | Du Pont | Process for hardening photohardenable images |
DE2251048A1 (de) * | 1971-10-18 | 1973-05-10 | Ici Ltd | Photopolymerisierbare masse |
DE2266023C2 (fr) * | 1971-10-18 | 1989-07-20 | Imperial Chemical Industries Plc, London, Gb | |
US3874376A (en) * | 1971-11-29 | 1975-04-01 | Ici Ltd | Photocurable resin impregnated fabric for forming rigid orthopaedic devices and method |
US3930868A (en) * | 1973-05-23 | 1976-01-06 | The Richardson Company | Light sensitive arylglyoxyacrylate compositions |
US4083724A (en) * | 1973-05-23 | 1978-04-11 | The Richardson Company | Method of making light sensitive polymerizable compositions |
US4077806A (en) * | 1973-05-23 | 1978-03-07 | The Richardson Company | Light sensitive composition and products thereof |
US4057657A (en) * | 1973-12-13 | 1977-11-08 | John Lyndon Garnett | Curable pre-polymer compositions, method of making and method of coating articles therewith |
US4295948A (en) * | 1974-08-16 | 1981-10-20 | Battelle Memorial Institute | Photocurable adhesive from acrylic acid, acrylamide, dimethylaminoethyl methacrylate, benzophenone and methyl ethyl ketone |
US3990437A (en) * | 1974-09-26 | 1976-11-09 | Boyden Jr John S | Article and method of forming a support structure |
US4459193A (en) * | 1981-03-04 | 1984-07-10 | Imperial Chemical Industries Plc | Dental compositions containing camphorquinone and organic peroxide as catalyst |
EP0059649A3 (en) * | 1981-03-04 | 1983-04-20 | Imperial Chemical Industries Plc | Dental compositions |
EP0059649A2 (fr) * | 1981-03-04 | 1982-09-08 | Imperial Chemical Industries Plc | Compositions dentaires |
EP0090493A2 (fr) * | 1982-03-04 | 1983-10-05 | Imperial Chemical Industries Plc | Compositions photopolymérisables |
EP0090493A3 (en) * | 1982-03-04 | 1986-03-19 | Imperial Chemical Industries Plc | Photopolymerisable compositions |
US4680244A (en) * | 1984-03-17 | 1987-07-14 | Hoechst Aktiengesellschaft | Light-sensitive recording material for the production of a printing form or printed circuit with photoconductive layer and light-sensitive overlayer |
US4777190A (en) * | 1985-05-13 | 1988-10-11 | Mitsubishi Rayon Company Limited | Photopolymerizable composition based on a vinyl compound, a sulfur-containing compound and an α-diketone |
EP0343984A2 (fr) * | 1988-05-26 | 1989-11-29 | Hoechst Celanese Corporation | Arrangement d'écran en couleur pour un dispositif d'affichage à cristal liquide |
EP0343984A3 (fr) * | 1988-05-26 | 1991-03-27 | Hoechst Celanese Corporation | Arrangement d'écran en couleur pour un dispositif d'affichage à cristal liquide |
US4983644A (en) * | 1988-06-21 | 1991-01-08 | Mitsubishi Rayon Company, Limited | Dental adhesive composition |
US5348828A (en) * | 1990-02-26 | 1994-09-20 | Canon Kabushiki Kaisha | Process for producing electrode substrate |
US5568291A (en) * | 1990-02-26 | 1996-10-22 | Cannon Kabushiki Kaisha | Electrode substrate with light shielding film having upper surface coplanar with upper surface of laminate electrodes |
EP0758103A1 (fr) | 1995-08-08 | 1997-02-12 | Agfa-Gevaert N.V. | Elément photosensible et procédé pour la formation d'images métalliques avec cet élément |
EP0762214A1 (fr) | 1995-09-05 | 1997-03-12 | Agfa-Gevaert N.V. | Elément photosensible contenant une couche génératrice d'images et couche photopolymérisable |
US6555288B1 (en) | 1999-06-21 | 2003-04-29 | Corning Incorporated | Optical devices made from radiation curable fluorinated compositions |
US6306563B1 (en) | 1999-06-21 | 2001-10-23 | Corning Inc. | Optical devices made from radiation curable fluorinated compositions |
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US20090201482A1 (en) * | 2005-06-24 | 2009-08-13 | Takao Ozaki | Exposure Method and Apparatus |
EP1925954A2 (fr) | 2006-11-21 | 2008-05-28 | FUJIFILM Corporation | Procédé pour la production d'un produit biréfringent à motifs |
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Also Published As
Publication number | Publication date |
---|---|
BE465271A (fr) | 1900-01-01 |
US2413973A (en) | 1947-01-07 |
GB567778A (en) | 1945-03-02 |
FR926637A (fr) | 1947-10-07 |
DE900275C (de) | 1953-12-21 |
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