NO129287B - - Google Patents
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- NO129287B NO129287B NO141169A NO141169A NO129287B NO 129287 B NO129287 B NO 129287B NO 141169 A NO141169 A NO 141169A NO 141169 A NO141169 A NO 141169A NO 129287 B NO129287 B NO 129287B
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- 229920001577 copolymer Polymers 0.000 claims description 17
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 9
- 229920006305 unsaturated polyester Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 241000790917 Dioxys <bee> Species 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000005690 diesters Chemical class 0.000 claims description 2
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 35
- 239000011347 resin Substances 0.000 description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 8
- 238000005266 casting Methods 0.000 description 8
- 230000032050 esterification Effects 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 229920000728 polyester Polymers 0.000 description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 7
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 4
- 150000001463 antimony compounds Chemical class 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000001530 fumaric acid Substances 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 3
- 229960001826 dimethylphthalate Drugs 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- DJKGDNKYTKCJKD-BPOCMEKLSA-N (1s,4r,5s,6r)-1,2,3,4,7,7-hexachlorobicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic acid Chemical compound ClC1=C(Cl)[C@]2(Cl)[C@H](C(=O)O)[C@H](C(O)=O)[C@@]1(Cl)C2(Cl)Cl DJKGDNKYTKCJKD-BPOCMEKLSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 2
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- -1 alkylene chlorohydrins Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/38207—Contact thermal transfer or sublimation processes characterised by aspects not provided for in groups B41M5/385 - B41M5/395
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B07—SEPARATING SOLIDS FROM SOLIDS; SORTING
- B07C—POSTAL SORTING; SORTING INDIVIDUAL ARTICLES, OR BULK MATERIAL FIT TO BE SORTED PIECE-MEAL, e.g. BY PICKING
- B07C3/00—Sorting according to destination
- B07C3/18—Devices or arrangements for indicating destination, e.g. by code marks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/26—Printing on other surfaces than ordinary paper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
- B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K1/00—Methods or arrangements for marking the record carrier in digital fashion
- G06K1/12—Methods or arrangements for marking the record carrier in digital fashion otherwise than by punching
- G06K1/121—Methods or arrangements for marking the record carrier in digital fashion otherwise than by punching by printing code marks
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Theoretical Computer Science (AREA)
- Optics & Photonics (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Luminescent Compositions (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Color Printing (AREA)
- Duplication Or Marking (AREA)
- Impression-Transfer Materials And Handling Thereof (AREA)
Description
Fremgangsmåte til fremstilling av tungt forbrennbare sampolymerisater på basis av halogenholdige, umettede polyestere. Process for the production of highly combustible copolymers based on halogen-containing, unsaturated polyesters.
Der er kjent tungt forbrennbare sampolymerisater av monomere vinylforbindelser, særlig styren og polymeriserbare, There are known heavily combustible copolymers of monomeric vinyl compounds, in particular styrene and polymerizable,
halogenholdige, umettede polyestere, eventuelt med tilsetning av antimon- og/eller halogen-containing, unsaturated polyesters, possibly with the addition of antimony and/or
fosforforbindelser. Slike polyestere er phosphorus compounds. Such polyesters are
fremstillet ved polykondensasjon av dioler produced by polycondensation of diols
med a,(3-umettede dikarbonsyrer, f. eks. with α,(3-unsaturated dicarboxylic acids, e.g.
maleinsyre og fumarsyre, eller anhydrider maleic acid and fumaric acid, or anhydrides
av sådanne, og halogenholdige dikarbonsyrer, f. eks. tetraklorftalsyre eller heksa-klorendometylen-tetrahydroftalsyre eller of such, and halogen-containing dicarboxylic acids, e.g. tetrachlorophthalic acid or hexa-chloroendomethylene-tetrahydrophthalic acid or
anhydrider av sådanne. anhydrides thereof.
Imidlertid er slike polyestere i almin-nelighet farvede. Videre gir de med monomere vinylforbindelser som f. eks. styren, However, such polyesters are generally colored. Furthermore, those with monomeric vinyl compounds such as e.g. styrene,
forholdsvis viskose væsker, hva der i mange relatively viscous liquids, what in many
tilfelle er ugunstig ved deres opparbeidelse case is unfavorable during their processing
eller anvendelse, særlig for vætning av or application, especially for wetting of
glassvev. Dertil har de herdede sluttpro-dukter i regelen en mindre mekanisk fasthet enn produkter som er fremstillet under anvendelse av halogenfrie polyestere. vitreous tissue. In addition, the cured end products generally have a lower mechanical strength than products produced using halogen-free polyesters.
Der ble nu funnet at man kan fremstille lite brennbare sampolymerisater med It was now found that low-flammability copolymers can be produced with
forbedrede egenskaper av monomere vinylforbindelser og polymeriserbare halogenholdige, umettede polyestere ved at man improved properties of monomeric vinyl compounds and polymerizable halogen-containing, unsaturated polyesters by man
bruker polyestere som på i og for seg kjent uses polyesters which are known in and of themselves
måte er fremstillet ved polykondensasjon method is produced by polycondensation
av oksyalkylerte, i kjernen halogenerte, of oxyalkylated, in the core halogenated,
aromatiske dioksyforbindelser, eventuelt i aromatic dioxy compounds, optionally i
blanding med andre dioler, og a,|3-umettede dikarbonsyrer eller anhydrider eller di-estere av sådanne og eventuelt andre dikarbonsyrer eller dikarbonsyrederivater. mixture with other diols, and α,|3-unsaturated dicarboxylic acids or anhydrides or diesters of such and possibly other dicarboxylic acids or dicarboxylic acid derivatives.
De sampolymerisater man får på denne måte utmerker seg foruten ved at de er tungt forbrennelige og vanskelig lar seg antenne, særlig ved stor mekanisk fasthet, meget god varmebestandighet, frem-tredende bestandighet mot vann, særlig varmt vann, og klar gjennomsiktighet samt ved at de er farveløse. The copolymers obtained in this way are also distinguished by the fact that they are highly combustible and difficult to ignite, particularly by high mechanical strength, very good heat resistance, outstanding resistance to water, especially hot water, and clear transparency, as well as by the fact that they are colorless.
F. eks. følgende oksyalkylerte, i kjernen halogenerte, aromatiske dioksyforbindelser som kan fremstilles ved hjelp av kjente ^fremgangsmåter ved halogenering i kjernen av de tilsvarende aromatiske dioksyforbindelser og omsetning av haloge-neringsproduktene med alkylenklorhydri-ner eller alkylenoksyder er egnet til fremstilling av nevnte polyestere: 1,4-dioksyetyl-tetra-klorhydrokinon, 1,4-dioksypropyl-tetraklorhydrokinon, 4,4'-dioksyetoksy-3,3',5-triklordifenyl, 4,4'-di-oksyetoksy-3,3',5,5'-tetraklordifenyl, 4,4'-dioksyetoksy-oktaklordifenyl-4,4'-dioksy-propoksy-3,3'5,5'-tetraklordifenyl, 4,4'-di-oksyetoksy-3,3'-diklor-difenylsulfon og særlig oksyalkylerte, i kjernen halogenerte dioksydiarylalkaner som 4,4'-dioksyetoksy-3,3',5,5'-tetraklordifenylmetan, 4,4'-dioksy-etoksy-3,3'-diklordifenylpropan, 4,4'-diok-syetoksy-3,3',5,5'-tetraklordifenylpropan, 4,4'-dioksypropoksy-3,3',5,5'-tetraklordife-nylpropan, 4,4'-dioksyetoksy-3,3',5,5'-tetra-klordifenylcykloheksan, 4,4'-dioksyetoksy-3,3',5,5'-tetrabromdifenylpropan eller 4,4'-dioksypropoksy-3,3',5,5'-tetra-bromdife-nylpropan. For example The following oxyalkylated, halogenated in the core, aromatic dioxy compounds which can be prepared using known methods by halogenation in the core of the corresponding aromatic dioxy compounds and reaction of the halogenation products with alkylene chlorohydrins or alkylene oxides are suitable for the production of said polyesters: 1,4 -dioxyethyl-tetrachlorohydroquinone, 1,4-dioxypropyl-tetrachlorohydroquinone, 4,4'-dioxyethoxy-3,3',5-trichlorodiphenyl, 4,4'-dioxyethoxy-3,3',5,5'- tetrachlorodiphenyl, 4,4'-dioxyethoxy-octachlorodiphenyl-4,4'-dioxy-propoxy-3,3'5,5'-tetrachlorodiphenyl, 4,4'-dioxyethoxy-3,3'-dichloro-diphenylsulfone and especially oxyalkylated core-halogenated dioxydiarylalkanes such as 4,4'-dioxyethoxy-3,3',5,5'-tetrachlorodiphenylmethane, 4,4'-dioxyethoxy-3,3'-dichlorodiphenylpropane, 4,4'-dioxyethoxy -3,3',5,5'-tetrachlorodiphenylpropane, 4,4'-dioxypropoxy-3,3',5,5'-tetrachlorodiphenylpropane, 4,4'-dioxyethoxy-3,3',5,5' -tetra-chlorodiphenylcyclohexane, 4,4'-dioxyethoxy-3,3',5,5'-tetrab romdiphenylpropane or 4,4'-dioxypropoxy-3,3',5,5'-tetrabromodiphenylpropane.
Andre dioler som de omtale oksyalkylerte, i kjernen halogenerte, aromatiske dioksyforbindelser delvis kan erstattes med er f. eks.: etylenglykol, dietylenglykol, 1,2-propylenglykol og 1,3-butandiol. Other diols with which the mentioned oxyalkylated, halogenated in the core, aromatic dioxy compounds can be partially replaced are, for example: ethylene glycol, diethylene glycol, 1,2-propylene glycol and 1,3-butanediol.
Andre a,|3-umettede dikarbonsyrer som kan komme i betraktning for fremstilling av polyestrene foruten de nevnte maleinsyre og fumarsyre, er itakonsyre og citra-konsyre. Other α,|3-unsaturated dicarboxylic acids that can be considered for the production of the polyesters, besides the mentioned maleic acid and fumaric acid, are itaconic acid and citraconic acid.
Som foran nevnt kan der sammen med disse umettede dikarbonsyrer brukes andre dikarbonsyrer. Eksempler på sådanne er ravsyre, ftalsyre, tereftalsyre, tetraklorftalsyre, tetrahydroftalsyre og heksaklor-endometylen-tetrahydroftalsyre. As mentioned above, other dicarboxylic acids can be used together with these unsaturated dicarboxylic acids. Examples of such are succinic acid, phthalic acid, terephthalic acid, tetrachlorophthalic acid, tetrahydrophthalic acid and hexachloro-endomethylene-tetrahydrophthalic acid.
Når man forestrer utelukkende halogenerte dioler av den nevnte art med maleinsyre eller fumarsyre, danner der seg harpikser med mykningspunkt over ca. 100° C. Disse harpikser lar seg lett pul-verisere og videre opparbeide til press-masser, f. eks. sammen med styren. Ved samtidig anvendelse av andre dioler syn-ker derimot de umettede polyesteres mykningspunkt til f. eks. omkring 60—70° C, hva der for deres videre anvendelse f. eks. som støpeharpikser medfører den fordel at de i smeiten lar seg blande med de monomere vinylforbindelser, særlig styren, allerede ved litt forhøyet temperatur. Herved kan man unngå tilsetning av for store mengder stabilisatorer som ville forsinke koldherdningen. En videre fordel ved anvendelsen av de nevnte dioler er en forkortelse av forestringstiden og dermed muligheten av å kunne fremstille særlig klare polyestere. When exclusively halogenated diols of the aforementioned type are esterified with maleic acid or fumaric acid, resins with a softening point above approx. 100° C. These resins can be easily pulverized and further processed into pressed compounds, e.g. together with the board. When other diols are used at the same time, on the other hand, the softening point of the unsaturated polyesters drops to e.g. around 60-70° C, what about their further use, e.g. as casting resins have the advantage that they can be mixed with the monomeric vinyl compounds, especially styrene, already at a slightly elevated temperature during the smelting process. In this way, the addition of excessive amounts of stabilizers, which would delay the cold hardening, can be avoided. A further advantage of the use of the mentioned diols is a shortening of the esterification time and thus the possibility of being able to produce particularly clear polyesters.
De nye umettede polyestere foreligger som praktisk talt farveløse, klare, sprø harpikser som lett kan oppløses i monomere vinylforbindelser, f. eks. styren, metylsty-ren, divinylbenzol, metylmetakrylat, vinyl-benzoat og diallylftalat til relativt lite viskose oppløsninger og i denne tilstand med fordel anvendes som f. eks. støpeharpikser. The new unsaturated polyesters exist as practically colourless, clear, brittle resins which can be easily dissolved in monomeric vinyl compounds, e.g. styrene, methylstyrene, divinylbenzene, methyl methacrylate, vinyl benzoate and diallyl phthalate to relatively low viscosity solutions and in this state advantageously used as e.g. casting resins.
Til utløsning av sampolymeriseringen tilsetter man på vanlig måte katalysatorer eller kombinasjoner av katalysatorer som f. eks. aziperoksyder som benzoylperoksyd. For koldherdningen kan man tilsette f. eks. koboltnaftenat og cykloheksanonperoksyd. Catalysts or combinations of catalysts such as e.g. aziperoxides such as benzoyl peroxide. For cold hardening, you can add e.g. cobalt naphthenate and cyclohexanone peroxide.
Som ved sampolymerisering av kjente halogenholdige umettede polyestere med monomere vinylforbindelser kan man også i foreliggende fremgangsmåte med fordel tilsette antimonforbindelser, f. eks. antimontrioksyd, til forhøyelse av blandinge-nes tungtantennelighet. Videre kan man, særlig for oppnåelse av klart gjennomsik-tige polymerisater tilsette blandingene oppløselige antimonforbindelser som angitt i patent nr. 96 039. Således lar det seg fremstille produkter som etter betingelsene i DIN-forskrift 4102, blad 3 og ASTM 635— 44 må betegnes som tungtantennelige med et klorinnhold på bare 14—15 pst. og et innhold av antimonforbindelser på omkring 5 pst. As with the copolymerization of known halogen-containing unsaturated polyesters with monomeric vinyl compounds, antimony compounds, e.g. antimony trioxide, to increase the low flammability of the mixtures. Furthermore, in particular to obtain clearly transparent polymers, soluble antimony compounds can be added to the mixtures as indicated in patent no. 96 039. Thus, it is possible to produce products which, according to the conditions in DIN regulation 4102, sheet 3 and ASTM 635-44, must be labeled as highly flammable with a chlorine content of only 14-15 per cent and a content of antimony compounds of around 5 per cent.
Sampolymerisatenes egenskaper kan på kjent måte forbedres ved innleiring av glasstykker, glassmatter eller glassvev. The properties of the copolymers can be improved in a known manner by embedding pieces of glass, glass mats or glass fabric.
I det følgende beskrives som eksempler noen utførelsesformer for oppfinnelsen. In the following, some embodiments of the invention are described as examples.
Eksempel 1. Example 1.
En blanding av 454 vektsdeler (1,0 mol) 4,4'-dioksyetoksy-3,3',5,5'-tetraklordife-nylpropan og 108 vektsdeler (1,1 mol) maleinsyreanhydrid oppvarmes under omrø-ring og overledning av oxygenfritt nitrogen i en glasskolbe med røreverk, vannutskiller og termometer. Til utførelse av forestringen holdes blandingen i 4 timer på 180° C og 4 timer på 200° C inntil vann ikke lenger avdestillerer. Herved økes rø-reverkets hastighet og forsterkes nitrogen-strømmen i de siste to timer. Man får en farveløs, klar, sprø harpiks med mykningspunkt 111° C og syretall 17. A mixture of 454 parts by weight (1.0 mol) of 4,4'-dioxyethoxy-3,3',5,5'-tetrachlorodiphenylpropane and 108 parts by weight (1.1 mol) of maleic anhydride is heated while stirring and passing oxygen-free nitrogen in a glass flask with a stirrer, water separator and thermometer. To carry out the esterification, the mixture is kept for 4 hours at 180° C and 4 hours at 200° C until water no longer distills off. This increases the speed of the stirrer and reinforces the nitrogen flow in the last two hours. A colourless, clear, brittle resin with a softening point of 111° C and an acid number of 17 is obtained.
Denne harpiks oppløses i styren til en 65 pst.'s oppløsning. Den erholdte farve-løse oppløsning stabiliseres med 0,01 pst. hydrokinon, tilsettes 4 pst. benzoylperoksydpasta (50 pst.'s i dimetylftalat) og man lar den stå 30 minutter ved 80° C. Der dannes et vannklart sampolymerisat med et totalinnhold av klor på 17,3 pst. og de egenskaper som angitt i tabellen på slutten av denne beskrivelse. This resin is dissolved in styrene to a 65% solution. The colorless solution obtained is stabilized with 0.01% hydroquinone, 4% benzoyl peroxide paste (50% in dimethyl phthalate) is added and it is allowed to stand for 30 minutes at 80° C. A water-clear copolymer is formed with a total chlorine content of 17.3 per cent and the properties stated in the table at the end of this description.
Eksempel 2. Example 2.
En blanding av 454 vektsdeler (1,0 mol) 4,4'-dioksyetoksy-3,3',5,5'-tetraklordife-nylpropan og 128 vektsdeler (1,1 mol) fumarsyre oppvarmes under omrøring og overledning av oxygenfritt nitrogen i en glasskolbe med røreverk, vannutskiller og termometer. For at forestringen skal fore-gå, holdes blandingen i 4 timer på 175— 180° C og i 5 timer på 195—200° C inntil vann ikke lengere destillerer av. Herved økes omrøringshastigheten og forsterkes nitrogenstrømmen i de tre siste timer. Man får en farveløs, klar, sprø harpiks med mykningspunkt 101° C og syretall 30. A mixture of 454 parts by weight (1.0 mol) 4,4'-dioxyethoxy-3,3',5,5'-tetrachlorodifenylpropane and 128 parts by weight (1.1 mol) fumaric acid is heated with stirring and passing oxygen-free nitrogen in a glass flask with stirrer, water separator and thermometer. In order for the esterification to take place, the mixture is kept for 4 hours at 175-180° C and for 5 hours at 195-200° C until water no longer distills off. This increases the stirring speed and reinforces the nitrogen flow in the last three hours. A colourless, clear, brittle resin with a softening point of 101° C and an acid value of 30 is obtained.
Denne harpiks oppløses i styren til en 65 pst.'s oppløsning som stabiliseres med 0,02 pst. hydrokinon. Der dannes en klar This resin is dissolved in styrene to a 65% solution which is stabilized with 0.02% hydroquinone. A clear is formed
støpeharpiks med et klorinnhold på 17,3 casting resin with a chlorine content of 17.3
pst. Etter flere timer blir harpiksen fullstendig krystallinsk. Når denne klebefrie, pst. After several hours, the resin becomes completely crystalline. When this nonstick,
i smuler foreliggende masse blandes godt med 30—40 pst. glasstykker og/eller andre fyllstoffer og 4 pst. benzoylperoksydpasta, får man en pressemasse som i varmen og under trykk herder fullstendig i løpet av få minutter. Formstykker fremstillet av denne pressmasse har en stor fasthet således som det fremgår av tabellen på slutten av denne beskrivelse, god varmebestandighet og en meget god bestandighet mot varmt vann. Et prøvelegeme bestående av 75 vektsdeler av sampolymerisatet og 25 vektsdeler glasstykker gir ved prøvning etter forskriftene i ASTM 635—44 en for-brenningsvarighet på 46 sekunder. Etter tilsetning av 5 pst. antimontrioksyd inn-trer øyeblikkelig slukning. the mass present in crumbs is mixed well with 30-40 per cent glass pieces and/or other fillers and 4 per cent benzoyl peroxide paste, a pressing mass is obtained which in the heat and under pressure hardens completely within a few minutes. Moldings produced from this pressing compound have a great firmness, as can be seen from the table at the end of this description, good heat resistance and a very good resistance to hot water. A test body consisting of 75 parts by weight of the copolymer and 25 parts by weight of glass pieces gives, when tested according to the regulations in ASTM 635-44, a combustion duration of 46 seconds. After the addition of 5 percent antimony trioxide, immediate extinguishment occurs.
Eksempel 3. Example 3.
En blanding av 908 vektsdeler (2,0 mol) 4,4'-dioksyetoksy-3,3',5,5'-tetraklordife-nylpropan, 11 vektsdeler (0,1 mol) dietylenglykol og 216 vektsdeler (2,2 mol) maleinsyreanhydrid oppvarmes under omrøring og overledning av oxygenfritt nitrogen i en 1 liters kolbe forsynt med røreverk, termometer og vannutskiller. Til foretagelse av forestringen holdes blandingen i 3 timer på 175° C og i 4 timer på 195° C inntil vann ikke lenger destillerer av. Herved økes omrøringshastigheten og forsterkes nitrogenstrømmen mot slutten av forestringen. Man får en svakt gulaktig, klar, sprø harpiks med mykningspunkt 85° C og syretall 26. A mixture of 908 parts by weight (2.0 mol) of 4,4'-dioxyethoxy-3,3',5,5'-tetrachlorodiphenylpropane, 11 parts by weight (0.1 mol) of diethylene glycol and 216 parts by weight (2.2 mol) maleic anhydride is heated while stirring and passing oxygen-free nitrogen in a 1 liter flask equipped with a stirrer, thermometer and water separator. To carry out the esterification, the mixture is kept for 3 hours at 175° C and for 4 hours at 195° C until water no longer distills off. This increases the stirring speed and strengthens the nitrogen flow towards the end of the esterification. A slightly yellowish, clear, brittle resin with a softening point of 85° C and an acid number of 26 is obtained.
Denne harpiks oppløses i styren til en 65 pst.'s oppløsning. Den klare oppløsning stabiliseres med 0,01 pst. hydrokinon og tilsettes 4 pst. benzoylperoksydpasta hvor-på man lar den stå 30 minutter ved 75° C. Der dannes et nesten vannklart sampolymerisat som inneholder 16,8 pst. klor. Dette sampolymerisat har de egenskaper som an-gis i tabellen på slutten av denne beskrivelse. This resin is dissolved in styrene to a 65% solution. The clear solution is stabilized with 0.01% hydroquinone and 4% benzoyl peroxide paste is added, after which it is left to stand for 30 minutes at 75° C. An almost water-clear copolymer is formed which contains 16.8% chlorine. This copolymer has the properties stated in the table at the end of this description.
Eksempel 4. Example 4.
En blanding av 1362 vektsdeler (3,0 mol) 4,4'-dioksyetoksy-3,3',5,5'-tetraklor-difenylpropan, 68,2 vektsdeler (1,1 mol) etylenglykol, 106 vektsdeler (1,0 mol) dietylenglykol og 514 vektsdeler (525 mol) maleinsyreanhydrid oppvarmes under om-røring og overledning av oxygenfritt nitrogen i en 2 liters kolbe forsynt med rø-reverk, termometer og vannutskiller. Til foretagelse av forestringen holdes blandingen i 5 timer på 180—185° C og i 2y2 time på 185—190° C inntil vann ikke lengere destillerer av. Herved økes omrøringshas-tigheten og forsterkes nitrogenstrømmen i de to siste timer. Man får en nesten far-veløs, sprø harpiks med mykningspunkt 67° C og syretall 29. A mixture of 1362 parts by weight (3.0 mol) 4,4'-dioxyethoxy-3,3',5,5'-tetrachlorodiphenylpropane, 68.2 parts by weight (1.1 mol) ethylene glycol, 106 parts by weight (1.0 mol) of diethylene glycol and 514 parts by weight (525 mol) of maleic anhydride are heated with stirring and the passing of oxygen-free nitrogen in a 2 liter flask equipped with a stirrer, thermometer and water separator. To carry out the esterification, the mixture is kept for 5 hours at 180-185° C and for 2y2 hours at 185-190° C until water no longer distills off. This increases the stirring speed and enhances the nitrogen flow in the last two hours. An almost colorless, brittle resin with a softening point of 67° C and an acid number of 29 is obtained.
Denne harpiks oppløses i styren til en 70 pst.'s oppløsning som tilsettes 0,01 pst. This resin is dissolved in styrene to a 70% solution to which 0.01% is added.
hydrokinon. Man får en klar, nesten farve-løs støpeharpiks med et innhold av klor på 14,2 pst. Etter tilsetning av 0,1 pst. koboltnaftenat og 4 pst. cykloheksanonperok-sydpasta (50 pst.'s i dimetylftalat) størk-ner harpiksen ved vanlig temperatur i kort tid til et klart sampolymerisat. Etter tilsetning av 4 pst. benzoylperoksydpasta fore-går ved 80° C herdning til et klart sampolymerisat i løpet av 20—30 minutter. Dette sampolymerisats egenskaper er anr gitt i tabellen på slutten av denne beskrivelse. hydroquinone. A clear, almost colorless casting resin with a chlorine content of 14.2% is obtained. After adding 0.1% cobalt naphthenate and 4% cyclohexanone peroxide paste (50% in dimethyl phthalate), the resin solidifies at normal temperature for a short time to a clear copolymer. After the addition of 4% benzoyl peroxide paste, curing takes place at 80° C into a clear copolymer within 20-30 minutes. The properties of this copolymer are listed in the table at the end of this description.
Eksempel 5. Example 5.
En blanding av 567,5 vektsdeler (1,25 mol) 4,4'-dioksyetoksy-3,3',5,5'-tetraklor-difenylpropan, 85,3 vektsdeler (1,37 mol) etylenglykol og 257 vektsdeler (2,62 mol) maleinsyreanhydrid forestres således som beskrevet i de foregående eksempler i 4 timer ved 175° C og 4 timer ved 185—190° C inntil vann ikke lenger destillerer av. Om-røringsastigheten økes og nitrogenstrøm-men forsterkes i de to siste timer. Der dannes en farveløs, klar, sprø harpiks med mykningspunkt 75° C og syretall 30. A mixture of 567.5 parts by weight (1.25 mol) 4,4'-dioxyethoxy-3,3',5,5'-tetrachlorodiphenylpropane, 85.3 parts by weight (1.37 mol) ethylene glycol and 257 parts by weight (2 .62 mol) of maleic anhydride is thus esterified as described in the previous examples for 4 hours at 175° C and 4 hours at 185-190° C until water no longer distills off. The stirring speed is increased and the nitrogen flow is intensified in the last two hours. A colourless, clear, brittle resin with a softening point of 75° C and an acid number of 30 is formed.
Denne harpiks oppløses i styren til en 70 pst.'s oppløsning og stabiliseres med 0,01 This resin is dissolved in styrene to a 70% solution and stabilized with 0.01
pst. hydrokinon. Der dannes en klar, far-veløs, lite viskos støpeharpiks med et innhold av klor på 14,6 pst. Denne harpiks lar seg ved de vanlige betingelser herde til et klart sampolymerisat hvis egenskaper er angitt i tabellen på slutten av denne beskrivelse. pst hydroquinone. A clear, colourless, low-viscosity casting resin is formed with a chlorine content of 14.6%. This resin can be cured under the usual conditions to a clear copolymer whose properties are indicated in the table at the end of this description.
Eksempel 6. Example 6.
En blanding av 328,3 vektsdeler (0,66 mol) 4,4'-dioksy-etoksy-3,3',5,5'-tetraklor-difenylcykloheksan, 14,5 vektsdeler (0,23 mol) etylenglykol og 81,6 vektsdeler (0,83 mol) maleinsyreanhydrid forestres således som beskrevet i eksemplene 1—4 i 4 timer ved 175° C og i 4 timer ved 185—190° C inntil vann ikke lenger avdestillerer. Om-røringshastigheten økes og nitrogenstrøm-men forsterkes i de to siste timer. Der dannes en farveløs, klar, sprø harpiks med mykningspunkt 106° C og syretall 15. A mixture of 328.3 parts by weight (0.66 mol) of 4,4'-dioxy-ethoxy-3,3',5,5'-tetrachloro-diphenylcyclohexane, 14.5 parts by weight (0.23 mol) of ethylene glycol and 81, 6 parts by weight (0.83 mol) of maleic anhydride are thus esterified as described in examples 1-4 for 4 hours at 175° C and for 4 hours at 185-190° C until water no longer distills off. The stirring rate is increased and the nitrogen flow is intensified in the last two hours. A colourless, clear, brittle resin with a softening point of 106° C and an acid number of 15 is formed.
Denne harpiks oppløses i styren til en 70 pst.'s oppløsning som stabiliseres med 0,01 pst. hydrokinon. Der dannes en klar, farveløs støpeharpiks med et klorinnhold på 16 pst. Denne harpiks lar seg ved de vanlige betingelser herde til et klart sampolymerisat med egenskaper som angitt i This resin is dissolved in styrene to a 70% solution which is stabilized with 0.01% hydroquinone. A clear, colorless casting resin with a chlorine content of 16% is formed. Under the usual conditions, this resin can be cured to a clear copolymer with properties as stated in
tabellen på slutten av denne beskrivelse. the table at the end of this description.
Eksempel 7. Example 7.
En blanding av 320 vektsdeler (0,66 mol) 4,4'-dioksypropoksy-3,3',5,5'-tetra-klordifenylpropan, 14,5 vektsdeler (0,23 mol) etylenglykol og 81,6 vektsdeler (0,83 mol) maleinsyreanhydrid forestres på den i foregående eksempler 1—4 beskrevne må-te i 4 timer ved 180° C og i 5 timer ved 200° C. Herved økes omrøringshastigheten og forsterkes nitrogenstrømmen på slutten av forestringen. Der dannes en farveløs, klar, sprø harpiks med mykningspunkt 93° C og syretall 18. A mixture of 320 parts by weight (0.66 mol) of 4,4'-dioxypropoxy-3,3',5,5'-tetrachlorodiphenylpropane, 14.5 parts by weight (0.23 mol) of ethylene glycol and 81.6 parts by weight (0 .83 mol) of maleic anhydride is esterified in the manner described in previous examples 1-4 for 4 hours at 180° C. and for 5 hours at 200° C. This increases the stirring speed and enhances the nitrogen flow at the end of the esterification. A colourless, clear, brittle resin with a softening point of 93° C and an acid value of 18 is formed.
268 vektsdeler av denne harpiks opp-løses i 196 vektsdeler styren og den klare oppløsning tilsettes 0,057 vektsdeler hydrokinon. Ved herdning med de vanlige katalysatorer dannes der et vannklart sampolymerisat med et totalt innhold av klor på 15,1 pst. og med egenskaper som angitt i tabellen på slutten av denne beskrivelse. 268 parts by weight of this resin are dissolved in 196 parts by weight of styrene and 0.057 parts by weight of hydroquinone is added to the clear solution. When curing with the usual catalysts, a water-clear copolymer is formed with a total chlorine content of 15.1 per cent and with properties as stated in the table at the end of this description.
Eksempel 8. Example 8.
En blanding av 283,5 vektsdeler (0,625 mol) 4,4'-dioksy-etoksy-3,3',5,5'-tetraklor-difenylpropan, 79 vektsdeler (0,125 mol) 4,4'-dloksyetoksy-3,3',5,5'-tetrabromdife-nylpropan, 18 vektsdeler (0,275 mol) etylenglykol, 26,5 vektsdeler (0,25 mol) dietylenglykol og 122,5 vektsdeler (1,25 mol) maleinsyreanhydrid forestres på vanlig måte. Forestringen utføres i 6 timer ved 190° C og i 4 timer ved 200° C, idet omrø-ringshastigheten økes og nitrogenstrøm-men forsterkes i de to siste timer. Man får en farveløs, klar, sprø harpiks med mykningspunkt 88° C og syretall 16. A mixture of 283.5 parts by weight (0.625 mol) 4,4'-dioxy-ethoxy-3,3',5,5'-tetrachloro-diphenylpropane, 79 parts by weight (0.125 mol) 4,4'-dloxyethoxy-3,3 ',5,5'-tetrabromodiphenylpropane, 18 parts by weight (0.275 mol) of ethylene glycol, 26.5 parts by weight (0.25 mol) of diethylene glycol and 122.5 parts by weight (1.25 mol) of maleic anhydride are esterified in the usual manner. The esterification is carried out for 6 hours at 190° C and for 4 hours at 200° C, the stirring speed being increased and the nitrogen flow intensified in the last two hours. A colourless, clear, brittle resin with a softening point of 88° C and an acid number of 16 is obtained.
493 vektsdeler av denne harpiks og 0,076 vektsdeler hydrokinon oppløses i 265 493 parts by weight of this resin and 0.076 parts by weight of hydroquinone are dissolved in 265
vektsdeler styren hvorved man får en tynt-flytende, klar, farveløs støpeharpiks med et totalinnhold av klor på 11,3 pst. og et totalinnhold av brom på 5,2 pst. Denne harpiks lar seg under de vanlige betingelser herde til et klart sampolymerisat med de mekaniske egenskaper som er angitt i tabellen på slutten av denne beskrivelse. På grunn av at denne harpiks foruten klor også inneholder brom, slukker prøvelege-mer bestående av 75 vektsdeler av harpiksen og 25 vektsdeler glassfibre etter få sekunder, selv uten tilsetning av antimonforbindelser. parts by weight of styrene, whereby a thin-flowing, clear, colorless casting resin is obtained with a total chlorine content of 11.3 percent and a total bromine content of 5.2 percent. This resin can be cured under the usual conditions to a clear copolymer with the mechanical properties indicated in the table at the end of this description. Because this resin, in addition to chlorine, also contains bromine, test specimens consisting of 75 parts by weight of the resin and 25 parts by weight of glass fibers extinguish after a few seconds, even without the addition of antimony compounds.
Eksempel 9. Example 9.
131,2 vektsdeler (0,333 mol) av en blanding av 4,4'-dioksyetoksy-3,3'5-triklordi-fenylog4,4'-dioksyetoksy-3,3',5,5'-tetraklor-difenyl i molforhold 1:1 blandes med 75,6 vektsdeler (0,166 mol) 4,4'-dioksyetoksy-3,3',5,5'-tetraklordifenylpropan, 11,6 vektsdeler (0,182 mol) etylenglykol, 17,6 vektsdeler (0,166 mol) dietylenglykol og 81,6 vektsdeler (0,833 mol) maleinsyreanhydrid. Den erholdte blanding forestres på vanlig måte i 7 timer ved 185—190° C og i 4 timer ved 200° C inntil vann ikke lenger 131.2 parts by weight (0.333 mol) of a mixture of 4,4'-dioxyethoxy-3,3'5-trichlorodi-phenyl and 4,4'-dioxyethoxy-3,3',5,5'-tetrachloro-diphenyl in a molar ratio of 1 :1 is mixed with 75.6 parts by weight (0.166 mol) of 4,4'-dioxyethoxy-3,3',5,5'-tetrachlorodiphenylpropane, 11.6 parts by weight (0.182 mol) of ethylene glycol, 17.6 parts by weight (0.166 mol) of diethylene glycol and 81.6 parts by weight (0.833 mol) of maleic anhydride. The resulting mixture is esterified in the usual way for 7 hours at 185-190° C and for 4 hours at 200° C until water no longer
destillerer av. I de siste 3 timer økes om-røringshastigheten og forsterkes nitrogen-strømmen. Man får en svakt gulaktig, sprø harpiks med mykningspunkt 84° C og syretall 16. distills off. In the last 3 hours, the stirring speed is increased and the nitrogen flow is increased. A slightly yellowish, brittle resin with a softening point of 84° C and an acid number of 16 is obtained.
272 vektsdeler av denne polyester og 0,27 vektsdeler ihydrokinon oppløses varmt i 117 vektsdeler styren. Man får en svakt gulaktig støpeharpiks som blir krystallinsk allerede ved 80° C. 272 parts by weight of this polyester and 0.27 parts by weight of hydroquinone are dissolved hot in 117 parts by weight of styrene. You get a slightly yellowish casting resin which becomes crystalline already at 80°C.
En blanding av 1 vektsdel av denne krystallinske harpiks, 1 vektsdel kritt, 1 vektsdel glasstykker og 0,04 vektsdeler benzoylperoksydpasta (50 pst.'s i dimetylftalat) gjennomarbeides godt i et kna-apparat i varmen og presses ved 150° C. Verdiene for de mekaniske egenskaper hos denne herdede pressmasse er angitt i følgende tabell: A mixture of 1 part by weight of this crystalline resin, 1 part by weight of chalk, 1 part by weight of glass pieces and 0.04 parts by weight of benzoyl peroxide paste (50 per cent in dimethyl phthalate) is worked through well in a kneader in the heat and pressed at 150° C. The values for the mechanical properties of this hardened pressing compound are indicated in the following table:
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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GB1577068A GB1270103A (en) | 1968-04-02 | 1968-04-02 | Improvements in and relating to printing apparatus and methods |
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NO129287B true NO129287B (en) | 1974-03-25 |
Family
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NO141169A NO129287B (en) | 1968-04-02 | 1969-04-02 |
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CH (1) | CH535128A (en) |
DE (1) | DE1916679A1 (en) |
FR (1) | FR2005398A1 (en) |
GB (1) | GB1270103A (en) |
NL (1) | NL6904967A (en) |
NO (1) | NO129287B (en) |
SE (1) | SE360821B (en) |
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IT1119017B (en) * | 1979-07-09 | 1986-03-03 | Olivetti & Co Spa | DEVICE AND PRINTING PROCEDURE WITHOUT IMPACT |
GB2144081B (en) * | 1983-07-23 | 1987-10-28 | Pa Consulting Services | Postal franking machines |
FR2669267B1 (en) * | 1990-11-16 | 1993-01-22 | Supermag | PERSONALIZATION MACHINE FOR CHIP CARDS. |
GB2307692A (en) * | 1995-11-29 | 1997-06-04 | Polygon Ind Co Ltd | Composition comprising luminescent powder, varnish and, optionally, an ink |
CN103386819A (en) * | 2013-07-02 | 2013-11-13 | 苏州威仕科贸有限公司 | Base moveable type solar film heat transfer printing marking machine |
-
1968
- 1968-04-02 GB GB1577068A patent/GB1270103A/en not_active Expired
-
1969
- 1969-03-31 NL NL6904967A patent/NL6904967A/xx unknown
- 1969-04-01 DE DE19691916679 patent/DE1916679A1/en active Pending
- 1969-04-02 FR FR6910057A patent/FR2005398A1/fr not_active Withdrawn
- 1969-04-02 NO NO141169A patent/NO129287B/no unknown
- 1969-04-02 SE SE478969A patent/SE360821B/xx unknown
- 1969-04-02 CH CH506869A patent/CH535128A/en not_active IP Right Cessation
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CH535128A (en) | 1973-03-31 |
SE360821B (en) | 1973-10-08 |
DE1916679A1 (en) | 1969-11-13 |
GB1270103A (en) | 1972-04-12 |
NL6904967A (en) | 1969-10-06 |
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