NO124868B - - Google Patents
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- Publication number
- NO124868B NO124868B NO2225/68A NO222568A NO124868B NO 124868 B NO124868 B NO 124868B NO 2225/68 A NO2225/68 A NO 2225/68A NO 222568 A NO222568 A NO 222568A NO 124868 B NO124868 B NO 124868B
- Authority
- NO
- Norway
- Prior art keywords
- phenol
- solvent
- polyester
- polyesters
- solutions
- Prior art date
Links
- 229920000728 polyester Polymers 0.000 claims description 44
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 14
- -1 polyethylene terephthalate Polymers 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 11
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 11
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 239000011877 solvent mixture Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- ACZVWYLTJHGUCP-UHFFFAOYSA-N n-(2,2,2-trichloro-1-hydroxyethyl)formamide Chemical compound ClC(Cl)(Cl)C(O)NC=O ACZVWYLTJHGUCP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 10
- 238000002166 wet spinning Methods 0.000 description 10
- 238000000578 dry spinning Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 238000002074 melt spinning Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- QACUUGBVDGMIQH-UHFFFAOYSA-N 4-(1-carboxybutoxy)benzoic acid Chemical compound CCCC(C(O)=O)OC1=CC=C(C(O)=O)C=C1 QACUUGBVDGMIQH-UHFFFAOYSA-N 0.000 description 1
- ZOPFZPGPAKRUFE-UHFFFAOYSA-N 4-(1-carboxyethoxy)benzoic acid Chemical compound OC(=O)C(C)OC1=CC=C(C(O)=O)C=C1 ZOPFZPGPAKRUFE-UHFFFAOYSA-N 0.000 description 1
- CQIJNTKWTVHOFV-UHFFFAOYSA-N 4-(1-carboxyhexoxy)benzoic acid Chemical compound CCCCCC(C(O)=O)OC1=CC=C(C(O)=O)C=C1 CQIJNTKWTVHOFV-UHFFFAOYSA-N 0.000 description 1
- MURBPOMIQLULQU-UHFFFAOYSA-N 4-(1-carboxypentoxy)benzoic acid Chemical compound CCCCC(C(O)=O)OC1=CC=C(C(O)=O)C=C1 MURBPOMIQLULQU-UHFFFAOYSA-N 0.000 description 1
- IKRCKEUYLJBWHG-UHFFFAOYSA-N 4-(1-carboxypropoxy)benzoic acid Chemical compound CCC(C(O)=O)OC1=CC=C(C(O)=O)C=C1 IKRCKEUYLJBWHG-UHFFFAOYSA-N 0.000 description 1
- LABJFIBQJFPXHZ-UHFFFAOYSA-N 4-(carboxymethoxy)benzoic acid Chemical compound OC(=O)COC1=CC=C(C(O)=O)C=C1 LABJFIBQJFPXHZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- RGCHNYAILFZUPL-UHFFFAOYSA-N trimethyl benzene-1,3,5-tricarboxylate Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(C(=O)OC)=C1 RGCHNYAILFZUPL-UHFFFAOYSA-N 0.000 description 1
- ZCBFZNUXFWUZLC-UHFFFAOYSA-N tripropyl benzene-1,3,5-tricarboxylate Chemical compound CCCOC(=O)C1=CC(C(=O)OCCC)=CC(C(=O)OCCC)=C1 ZCBFZNUXFWUZLC-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
- B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING
- B63B27/00—Arrangement of ship-based loading or unloading equipment for cargo or passengers
- B63B27/04—Arrangement of ship-based loading or unloading equipment for cargo or passengers of derricks, i.e. employing ships' masts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B66—HOISTING; LIFTING; HAULING
- B66C—CRANES; LOAD-ENGAGING ELEMENTS OR DEVICES FOR CRANES, CAPSTANS, WINCHES, OR TACKLES
- B66C1/00—Load-engaging elements or devices attached to lifting or lowering gear of cranes or adapted for connection therewith for transmitting lifting forces to articles or groups of articles
- B66C1/10—Load-engaging elements or devices attached to lifting or lowering gear of cranes or adapted for connection therewith for transmitting lifting forces to articles or groups of articles by mechanical means
- B66C1/101—Load-engaging elements or devices attached to lifting or lowering gear of cranes or adapted for connection therewith for transmitting lifting forces to articles or groups of articles by mechanical means for containers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B66—HOISTING; LIFTING; HAULING
- B66C—CRANES; LOAD-ENGAGING ELEMENTS OR DEVICES FOR CRANES, CAPSTANS, WINCHES, OR TACKLES
- B66C13/00—Other constructional features or details
- B66C13/04—Auxiliary devices for controlling movements of suspended loads, or preventing cable slack
- B66C13/08—Auxiliary devices for controlling movements of suspended loads, or preventing cable slack for depositing loads in desired attitudes or positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B66—HOISTING; LIFTING; HAULING
- B66C—CRANES; LOAD-ENGAGING ELEMENTS OR DEVICES FOR CRANES, CAPSTANS, WINCHES, OR TACKLES
- B66C23/00—Cranes comprising essentially a beam, boom, or triangular structure acting as a cantilever and mounted for translatory of swinging movements in vertical or horizontal planes or a combination of such movements, e.g. jib-cranes, derricks, tower cranes
- B66C23/60—Derricks
- B66C23/605—Derricks employing ships' masts
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Ocean & Marine Engineering (AREA)
- Jib Cranes (AREA)
- Carriers, Traveling Bodies, And Overhead Traveling Cranes (AREA)
- Load-Engaging Elements For Cranes (AREA)
- Artificial Filaments (AREA)
Description
Polyesteroppløsning egnet til fremstilling av fibre. Polyester solution suitable for the production of fibres.
Foreliggende oppfinnelse angår nye produkter bestående av eller inneholdende oppløsninger av syntetiske, lineære ved kondensasjon fremstillede polyestere. Oppfinnelsen angår særlig nye produkter som kan formes til nyttegjenstander som bånd, filmer, bust, fibre, tråder og lignende. The present invention relates to new products consisting of or containing solutions of synthetic, linear polyesters produced by condensation. The invention particularly relates to new products that can be shaped into useful items such as ribbons, films, bristles, fibres, threads and the like.
For enkelhets skyld vil oppfinnelsen i For simplicity, the invention will i
det følgende bli beskrevet i forbindelse med dens anvendelse på fremstilling av fibre og tråder eller filamenter. Produktene ifølge oppfinnelsen er imidlertid ikke begrenset til disse anvendelser. Der kjennes forskjellige metoder til å overføre polyestere til tråder og fibre. Noen av disse metoder er den såkalte smeitespinning, våtspinning og tørrspinning. the following will be described in connection with its application to the manufacture of fibers and threads or filaments. However, the products according to the invention are not limited to these applications. Different methods are known to transfer polyesters to threads and fibres. Some of these methods are the so-called melt spinning, wet spinning and dry spinning.
I smeltespinningsmetoden smelter man In the melt spinning method, you melt
span av en polyester på en oppvarmet rist og leder smeiten gjennom et filterskikt bestående av små partikler som sand eller lignende. Derefter presses smeiten gjennom en spinnedyse og de herved erholdte filamenter avkjøles. Smeltespinning er imidlertid beheftet med visse ulemper som anvendelse av høye temperaturer, hva der gjør tilsetning av plastiseringsmidler og modifiseringsmidler vanskelig, fordi slike midler er tilbøyelige til å missfarves og å spaltes. span of a polyester on a heated grid and guides the melt through a filter layer consisting of small particles such as sand or the like. The melt is then pressed through a spinning nozzle and the resulting filaments are cooled. However, melt spinning is subject to certain disadvantages such as the use of high temperatures, which makes the addition of plasticizers and modifiers difficult, because such agents are prone to discolouration and splitting.
I tørrspinnemetoden oppløses polyesteren i et oppløsningsmiddel for samme og ekstruderes gjennom en spinnedyse på van-lig måte. Oppløsningen ekstruderes i en atmosfære av inert gass som kan være oppvarmet. Strømninger i den inerte gass-atmosfære, den ekstruderte fiber og anvendelse av varme understøtter alle fjer-nelse av det flyktige oppløsningsmiddel. In the dry spinning method, the polyester is dissolved in a solvent for the same and extruded through a spinning die in the usual way. The solution is extruded in an atmosphere of inert gas which may be heated. Flows in the inert gas atmosphere, the extruded fiber and the application of heat all support the removal of the volatile solvent.
I våtspinnemetoden ekstruderes en oppløsning av polyesteren i et bad inneholdende en væske som ikke er oppløsnings-middel for polyesteren. Denne spinneme-tode har flere fordeler fremfor smeltespinnemetoden. Således er f. eks. våtspinnemetoden i alminnelighet mere økonomisk og kan utføres ved lavere temperaturer enn smeltespinnemetoden. Plastiseringsmidler og andre midler kan derfor tilsettes med minimal risiko for missfarvning og spalt-ning. Videre er visse typer plastiseringsmidler og modifiseringsmidler tilbøyelige til å være relativt lite egnet for innblanding i smelter ved høyere temperatur, mens de lett kan innblandes i polyester-oppløsnin-ger ved lave temperaturer. Polyester-opp-løsninger gir den ytterligere fordel at de lett kan støpes til filmer eller overtrekk med jevn tykkelse. Dette er ytterst vanskelig med smeltede materialer på grunn av deres relativt store viskositet. In the wet spinning method, a solution of the polyester is extruded in a bath containing a liquid which is not a solvent for the polyester. This spinning method has several advantages over the melt spinning method. Thus, e.g. the wet spinning method is generally more economical and can be carried out at lower temperatures than the melt spinning method. Plasticizers and other agents can therefore be added with minimal risk of discolouration and splitting. Furthermore, certain types of plasticizers and modifiers tend to be relatively unsuited for mixing into melts at higher temperatures, while they can easily be mixed into polyester solutions at low temperatures. Polyester solutions offer the further advantage that they can be easily molded into films or covers of uniform thickness. This is extremely difficult with molten materials due to their relatively high viscosity.
Våtspinning av polyestere er imidlertid ikke anvendt i industriell målestokk på grunn av mangelen på passende oppløs-ningsmidler. I alminnelighet er polyestere uoppløselige i de mere alminnelige, organ-iske oppløsningsmidler. Det foreligger få oppløsningsmidler for de mere vanlige poly-estertyper som både er billige, i besittelse av gode oppløsningsegenskaper, lett lar seg gjenvinne og ikke er korroderende. However, wet spinning of polyesters has not been used on an industrial scale due to the lack of suitable solvents. In general, polyesters are insoluble in the more common organic solvents. There are few solvents for the more common polyester types which are both cheap, possess good dissolving properties, can be easily recycled and are not corrosive.
Ved hjelp av foreliggende oppfinnelse skaffes der polyester-oppløsninger som lar seg overføre til formede gjenstander. Således kan oppløsninger ifølge oppfinnelsen spinnes til tråder eller filamenter. Videre er oppløsninger av syntetiske lineære ved kondensasjon fremstillede polyestere sta-bile og har slike egenskaper at de ikke går over i gel. With the help of the present invention, polyester solutions are obtained which can be transferred to shaped objects. Thus, solutions according to the invention can be spun into threads or filaments. Furthermore, solutions of synthetic linear polyesters produced by condensation are stable and have such properties that they do not turn into a gel.
Ifølge oppfinnelsen oppløser man syntetiske, lineære, ved kondensasjon fremstillede polyestere i blandinger av fenol og vann eller blandinger fremstillet ved smelt-ning av fenol sammen med resorcinol eller kloralamid. En oppløsningsmiddel-blanding inneholdende slike bestanddeler har ikke den egenskap at den går over i fast form ved 40 til 43° C, hva der er tilfelle når fenol alene brukes som oppløsningsmiddel. Slike blandinger av fenol med vann, resorcinol og kloralamid, er kjent i handelen som «flytende fenol» og det er funnet at på grunn av smeltepunktnedsettelsen kan opp-løsninger med god stabilitet ved lavere temperaturer og relativt høye innhold av faste stoffer, fremstilles ved å oppløse syntetiske, lineære, ved kondensasjon fremstillede polyestere i slike oppløsninger. Når fenol som er et kjent oppløsningsmiddel for syntetiske, lineære, ved kondensasjon fremstillede polyestere brukes alene, er stabili-teten av de erholdte oppløsninger ikke så stor som for oppløsninger med «flytende fenol» som oppløsningsmiddel, heller ikke kan der oppnåes et så høyt innhold av faste stoffer som i oppløsninger fremstillet med sistnevnte oppløsningsmidler. According to the invention, synthetic linear polyesters produced by condensation are dissolved in mixtures of phenol and water or mixtures produced by melting phenol together with resorcinol or chloralamide. A solvent mixture containing such components does not have the property of turning into solid form at 40 to 43° C, which is the case when phenol alone is used as solvent. Such mixtures of phenol with water, resorcinol and chloralamide are known in the trade as "liquid phenol" and it has been found that due to the lowering of the melting point, solutions with good stability at lower temperatures and relatively high contents of solids can be prepared by dissolve synthetic, linear, condensation-produced polyesters in such solutions. When phenol, which is a known solvent for synthetic, linear polyesters produced by condensation, is used alone, the stability of the solutions obtained is not as great as for solutions with "liquid phenol" as solvent, nor can such a high content be achieved of solids as in solutions prepared with the latter solvents.
Oppløsninger med et høyt innhold av faste stoffer og god stabilitet kan fremstilles ved å innblande polyesteren i den flytende fenol og oppvarme blandingen til en temperatur i området fra 25° C til blan-dingens kokepunkt. Om ønskes kan blandingen omrøres under oppvarming. Dette er imidlertid ikke nødvendig for å oppnå oppløsning. Solutions with a high content of solids and good stability can be prepared by mixing the polyester into the liquid phenol and heating the mixture to a temperature in the range from 25° C to the boiling point of the mixture. If desired, the mixture can be stirred while heating. However, this is not necessary to achieve resolution.
Ved fremstilling av oppløsninger av polyestere i oppløsningsmiddel-blandinger kan fenolen brukes i mengdeforhold på 95 —85 pst. beregnet på hele oppløsningsmid-lets vekt og vannet, resorcinol eller kloralamid, i et mengdeforhold på 5 til 15 pst. When preparing solutions of polyesters in solvent mixtures, the phenol can be used in a quantity ratio of 95 to 85 percent calculated on the entire weight of the solvent and the water, resorcinol or chloralamide, in a quantity ratio of 5 to 15 percent.
Den maksimale konsentrasjon av poly- The maximum concentration of poly-
estere som kan oppnås i slike oppløsninger og oppløsningens viskositet er avhengig av polyesterens natur, den oppløsnings-middel-blanding som brukes og av tempe-raturen. Ved fremstilling av filamenter eller fibre bruker man polyestere med molekylvekt på minst 10.000 ved fremstilling av slike oppløsninger. Når oppløsningen skal brukes som overtrekksmiddel f. eks. som lakk, kan man bruke polyestere med lavere molekylvekt. Oppløsninger inneholdende opp til 25 vektpst. polyestere er egnet for fremstilling av fibre og filamenter, men oppløsninger inneholdende 10—25 vektpst. av sådanne estere foretrekkes. esters that can be obtained in such solutions and the viscosity of the solution depends on the nature of the polyester, the solvent-agent mixture used and the temperature. When producing filaments or fibers, polyesters with a molecular weight of at least 10,000 are used when producing such solutions. When the solution is to be used as a coating agent, e.g. as varnish, polyesters with a lower molecular weight can be used. Solutions containing up to 25 wt. polyesters are suitable for the production of fibers and filaments, but solutions containing 10-25 wt. of such esters is preferred.
De syntetiske, lineære, ved kondensasjon fremstillede polyestere som brukes ved utførelsen av foreliggende oppfinnelse, er dem som er dannet av dikarbonsyrer og glykoler og sampolymeriserte estere samt modifikasjoner av slike polyestere og sampolymeriserte estere. I høyt polymerisert tilstand kan slike polyestere og sampolymeriserte estere formes til filamenter eller tråder og lignende og derefter orienteres permanent ved koldtrekning. The synthetic, linear, condensation-produced polyesters used in the practice of the present invention are those formed from dicarboxylic acids and glycols and copolymerized esters as well as modifications of such polyesters and copolymerized esters. In a highly polymerized state, such polyesters and copolymerized esters can be formed into filaments or threads and the like and then permanently oriented by cold drawing.
De polyestere og sampolymeriserte estere som er særlig fordelaktige i forbindelse med foreliggende oppfinnelse er dem som fåes ved oppvarming av én eller flere glykoler av rekken HO(CH2)„-OH (i hvilken n er et helt tall fra 2 til 10) med én eller flere dikarbonsyrer eller ester-dannende derivater av slike syrer. Blant de dikarbonsyrer og ester-dannende derivater av sådanne som er fordelaktige i forbindelse med foreliggende oppfinnelse, nevnes tereftalsyre, isoftalsyre, sebacinsyre, adipinsyre, p-karboksyfenoleddiksyre, ravsyre, p,p'-dikarboksybifenyl, p,p'-dikarboksykar-banilid, p,p'-dikarboksytiokarbanilid, p,p'-dikarboksydifenylsulfon, p-karboksyfen-oksyeddiksyre, p-karboksyfenoksypropion-syre, p-karboksyfenoksysmørsyre, p-karboksyfenoksyvalerinsyre, p-karboksy-fenoksy-heksansyre, p-karboksyfenoksy-heptansyre, p,p'-dikarboksydifenylmetan, p,p'-dikarboksydifenyletan, The polyesters and copolymerized esters which are particularly advantageous in connection with the present invention are those obtained by heating one or more glycols of the series HO(CH2)„-OH (in which n is an integer from 2 to 10) with one or several dicarboxylic acids or ester-forming derivatives of such acids. Among the dicarboxylic acids and ester-forming derivatives thereof which are advantageous in connection with the present invention, mention is made of terephthalic acid, isophthalic acid, sebacic acid, adipic acid, p-carboxyphenolacetic acid, succinic acid, p,p'-dicarboxybiphenyl, p,p'-dicarboxycarbanilide, p,p'-dicarboxythiocarbanilide, p,p'-dicarboxydiphenylsulfone, p-carboxyphenoxyacetic acid, p-carboxyphenoxypropionic acid, p-carboxyphenoxybutyric acid, p-carboxyphenoxyvaleric acid, p-carboxyphenoxyhexanoic acid, p-carboxyphenoxyheptanoic acid, p, p'-dicarboxydiphenylmethane, p,p'-dicarboxydiphenylethane,
p,p'-dikarboksyfenylpropan, p,p'-dikarboksydifenylbutan, p,p'-dikarboksydifenylpentan, p,p'-dikarboksydifenylheksan, p,p'-dikarboksydifenylheptan, p,p'-dikarboksydifenyloktan, p,p'-dikarboksydifenoksyetan, p,p'-dikarboksydifenoksypropan, p,p'-dikarboksydifenoksybutan, p,p'-dikarboksydifenoksypentan, p,p'-dikarboksydifenoksyheksan, 3-alkyl 4-((3-karboksyetoksy) p,p'-dicarboxydiphenylpropane, p,p'-dicarboxydiphenylbutane, p,p'-dicarboxydiphenylpentane, p,p'-dicarboxydiphenylhexane, p,p'-dicarboxydiphenylheptane, p,p'-dicarboxydiphenyloctane, p,p'-dicarboxydiphenoxyethane, p ,p'-dicarboxydiphenoxypropane, p,p'-dicarboxydiphenoxybutane, p,p'-dicarboxydiphenoxypentane, p,p'-dicarboxydiphenoxyhexane, 3-alkyl 4-((3-carboxyethoxy)
benzoesyre, oksalsyre, glutarsyre, pimelin-syre, suberinsyre, azelainsyre og dioksy-syrer av etylen med den generelle formel: benzoic, oxalic, glutaric, pimelic, suberic, azelaic and dioxy acids of ethylene with the general formula:
(i hvilken R betegner (CH2)n og n er et helt tall fra 1 til 4) samt arylestere og (in which R denotes (CH2)n and n is an integer from 1 to 4) as well as aryl esters and
-halvestere av alifatiske og cykloalifatiske syrer, ammoniumsalter, aminsalter og syre-halogenider av sådanne syrer. Eksempler - half-esters of aliphatic and cycloaliphatic acids, ammonium salts, amine salts and acid halides of such acids. Examples
på glykoler som kan brukes ved utførelsen av foreliggende oppfinnelse er etylenglykol, trimetylenglykol, tetraemtylenglykol og dekametylenglykol. Imidlertid foretrekkes polyetylen-tereftalat fordi tereftalsyre og etylenglykol fra hvilke denne forbindelse fremstilles, er lett tilgjengelige. Polyetylen -tereftalat har også et relativt høyt smelte-punkt, nemlig omkring 250 til 255° C og denne egenskap er særlig fordelaktig ved fremstilling av filamenter for tekstilindu-strien. Blant de modifiserte polyestere og sampolymeriserte estere som er fordelaktige ved utførelse av foreliggende oppfinnelse er de ovenfor nevnte polyestere og sampolymeriserte estere modifisert med kjedeavsluttende grupper som har hydrofile egenskaper, som monofunksjonelle estere som danner polyetere med den generelle formel of glycols that can be used in the execution of the present invention are ethylene glycol, trimethylene glycol, tetraethylene glycol and decamethylene glycol. However, polyethylene terephthalate is preferred because terephthalic acid and ethylene glycol from which this compound is prepared are readily available. Polyethylene terephthalate also has a relatively high melting point, namely around 250 to 255° C and this property is particularly advantageous when producing filaments for the textile industry. Among the modified polyesters and copolymerized esters that are advantageous in carrying out the present invention are the above-mentioned polyesters and copolymerized esters modified with chain-terminating groups that have hydrophilic properties, such as monofunctional esters that form polyethers of the general formula
i hvilken R betegner en alkylgruppe inneholdende fra 1 til 4 kullstoffatomer, m og n er hele tall fra 2 til 22 og x er et helt tall som angir polymerisasjonsgraden, dvs. x er et helt tall fra 1 til 100 eller mer. Eksempler på slike forbindelser er metok-sypolyetylen-glykol, etoksypolyetylen-glykol, n-propoksypolyetylen-glykol, iso-propoksypolyetylen-glykol. En annen me-get fordelaktig kjedeavsluttende forbindelse er polyvinylmetyleter med en OH gruppe i endestilling. in which R denotes an alkyl group containing from 1 to 4 carbon atoms, m and n are integers from 2 to 22 and x is an integer indicating the degree of polymerization, i.e. x is an integer from 1 to 100 or more. Examples of such compounds are methoxypolyethylene glycol, ethoxypolyethylene glycol, n-propoxypolyethylene glycol, isopropoxypolyethylene glycol. Another very advantageous chain-terminating compound is polyvinyl methyl ether with an OH group in the terminal position.
Modifikasjoner kan også frembringes ved anvendelse av midler som danner kryssvise bindinger sammen med de kjedeavsluttende grupper. Midler for dannelse av kryssvise bindinger som ifølge oppfinnelsen anvendes til å modifisere polyestere, er polyfunksjonelle syrer og alkoholer med flere funksjoner enn 2 eller enkle derivater av sådanne. Syrene og deres derivater er forbindelser med den generelle formel Modifications can also be produced by the use of agents which form cross-links together with the chain-terminating groups. Means for forming cross-linked bonds which, according to the invention, are used to modify polyesters, are polyfunctional acids and alcohols with more functions than 2 or simple derivatives thereof. The acids and their derivatives are compounds of the general formula
(II) (II)
i hvilken R, R' og R" betegner alkylgrupper med 1 til 3 kullstoffatomer og R'" betegner hydrogen eller alkylgrupper med 1 til 2 kullstoffatomer. Blant slike forbindelser er trimetyl-trimesat, tripropyl-trimesat og i ringen alkylerte estere av benzen-1,3,5-trikarbonsyre osv. De polyfunksjonelle alkoholer og enkle derivater av sådanne som kan brukes som midler for dannelse av kryssvise bindinger, er de mettede, alifatiske eller cykloalifatiske, flerverdige alkoholer inneholdende bare kullstoff, hydrogen og oxygen og med 3 til 6 kullstoffatomer i molekylet og i hvilke n er større enn 2. Den generelle formel for disse er in which R, R' and R" denote alkyl groups of 1 to 3 carbon atoms and R'" denotes hydrogen or alkyl groups of 1 to 2 carbon atoms. Among such compounds are trimethyl trimesate, tripropyl trimesate and ring alkylated esters of benzene-1,3,5-tricarboxylic acid, etc. The polyfunctional alcohols and simple derivatives thereof which can be used as cross-linking agents are the saturated , aliphatic or cycloaliphatic, polyhydric alcohols containing only carbon, hydrogen and oxygen and with 3 to 6 carbon atoms in the molecule and in which n is greater than 2. The general formula for these is
i hvilken R betegner en mettet, alifatisk gruppe eller en cykloalifatisk gruppe. Eksempler på slike forbindelser er pentaery-tritol, sorbitol, glycerol, mannitol. Andre polyestere som kan brukes ved utførselen av foreliggende oppfinnelse er forbindelser som sampolymerisater av polyetylenterafta-lat og polyetylen-isoftalat, modifisert med de ovenfor nevnte kjedeavsluttende midler såvel som med de ovenfor nevnte midler for dannelse av kryssvise bindinger. in which R represents a saturated aliphatic group or a cycloaliphatic group. Examples of such compounds are pentaerythritol, sorbitol, glycerol, mannitol. Other polyesters that can be used in the implementation of the present invention are compounds such as copolymers of polyethylene terephthalate and polyethylene isophthalate, modified with the above-mentioned chain terminating agents as well as with the above-mentioned agents for forming cross-links.
En del av ovennevnte midler til modifi-sering av polyestere er beskrevet i patent nr. 96 310. Some of the above-mentioned agents for modifying polyesters are described in patent no. 96 310.
Når det ønskes av polyesteroppløsnin-gene ifølge foreliggende oppfinnelse å frem-stille formede gjenstander med modifisert utseende eller modifiserte egenskaper, kan der før fremstillingen av vedkommende gjenstand tilsettes polyesteroppløsningene forskjellige stoffer som gir sådanne effek-ter uten å forårsake noen ufordelaktige virkninger. Som slike tilsetningsmidler kan der brukes plastiseringsmidler, pigmenter, farvestoffer, anti-statiske midler, midler som nedsetter brennbarheten osv. When it is desired from the polyester solutions according to the present invention to produce shaped objects with modified appearance or modified properties, before the production of the relevant object, different substances can be added to the polyester solutions which produce such effects without causing any disadvantageous effects. As such additives, plasticizers, pigments, dyes, anti-static agents, agents that reduce flammability etc. can be used.
I det følgende beskrives som eksempler noen utførelsesformer for oppfinnelsen. I disse eksempler er mengdeforholdene an-gitt i vektprosent eller vektsdeler når ikke annet er anført. In the following, some embodiments of the invention are described as examples. In these examples, the quantity ratios are stated in percentage by weight or parts by weight when not stated otherwise.
Eksempel I. Example I.
9 gram av en oppløsningsmiddel-blanding bestående av 88 pst. fenol og 12 pst. vann samt 1 g polyetylen-tereftalat ble blandet og blandingen oppvarmet under omrøring til 100° C. Herved oppløstes polymerisatet lett så at man fikk en klar, lett-flytende oppløsning som er egnet både for våtspinning og tørrspinning. Oppløsningen var stabil ved temperaturer over 25° C. 9 grams of a solvent mixture consisting of 88 percent phenol and 12 percent water as well as 1 g of polyethylene terephthalate were mixed and the mixture heated with stirring to 100° C. This dissolved the polymer easily so that a clear, easily flowing solution that is suitable for both wet spinning and dry spinning. The solution was stable at temperatures above 25°C.
Eksempel II. Example II.
9 gram av en oppløsningsmiddel-blanding bestående av 88 pst. fenol og 12 pst. 9 grams of a solvent mixture consisting of 88 percent phenol and 12 percent
vann samt 1 g polyetylen-tereftalat modifisert med 10 pst. etoksypolyetylen-glykol ble blandet og blandingen oppvarmet under omrøring til 100° C. Herved oppløstes polymerisatet lett så at man fikk en klar, lett-flytende oppløsning som er egnet både for våtspinning og tørrspinning. Oppløsnin-gen var stabil ved temperaturer over 25° C. water and 1 g of polyethylene terephthalate modified with 10 percent ethoxypolyethylene glycol were mixed and the mixture heated with stirring to 100° C. This dissolved the polymer easily so that a clear, easily flowing solution was obtained which is suitable for both wet spinning and dry spinning . The solution was stable at temperatures above 25°C.
Eksempel III. 9 gram av en oppløsningsmiddel-blanding bestående av 88 pst. fenol og 12 pst. vann samt 1 g polyetylentereftalat modifisert med 20 pst. etoksypolyetylen-glykol ble blandet og blandingen oppvarmet under omrøring til 100° C. Herved oppløstes polymerisatet lett så at man fikk en klar, lett-flytende oppløsning egnet for både våtspinning og tørrspinning. Oppløsningen var stabil ved temperaturer over 25° C. Example III. 9 grams of a solvent mixture consisting of 88 per cent phenol and 12 per cent water as well as 1 g of polyethylene terephthalate modified with 20 per cent ethoxypolyethylene glycol were mixed and the mixture heated with stirring to 100° C. This dissolved the polymer easily so that one got a clear, easy-flowing solution suitable for both wet spinning and dry spinning. The solution was stable at temperatures above 25°C.
Eksempel IV. Example IV.
8,2 gram fenol ble smeltet sammen med 82 g resorcinol. Smeiten ble blandet med 1 g polyetylentereftalat og oppvarmet under omrøring til 90° C, hvorved 1 g polyetylen-tereftalat begynte å gå i oppløsning. Tem-peraturen ble hevet til 115° C hvorved polymerisatet gikk fullstendig i oppløsning så at man fikk en klar, homogen oppløs-ning som er egnet for både våtspinning og tørrspinning. Oppløsningen var stabil ved temperaturer over 36° C. 8.2 grams of phenol were fused with 82 grams of resorcinol. The melt was mixed with 1 g of polyethylene terephthalate and heated with stirring to 90° C., whereupon 1 g of polyethylene terephthalate began to dissolve. The temperature was raised to 115° C, whereby the polymer completely dissolved so that a clear, homogeneous solution was obtained which is suitable for both wet spinning and dry spinning. The solution was stable at temperatures above 36°C.
Eksempel V. Example V.
8,2 g fenol sammensmeltet med 0,82 g kloralamid ble blandet med 1 g polyetylen-tereftalat og under omrøring oppvarmet til 100° C, hvorved polymerisatet oppløstes og man fikk en klar oppløsning egnet både til våtspinning og tørrspinning. 8.2 g of phenol fused with 0.82 g of chloralamide was mixed with 1 g of polyethylene terephthalate and, with stirring, heated to 100° C, whereby the polymer was dissolved and a clear solution suitable for both wet spinning and dry spinning was obtained.
Polyesterproduktene ifølge foreliggende oppfinnelse kan med fordel brukes på området overtrekksmidler, f. eks. ved påføring av overtrekk på tekstilstoffer. Således kan et tekstilmateriale overtrekkes og/eller impregneres med polyester-oppløsninger ifølge oppfinnelsen og derpå behandles med, dvs. gjennomtrekkes med en væske som ikke er oppløsningsmiddel for polyesteren, hvorved polyesteren utfelles i og på tekstil-materialet. Metaller, papir og ugjennom-trengelige hinner kan også overtrekkes med polyester-produktene ifølge oppfinnelsen ved hjelp av vanlige og velkjente frem-gangsmåter. The polyester products according to the present invention can be advantageously used in the area of coating agents, e.g. when applying coatings to textile fabrics. Thus, a textile material can be coated and/or impregnated with polyester solutions according to the invention and then treated with, i.e. permeated with, a liquid which is not a solvent for the polyester, whereby the polyester is precipitated in and on the textile material. Metals, paper and impermeable films can also be coated with the polyester products according to the invention using common and well-known methods.
En av hovedfordelene ved foreliggende oppfinnelse er at den skaffer polyester-produkter som lett lar seg overføre til far-vede gjenstander ved hjelp av våtspinning eller tørrspinning-metoder som begge er mer økonomiske enn smeltespinningsmetoden. One of the main advantages of the present invention is that it provides polyester products which can easily be transferred to colored objects by means of wet spinning or dry spinning methods, both of which are more economical than the melt spinning method.
Claims (3)
Applications Claiming Priority (1)
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GB26844/67A GB1162878A (en) | 1967-06-09 | 1967-06-09 | Improvements relating to Cranes for Handling Containers |
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NO124868B true NO124868B (en) | 1972-06-19 |
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NL (1) | NL6807671A (en) |
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DE2630182A1 (en) * | 1976-07-05 | 1978-01-19 | Hans Tax | CONTAINER LOADING CRANE |
IT1143860B (en) * | 1977-11-23 | 1986-10-22 | Genovesi Cost Mecc Ind Spa | CONTAINER ROTATION DEVICE |
LU78596A1 (en) * | 1977-11-28 | 1979-06-13 | Ciba Geigy Ag | MONOAZO DYES, METHOD OF MANUFACTURING AND USE |
US4217076A (en) * | 1978-09-13 | 1980-08-12 | Raygo Wagner, Inc. | Load handling vehicle with rotating grapple mechanism |
US4374790A (en) * | 1980-07-08 | 1983-02-22 | Marley Company | Method and apparatus for pumping concrete to form structure at elevated heights |
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US4932541A (en) * | 1989-04-24 | 1990-06-12 | Calspan Corporation | Stabilized shipboard crane |
US5253771A (en) * | 1991-11-18 | 1993-10-19 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Counter-balanced, multiple cable construction crane |
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DE1756572B2 (en) | 1974-03-07 |
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US3567040A (en) | 1971-03-02 |
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