NO141467B - ELECTRICAL WIRE ELEMENT FOR CRACK PROTECTION MONITORING OF TRANSPORT BELTS - Google Patents
ELECTRICAL WIRE ELEMENT FOR CRACK PROTECTION MONITORING OF TRANSPORT BELTS Download PDFInfo
- Publication number
- NO141467B NO141467B NO3649/73A NO364973A NO141467B NO 141467 B NO141467 B NO 141467B NO 3649/73 A NO3649/73 A NO 3649/73A NO 364973 A NO364973 A NO 364973A NO 141467 B NO141467 B NO 141467B
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- Prior art keywords
- parts
- cycloaliphatic
- ring
- cyclohexene
- dimethanol
- Prior art date
Links
- 238000012544 monitoring process Methods 0.000 title 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 150000002170 ethers Chemical class 0.000 claims description 5
- 150000003944 halohydrins Chemical group 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- SSZWWUDQMAHNAQ-UHFFFAOYSA-N 3-chloropropane-1,2-diol Chemical compound OCC(O)CCl SSZWWUDQMAHNAQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 3
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims 2
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical group C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 150000002118 epoxides Chemical class 0.000 description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 7
- 229910052794 bromium Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004848 polyfunctional curative Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 235000002639 sodium chloride Nutrition 0.000 description 3
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241001639412 Verres Species 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- YOZBUSDPJJIARI-UHFFFAOYSA-N [3,4-dibromo-1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCC(Br)C(Br)C1 YOZBUSDPJJIARI-UHFFFAOYSA-N 0.000 description 1
- YVIMHTIMVIIXBQ-UHFFFAOYSA-N [SnH3][Al] Chemical compound [SnH3][Al] YVIMHTIMVIIXBQ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000003945 chlorohydrins Chemical class 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical class C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- -1 glycerin monochlorohydrin ethers Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012262 resinous product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65G—TRANSPORT OR STORAGE DEVICES, e.g. CONVEYORS FOR LOADING OR TIPPING, SHOP CONVEYOR SYSTEMS OR PNEUMATIC TUBE CONVEYORS
- B65G43/00—Control devices, e.g. for safety, warning or fault-correcting
- B65G43/02—Control devices, e.g. for safety, warning or fault-correcting detecting dangerous physical condition of load carriers, e.g. for interrupting the drive in the event of overheating
Landscapes
- Ropes Or Cables (AREA)
- Belt Conveyors (AREA)
- Insulated Conductors (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Control Of Conveyors (AREA)
Description
Fremgangsmåte til fremstilling av nye, halogenholdige glycidyletere. Process for the production of new, halogen-containing glycidyl ethers.
Gjenstanden for foreliggende oppfin-nelse er nye halogenholdige glycidyletere The object of the present invention is new halogen-containing glycidyl ethers
med den generelle formel with the general formula
hvori n betyr et helt lite tall og A en cykloalifatisk rest med n frie valenser, hvilke minst inneholder en gang grupperingen . in which n means a very small number and A a cycloaliphatic residue with n free valences, which contain at least once the grouping.
hvori begge restene Hal betyr klor- eller in which both residues Hal mean chlorine- or
bromatomer. bromine atoms.
De nye glycidyletere kan fås, idet man The new glycidyl ethers can be obtained by
i glycerinmonohalogenhydrinetere eller in glycerin monohalohydrin ethers or
glycidyletere av cykloalifatiske mono- eller glycidyl ethers of cycloaliphatic mono- or
polyalkoholer som minst inneholder en polyalcohols containing at least one
gang grupperingen times the grouping
til dobbeltbindingen tilleirer halogen og eventuelt deretter dehydrohalogenerer ha-logenhydringruppen eller -gruppene. Man kan videre fremstille de nye glycidyletere også idet man omsetter cykloalifatiske mono- eller polyalkoholer som minst en gang inneholder grupperingen adds halogen to the double bond and optionally then dehydrohalogenates the halohydrin group or groups. The new glycidyl ethers can also be prepared by reacting cycloaliphatic mono- or polyalcohols which at least once contain the grouping
med epihalogenhydriner eller glycerinmo-nohalogenhydriner og dehydrohalogenerer de intermediært dannede halogenhydrin-grupper. with epihalohydrins or glycerin monohalohydrins and dehydrohalogenate the intermediately formed halohydrin groups.
Egnede umettede cykloalifatiske mo-no- eller polyalkoholer, av hvilke de som utgangsstoffer anvendte monohalogenhy-driner henholdsvis glycidyletere avledes, er for eksempel: Cykloheksen-3-01-1, A<3->tetrahydrobenzyl-alkohol, 6-metyl-A<8->tetrahydrobenzylalko-hol; 2,5-endometylen-A<3->tetrahydroben-zylalkohol: dihydrodicyklo-pentadienol-8; A<3->clykloheksen-l,l-dimetanol, 6-metyl-A<:t->cykloheksen-l,l-dimetanol, 2,5-endometylen - A'!cykloheksen-1,1 -dimetanol. Suitable unsaturated cycloaliphatic mono- or polyalcohols, from which the monohalohydrins or glycidyl ethers used as starting materials are derived, are for example: Cyclohexene-3-01-1, A<3->tetrahydrobenzyl alcohol, 6-methyl-A< 8->tetrahydrobenzyl alcohol; 2,5-endomethylene-A<3->tetrahydrobenzyl alcohol: dihydrodicyclopentadienol-8; A<3->cyclohexene-1,1-dimethanol, 6-methyl-A<:t->cyclohexene-1,1-dimethanol, 2,5-endomethylene - A'!cyclohexene-1,1-dimethanol.
Fortrinnsvis går man ut fra glycerin-monoklorhydrinetere som man først halo-generer og deretter dehydrohalogenerer til de tilsvarende glycidyletere. Det er derved ytterst overraskende at halogeneringen går glatt og uten merkbare bireaksjoner, hvilket ikke på forhånd kunne ventes da det er kjent at det generelt ved halogenering av umettede glykoler oppnås dårlige til utilfredsstillende utbytter. For eksempel gir klorering av butin-2-diol-l,4 ved siden av meget harpiksprodukter bare 35 % 2,2, 3,3-tetraklorkutandiol-l,4 (sammenlikn tysk patent nr. 1 034 166). Preferably, the starting point is glycerin monochlorohydrin ethers which are first halogenerated and then dehydrohalogenated to the corresponding glycidyl ethers. It is therefore extremely surprising that the halogenation proceeds smoothly and without noticeable side reactions, which could not be expected in advance as it is known that poor to unsatisfactory yields are generally obtained by halogenating unsaturated glycols. For example, chlorination of butyn-2-diol-1,4 next to highly resinous products yields only 35% 2,2,3,3-tetrachlorocutanediol-1,4 (cf. German Patent No. 1,034,166).
Underkaster man i stedet for mono-halogenhydrineteren direkte glycidyleteren halogenering er utbyttene av sluttproduk-ter ifølge oppfinnelsen lavere fordi det kommer til bireaksjoner under oppspalt-ning av epoksydringen. If, instead of the monohalohydrin ether, the glycidyl ether is subjected to halogenation directly, the yields of end products according to the invention are lower because side reactions occur during cleavage of the epoxidation ring.
Halogeneringen av de umettede monoklorhydrin- henholdsvis glycidyletere fore-går hensiktsmessig ved hjelp av innvirk-ning av halogenet, spesielt Cl, eller Br3 på de umettede etere i et egnet oppløsnings-middel slik som CC1, eller benzol for eksempel ved temperaturer mellom 0 og 25° C, fortrinnsvis 5—15° C. Det innledes tilstrek-kelig halogen henholdsvis anvendes til-strekkelig til at dobbeltbindingen i den umettede eter avmettes kvantitativt. The halogenation of the unsaturated monochlorohydrin or glycidyl ethers takes place appropriately by means of the influence of the halogen, especially Cl, or Br3 on the unsaturated ethers in a suitable solvent such as CC1, or benzene, for example at temperatures between 0 and 25 ° C, preferably 5-15 ° C. Sufficient halogen is introduced or sufficient is used so that the double bond in the unsaturated ether is quantitatively desaturated.
Den eventuelt derpå følgende halo-genhydrogenavspaltning ved halogenhydri-net henholdsvis klorhydrinene utføres på kjent måte med faste alkalier eller vandige alkalioppløsninger. The optionally subsequent halogen-hydrogen separation by the halohydrin or the chlorohydrins is carried out in a known manner with solid alkalis or aqueous alkali solutions.
Blant de nye glycidyletere ifølge oppfinnelsen utmerker slike seg med den generelle formel Among the new glycidyl ethers according to the invention, those with the general formula stand out
hvori begge restene Hal, betyr klor- eller bromatom, R;! betyr et hydrogenatom eller en metylgruppe og n betyr tallet 1 eller 2, ved særlig lett tilgjengelighet. in which both residues Hal, mean chlorine or bromine atom, R;! means a hydrogen atom or a methyl group and n means the number 1 or 2, in particularly easy availability.
De halogenerte glycidyletere ifølge oppfinnelsen har i motsetning til de hittil kjente klorholdige epoksyharpikser bare litt farge og særlig derivater av A<:H->cykloheksen-l,l-dimetanol er, overraskende, nesten fargeløse. Videre er de delvis meget lavtviskøse. Di- henholdsvis polyglycidyl-eterne fremstilt ifølge oppfinnelsen reagerer med de vanlige herdere for epoksyharpikser og lar seg derfor analogt med andre polyfunksjonelle epoksydforbindelser ved tilsetning av slike herdere utherde kaldt eller varmt under nettdannelse. Slike herdere kan være basiske eller sure forbindelser. The halogenated glycidyl ethers according to the invention, in contrast to the hitherto known chlorine-containing epoxy resins, have only a little color and, in particular, derivatives of A<:H->cyclohexene-1,1-dimethanol are, surprisingly, almost colorless. Furthermore, they are partly very low-viscosity. The di- and polyglycidyl ethers produced according to the invention react with the usual hardeners for epoxy resins and can therefore, analogously to other polyfunctional epoxy compounds, be cured cold or hot under network formation by adding such hardeners. Such hardeners can be basic or acidic compounds.
Monoglycidyletrene ifølge oppfinnelsen alene reagerer likeledes med de nevnte herdere, men i de fleste tilfelle under dan-nelse av ikke-nettdannede lineære omset-ningsprodukter; med flerbasiske karbon-syrer og deres anhydrider, for eksempel kan de bringes til nettdannelse, henholdsvis herdes. Uttrykket «herdning» som brukes her betyr omdannelsen av glycidyletere til uoppløselige og usmeltbare harpikser. The monoglycidyl ethers according to the invention alone also react with the aforementioned hardeners, but in most cases with the formation of non-network-formed linear reaction products; with polybasic carboxylic acids and their anhydrides, for example, they can be brought to network formation, respectively hardened. The term "curing" as used herein means the conversion of glycidyl ethers into insoluble and infusible resins.
De herdbare glycidyletere henholdsvis deres blandinger med herdere kan før herdningen i en eller annen fase tilsettes andre flammehemmende stoffer, slik som for eksempel fosfater, videre fyllmidler, mykgjørere, fargegivende stoffer etc. Som strekk- og fyllmidler kan det for eksempel anvendes asfalt, bitumen, glassfibre, glim-mer, kvartsmel, cellulose, kaolin, findelt kiselsyre («AEROSIL») eller metallpulver. The curable glycidyl ethers or their mixtures with hardeners can be added before curing in one phase or another to other flame retardant substances, such as for example phosphates, further fillers, plasticisers, coloring substances etc. As stretchers and fillers, asphalt, bitumen, glass fibres, mica, quartz flour, cellulose, kaolin, finely divided silicic acid ("AEROSIL") or metal powder.
Blandingene av glycidyletrene og herd-erne kan i ufylt eller fylt tilstand samt i oppløsning eller emulsjon tjene som tek-stilhjelpemiddel, lamineringsharpiks og lakker, maling, dyppeharpikser, støpehar-pikser, stryke-, fylle- og sparkelmasser, klebemiddel og liknende og til fremstilling av slike midler. The mixtures of the glycidyl ethers and the hardeners can, in the unfilled or filled state as well as in solution or emulsion, serve as text styling aids, laminating resins and varnishes, paints, dipping resins, casting resins, ironing, filling and putty compounds, adhesives and the like and for manufacturing of such funds.
De nye glycidyletere kan videre tjene som mellomprodukter samt som flammehemmende aktive fortynnings- henholdsvis modifiseringsmidler for de kjente epoksyharpikser, slik som de for eksempel fås ved omsetning av epiklorhydrin med flerver-dige fenoler, slik som resorcin eller bis-[4-oksyfenyl-]dimetylmetan, i alkalisk me-dium. The new glycidyl ethers can further serve as intermediate products as well as flame retardant active diluents and/or modifiers for the known epoxy resins, as they are obtained, for example, by reacting epichlorohydrin with polyvalent phenols, such as resorcinol or bis-[4-oxyphenyl-]dimethylmethane , in alkaline medium.
I de følgende eksempler betyr deler vektsdeler, prosenter vektsprosenter og for-holdet mellom vektsdeler og volumdeler er det samme som ved kg og 1. Temperaturen er angitt i Celsiusgrader. De i epoksydekvi-valenter/kg angitte epoksyinnhold ble be-stemt ifølge den fremgangsmåte som er beskrevet av A. J. Durbetaki i «Analytical Chemistry» volum 28, nr. 12, desember 1956, sidene 2 000—2 001 med bromhydrogen i is-eddik. In the following examples, parts mean parts by weight, percentages by weight and the ratio between parts by weight and parts by volume is the same as for kg and 1. The temperature is indicated in degrees Celsius. The epoxy content stated in epoxy equivalents/kg was determined according to the method described by A. J. Durbetaki in "Analytical Chemistry" volume 28, no. 12, December 1956, pages 2000-2001 with hydrogen bromide in glacial acetic acid.
Eksempel 1: Example 1:
I et reaksjonskar som er forsynt med rører, termometer, gassinnledningsrør og kjølebad anbringes 327 deler (1 mol) A:<i->cykloheksen-1,1 -dimetanol-bis- (a-monoklorhydrin)-eter suspendert i 200 volumdeler CC1,. Mellom 10 og 15° ledes nu inn under god omrøring i løpet av en time 71 deler (1 mol) klor. Deretter tildryppes sta-dig under god avkjøling 240 deler 50 %-ig natronlut (3 mol) på en slik måte at temperaturen ikke overskrider 35° C. Til å be-gynne med er reaksjonen sterkt eksoterm og mot slutten må det ikke lenger kjøles. For fullstendiggjørelse av HCl-avspaltnin-gen rører man ennu 30 minutter ved 50° C og avkjøler, oppløser det dannede koksalt ved tilsetning av 300 volumdeler vann og skiller den organiske fase fra. Etter tørk-ning av den samme over kalsiumklorid befris den i vakuum for oppløsningsmiddel og det blir tilbake 298 deler av en nesten far-geløs middelviskøs væske med et epoksydinnhold på 4,05 epoksydekvivalenter/kg og et klorinnhold på 6,98 ekvivalenter klor/kg. Produktet består i hovedsaken av den diklorerte diglycidyleter med formelen 327 parts (1 mol) of A:<i->cyclohexene-1,1-dimethanol-bis-(a-monochlorohydrin)-ether suspended in 200 parts by volume of CC1 are placed in a reaction vessel equipped with stirrers, thermometer, gas inlet pipe and cooling bath. . Between 10 and 15°, 71 parts (1 mol) of chlorine are now introduced with good stirring during one hour. Then, with good cooling, 240 parts of 50% caustic soda (3 mol) are added drop by drop in such a way that the temperature does not exceed 35° C. To begin with, the reaction is strongly exothermic and towards the end it must no longer be cooled. To complete the HCl decomposition, stir for a further 30 minutes at 50° C and cool, dissolve the formed common salt by adding 300 parts by volume of water and separate the organic phase. After drying the same over calcium chloride, it is freed of solvent in vacuum and 298 parts of an almost colorless medium-viscous liquid with an epoxide content of 4.05 epoxide equivalents/kg and a chlorine content of 6.98 chlorine equivalents/kg remain. . The product mainly consists of the dichlorinated diglycidyl ether with the formula
Herdes forbindelsen i 24 timer med 0,85 mol fthalsyreanhydrid pr. ekvivalente epoksydgrupper under tilsetning av 13,5 % trixylenylfosfat ved 140° C, oppviser de støpte gjenstander en VDE-brennbarhet på 39 sekunder. The compound is cured for 24 hours with 0.85 mol of phthalic anhydride per equivalent epoxy groups under the addition of 13.5% trixylenyl phosphate at 140°C, the molded articles exhibit a VDE flammability of 39 seconds.
Eksempel 2: Example 2:
I det i eksempel 1 bekrevne reaksjonskar hvor bare gassinnledningsrøret er er-stattet med en dryppetrakt suspenderes 327 deler (1 mol) A<*->cykloheksen-l,l-dimetanol-bis- (a-monoklorhydrin) -eter i 100 volumdeler CC1,. Fra dryppetrakten lar man deretter 160 deler (1 mol) brom opp- løst i 200 volumdeler CC14 dryppe til under opprettholdelse av en temperatur på 10—15° C innen iy2 time. Deretter tildryppes som beskrevet i eksempel 1 240 deler 50 %-ig natronlut (3 mol) og deretter etter-røres i 30 minutter ved 50° C. Etter avkjøl-ing oppløses det utskilte koksalt ved tilsetning av 300 volumdeler vann, den organiske fase skilles fra og det opparbeides som beskrevet i eksempel 1. Man får 401 deler av en middelviskøs, nesten fargeløs væske som oppviser et epoksydinnhold på 4,1 epoksyd-ekvivalenter/kg og et brominnhold på 6,25 ekvivalenter brom/kg. Produktet består i hovedsaken av den dibromerte diglycidyleter med formelen In the reaction vessel described in example 1, where only the gas inlet pipe has been replaced with a dropping funnel, 327 parts (1 mol) of A<*->cyclohexene-1,1-dimethanol-bis-(a-monochlorohydrin)-ether are suspended in 100 parts by volume of CC1 ,. From the dropping funnel, 160 parts (1 mol) of bromine are then allowed to dissolved in 200 parts by volume of CC14 drop by drop while maintaining a temperature of 10—15° C within iy2 hours. Then, as described in example 1, 240 parts of 50% caustic soda (3 mol) are added dropwise and then stirred for 30 minutes at 50° C. After cooling, the secreted common salt is dissolved by adding 300 parts by volume of water, the organic phase is separated from and it is worked up as described in example 1. 401 parts of a medium-viscous, almost colorless liquid is obtained which exhibits an epoxide content of 4.1 epoxide equivalents/kg and a bromine content of 6.25 bromine equivalents/kg. The product mainly consists of the dibrominated diglycidyl ether with the formula
Herdes denne forbindelse med 1/5 mol dietylentriamin pr. ekvivalent epoksydgruppe under tilsetning av 13,5% trixylenylfosfat i 24 timer ved romtemperatur, viser de støpte gjenstander en VDE-brennbarhet på 0,5 sekunder. This compound is cured with 1/5 mol of diethylenetriamine per equivalent epoxy group under the addition of 13.5% trixylenyl phosphate for 24 hours at room temperature, the molded articles show a VDE flammability of 0.5 seconds.
Herder man forbindelsen med 0,85 mol ftalsyreanhydrid pr. ekvivalente epoksydgrupper under tilsetning av 13,5 % trixylenylfosfat i 24 timer ved 140° C får man støpte gjenstander med en VDE-brennbarhet på 0 sekunder. The compound is cured with 0.85 mol of phthalic anhydride per equivalent epoxy groups with the addition of 13.5% trixylenyl phosphate for 24 hours at 140° C, cast objects with a VDE flammability of 0 seconds are obtained.
Eksempel 3: Example 3:
I den apparatur som ble benyttet i eksempel 1 oppløses 254 deler (1 mol) A<3->cykloheksen -1,1 -dimetanoldigly cidyleter i 300 cm8 benzol. Innen 1V4 time innleder man nu ved 8—10° C 71 deler (1 mol) klor og avdamper deretter oppløsningsmidlet i vakuum. Det blir tilbake 320 deler av en middelviskøs væske med et epoksydinnhold på 3,22 epoksydekvivalenter/kg og et halogeninnhold på 7,88 ekvivalenter klor/kg som i hovedsaken består av den i eksempel 1 beskrevne diklorerte diglycidyleter. In the apparatus used in example 1, 254 parts (1 mol) of A<3->cyclohexene-1,1-dimethanol diglycidyl ether are dissolved in 300 cm8 of benzene. Within 1V4 hours, 71 parts (1 mol) of chlorine are now introduced at 8-10° C. and the solvent is then evaporated in a vacuum. There remain 320 parts of a medium-viscous liquid with an epoxide content of 3.22 epoxide equivalents/kg and a halogen content of 7.88 chlorine equivalents/kg, which mainly consists of the dichlorinated diglycidyl ether described in example 1.
Eksempel 4: Example 4:
254 deler (1 mol) A<8->cykloheksen-l,l-dimetanoldiglycidyleter oppløst i 100 volumdeler benzol tildryppes innen 1 time mellom 5 og 10° C 160 deler brom (1 mol) oppløst i 200 volumdeler benzol. Deretter avdampes oppløsningsmidlet i vakuum og man får 397 deler av en væske med et epoksydinnhold på 3,40 epoksydekvivalen-ter/kg og et halogeninnhold på 6,32 ekvivalenter brom/kg, hvilket i hovedsaken består av den i eksempel 2 beskrevne dibromerte diglycidyleter. 254 parts (1 mol) of A<8->cyclohexene-1,1-dimethanol diglycidyl ether dissolved in 100 parts by volume of benzene are added dropwise within 1 hour between 5 and 10° C. 160 parts of bromine (1 mol) dissolved in 200 parts by volume of benzene. The solvent is then evaporated in vacuum and 397 parts of a liquid with an epoxide content of 3.40 epoxide equivalents/kg and a halogen content of 6.32 bromine equivalents/kg are obtained, which mainly consists of the dibrominated diglycidyl ether described in example 2.
Eksempel 5: Example 5:
Analogt med det isom er beskrevet i eksempel 2 inndryppes i oppløsningen av 204,5 deler (1 mol) A<8->tetrahydrobenzyl-alkohol-a-monoklorhydrineter i 100 volumdeler benzol innen 1 time mellom 5 og 10° C oppløsningen av 160 deler (1 mol) brom i 200 volumdeler benzol. Den påfølgende HCl-avspaltning ut-føres i 2 trinn: Man drypper inn reaksjons-blandingen først 165 deler 36,4 %-ig natronlut (1,5 mol) og lar temperaturen stige mot 50° C. Det etterrøres i 30 minutter uten å avkjøle eller å oppvarme. Deretter avkjø-ler man, tilsetter 100 volumdeler vann, skiller fra den organiske fase og rører på ny med 80 deler 50 %-ig natronlut (1 mol) i 40 minutter ved 50° C. Man avkjøler på ny og skiller etter tilsetning av 100 volumdeler vann fra den organiske fase og den siste befris etter tørkning over kalsiumklorid i vakuum for oppløsningsmiddel. Det blir tilbake 291 deler 3,4-dibrom-cykloheksan-l-metylglycidyleter med formelen Analogously to what is described in example 2, drop into the solution of 204.5 parts (1 mol) A<8->tetrahydrobenzyl alcohol-a-monochlorohydrin ether in 100 parts by volume of benzene within 1 hour between 5 and 10° C the solution of 160 parts (1 mole) of bromine in 200 parts by volume of benzene. The subsequent HCl separation is carried out in 2 steps: First, 165 parts of 36.4% caustic soda (1.5 mol) are dripped into the reaction mixture and the temperature is allowed to rise towards 50° C. It is stirred for 30 minutes without to cool or to heat. Then cool, add 100 parts by volume of water, separate from the organic phase and stir again with 80 parts of 50% caustic soda (1 mol) for 40 minutes at 50° C. Cool again and separate after adding 100 parts by volume of water from the organic phase and the last is freed after drying over calcium chloride in vacuum for solvent. This leaves 291 parts of 3,4-dibromo-cyclohexane-1-methylglycidyl ether with the formula
som lett bevegelig nesten fargeløs olje med et epoksydinnhold på 2,4 epoksydekvivalen-ter/kg og et halogeninnhold på 7,14 ekvivalenter brom/kg. as an easily mobile almost colorless oil with an epoxide content of 2.4 epoxide equivalents/kg and a halogen content of 7.14 bromine equivalents/kg.
Eksempel 6: Example 6:
I 242,5 deler (1 mol) ct-monoklorhy-drineter av 8-hydroksy-dihydro-dicyklo-pentadien (8-hydroksy-trycyklo-[5.2.1.0 2 fi]-decen-4) oppløst i 100 volumdeler benzol, ledes inn innen 2 timer ved 0—5° C 71 deler (1 mol) klor. Man fortynner deretter med 100 volumdeler benzol, tildrypper 165 vektsdeler 36,4 %-ig natronlut (1,5 mol) idet man lar temperaturen stige mot 50° C. Man rører uten avkjøling eller oppvarmning i 30 minutter, avkjøler deretter og opparbeider produktet som beskrevet i eksempel 8, idet man nok en gang etterbehandler med 1 mol 50 %-ig natronlut i 40 minutter ved 50° C. Man får sluttelig 230,5 deler diklorert di-hydrodicyklopentadienglycidyleter med formelen In 242.5 parts (1 mol) of ct-monochlorohydrin ethers of 8-hydroxy-dihydro-dicyclo-pentadiene (8-hydroxy-tricyclo-[5.2.1.0 2 fi ]-decen-4) dissolved in 100 parts by volume of benzene, is led in within 2 hours at 0-5° C 71 parts (1 mol) chlorine. It is then diluted with 100 parts by volume of benzene, 165 parts by weight of 36.4% caustic soda (1.5 mol) are added drop by drop while allowing the temperature to rise to 50° C. Stir without cooling or heating for 30 minutes, then cool and work up the product as described in example 8, once again post-treating with 1 mol of 50% caustic soda for 40 minutes at 50° C. You finally get 230.5 parts of dichlorinated dihydrodicyclopentadiene glycidyl ether with the formula
som brun viskøs væske med et epoksydinnhold på 1,77 epoksydekvivalenter/kg og et klorinnhold på 24,5 %. as a brown viscous liquid with an epoxide content of 1.77 epoxide equivalents/kg and a chlorine content of 24.5%.
Eksempel 7: Example 7:
290 deler (0,96 mol) 3,4-dibromcyklo-heksan-l,l-dimetanol (smeltepunkt 137— 138° C) blandes med 300 deler benzol og tilsettes 2 deler tinntetraklorid. Man oppvar-mer blandingen til 70° C og lar under om-røring innen 20 minutter 187 deler (2,02 mol) epiklorhydrin dryppe til, idet temperaturen ved hjelp (av avkjøling holdes ved 70—75° C. Man rører deretter ennu i 30 minutter ved samme temperatur, avkjøler til 25° C og tilsetter 324 deler (2,4 mol) 29,6 %-ig natronlut. Temperaturen stiger derved bare lite og holdes ved oppvarmning ennu 1 time ved 70° C. Man lar det deretter avkjøle ennå noe, tilsetter 100 deler vann for oppløsning av saltet og skiller fra det benzoliske lag som nok en gang utrøres i 1 time med et 70 deler (0,96 mol) 50 %-ig natronlut ved 70° C. Man lar det igjen av-kjøle noe, tilsetter 90 deler vann og skiller fra det benzoliske lag som etter tørkning over kalsiumklorid og avdampning av opp-løsningsmidlet gir 391 deler av en nesten fargeløs væske som i sine egenskaper stem-mer overens med den diglycidyleter som fås ifølge eksempel 2. 290 parts (0.96 mol) of 3,4-dibromocyclohexane-1,1-dimethanol (melting point 137-138° C) are mixed with 300 parts of benzene and 2 parts of stannous tetrachloride are added. The mixture is heated to 70° C and, with stirring, within 20 minutes, 187 parts (2.02 mol) of epichlorohydrin are allowed to drip in, the temperature being kept at 70-75° C by means of cooling. 30 minutes at the same temperature, cools to 25° C and adds 324 parts (2.4 mol) of 29.6% caustic soda. The temperature thereby rises only slightly and is maintained by heating for another 1 hour at 70° C. It is then allowed to cool some more, add 100 parts of water to dissolve the salt and separate from the benzolic layer which is once again stirred for 1 hour with 70 parts (0.96 mol) of 50% caustic soda at 70° C. It is left again cool slightly, add 90 parts of water and separate from the benzol layer which, after drying over calcium chloride and evaporation of the solvent, gives 391 parts of an almost colorless liquid which in its properties corresponds to the diglycidyl ether obtained according to example 2 .
Følgende eksempler angår anvendelse av fremgangsmåteproduktene. The following examples relate to the use of the process products.
Eksempel 8: Example 8:
20 deler av den ifølge eksempel 2 dibromerte diglycidyleter oppløses i 8 deler av >en blanding av 3 deler butanol, 1 del etylenglykolmonoetyleter og 4 deler xylol. Denne oppløsning blandes med 15 deler av en 80 %-ig oppløsning av en polyamidhar-piks («Versamid 115») i etylenglykolmonoetyleter + xylol 1 : 1 og som fås ved kon-densasjon av dimerisert umettet plante-fettsyre og dietylentriamin. Lakkoppløs-ningen påføres aluminiumblikk i en lag-tykkelse på 150—200 p. Ved en times tørk-ning ved 20° C og påfølgende to timers herdning ved 70° C oppstår et høyglanset, hårdt, men ennu meget fleksibelt overtrekk. 20 parts of the dibrominated diglycidyl ether according to example 2 are dissolved in 8 parts of a mixture of 3 parts butanol, 1 part ethylene glycol monoethyl ether and 4 parts xylol. This solution is mixed with 15 parts of an 80% solution of a polyamide resin ("Versamid 115") in ethylene glycol monoethyl ether + xylol 1:1 and which is obtained by condensation of dimerized unsaturated plant fatty acid and diethylenetriamine. The varnish solution is applied to aluminum sheet metal in a layer thickness of 150-200 µm. After one hour of drying at 20° C and subsequent two hours of curing at 70° C, a high-gloss, hard, but still very flexible coating is produced.
Eksempel 9: Example 9:
100 deler av den ifølge eksempel 2 er- holdte diglycidyleter, 12 deler trietylente- 100 parts of it according to example 2 are- held diglycidyl ether, 12 parts of triethylene tere-
tramin og 4 deler tris-(l,2,4-dimetylamino-metyl)-fenol blandes grundig. Eketrespla-ter med en dimensjon på 22 x 9 x 1 cm bestrykes med blandingen og det legges inn en glassduk («ASI—314» fra firma Fibres de Verre, Lausanne) og etter gelering på-føres nok et dekklag. Det resulterer i et glatt, godt heftende beskyttelseslag. En brennbarhetsprøve som er utført ifølge fremgangsmåten DIN 53382 viser at ma-terialet nok er brennbart, men slukker så snart flammen fjernes. tramine and 4 parts of tris-(1,2,4-dimethylamino-methyl)-phenol are thoroughly mixed. Oak boards with a dimension of 22 x 9 x 1 cm are coated with the mixture and a glass cloth is inserted ("ASI-314" from the company Fibres de Verre, Lausanne) and, after gelling, another covering layer is applied. This results in a smooth, well-adherent protective layer. A flammability test carried out according to the method DIN 53382 shows that the material is probably flammable, but extinguishes as soon as the flame is removed.
Eksempel 10: Example 10:
100 deler av den diglycidyleter som er fremstilt ifølge eksempel 2, 15 deler trietylentetramin og 2,5 deler av et med butanol foretret melamin-formaldehyd-kondensa-sjonsprodukt blandes grundig og påføres i ca. 250 ^i tykt lag på aluminiumblikk. Ved romtemperatur herder dette lag natten over til et hårdt, men allikevel fleksibelt og høyglinsende overtrekk. 100 parts of the diglycidyl ether prepared according to example 2, 15 parts of triethylenetetramine and 2.5 parts of a butanol etherified melamine-formaldehyde condensation product are thoroughly mixed and applied for approx. 250 ^in a thick layer on aluminum tin. At room temperature, this layer hardens overnight into a hard, yet flexible and high-gloss coating.
Eksempel 11: Example 11:
Det tilberedes en blanding av 65 deler av en ved romtemperatur flytende diglycidyleter av bis-(4-oksyfenyl)-dimetylmetan med et epoksydinnhold på 5,2 epoksydekvi-valenter/kg og 35 kg av den ifølge eksempel 2 fremstilte dibromerte diglycidyleter med et epoksydinnhold på 4,1 ekvivalenter/kg. Harpiksblandingen røres grundig ut med 11,75 deler trietylentetramin som herder og med denne blanding fremstilles ved hjelp av håndpålegningsfremgangsmåten et 12-lags glassfiberforsterket laminat (A), idet det som glassduk ble benyttet «Vertrotex-duk type 354 AF1» fra firma Fibres de Verre, Lausanne. Dette laminat herdes i 24 timer ved 40° C. A mixture of 65 parts of a room-temperature liquid diglycidyl ether of bis-(4-oxyphenyl)-dimethylmethane with an epoxide content of 5.2 epoxide equivalents/kg and 35 kg of the dibrominated diglycidyl ether produced according to example 2 with an epoxide content of 4.1 equivalents/kg. The resin mixture is thoroughly stirred with 11.75 parts of triethylenetetramine which hardens and with this mixture a 12-layer glass fiber reinforced laminate (A) is produced using the hand application method, with "Vertrotex cloth type 354 AF1" from the company Fibers de Verre being used as glass cloth , Lausanne. This laminate is cured for 24 hours at 40°C.
For sammenlikning fremstilles under samme betingelser et annet laminat (B) hvor imidlertid den dibromerte diglycidyleter ifølge eksempel 2 ble utelatt. For comparison, a different laminate (B) is prepared under the same conditions, where, however, the dibrominated diglycidyl ether according to example 2 was omitted.
Verdiene i følgende tabell viser at la-minatet A er selvslukkende og mere vann-fast en laminat B. The values in the following table show that laminate A is self-extinguishing and more water-resistant than laminate B.
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2246139A DE2246139C3 (en) | 1972-09-20 | 1972-09-20 | Electrical conductor element for monitoring slits on conveyor belts |
Publications (2)
Publication Number | Publication Date |
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NO141467B true NO141467B (en) | 1979-12-10 |
NO141467C NO141467C (en) | 1980-03-19 |
Family
ID=5856851
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO3649/73A NO141467C (en) | 1972-09-20 | 1973-09-18 | ELECTRICAL WIRING ELEMENT FOR TRANSPORT TAPE PROTECTION PROTECTION MONITORING |
Country Status (7)
Country | Link |
---|---|
JP (1) | JPS4971676A (en) |
DE (1) | DE2246139C3 (en) |
ES (1) | ES418883A1 (en) |
IT (1) | IT993313B (en) |
NO (1) | NO141467C (en) |
SE (1) | SE404517B (en) |
ZA (1) | ZA737457B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3441742C2 (en) * | 1984-11-15 | 1996-01-11 | Bergwerksverband Gmbh | Conductor loops for monitoring conveyor belts at risk of slitting |
DE3927746C2 (en) * | 1989-08-23 | 1999-02-11 | Raetz Walter | Installation short-circuit ring for slit monitoring on conveyor belts |
DE4013764C2 (en) * | 1990-04-28 | 1999-04-01 | Raetz Walter | Installation short-circuit rings for electronic slit monitoring on conveyor belts |
DE19722673B4 (en) * | 1997-05-30 | 2004-08-05 | Contitech Transportbandsysteme Gmbh | Conductive loop for embedding in a belt, belt, conveyor belt |
-
1972
- 1972-09-20 DE DE2246139A patent/DE2246139C3/en not_active Expired
-
1973
- 1973-09-18 NO NO3649/73A patent/NO141467C/en unknown
- 1973-09-19 IT IT29132/73A patent/IT993313B/en active
- 1973-09-19 JP JP48105088A patent/JPS4971676A/ja active Pending
- 1973-09-19 SE SE7312775A patent/SE404517B/en unknown
- 1973-09-19 ES ES418883A patent/ES418883A1/en not_active Expired
- 1973-09-20 ZA ZA737457*A patent/ZA737457B/en unknown
Also Published As
Publication number | Publication date |
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ES418883A1 (en) | 1976-03-16 |
DE2246139A1 (en) | 1974-03-28 |
NO141467C (en) | 1980-03-19 |
ZA737457B (en) | 1974-08-28 |
IT993313B (en) | 1975-09-30 |
DE2246139B2 (en) | 1977-12-01 |
DE2246139C3 (en) | 1978-07-20 |
JPS4971676A (en) | 1974-07-11 |
SE404517B (en) | 1978-10-09 |
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