NO791717L - PROCEDURE FOR THE PREPARATION OF SATURATED POLYESTERIC PAPERS - Google Patents
PROCEDURE FOR THE PREPARATION OF SATURATED POLYESTERIC PAPERSInfo
- Publication number
- NO791717L NO791717L NO791717A NO791717A NO791717L NO 791717 L NO791717 L NO 791717L NO 791717 A NO791717 A NO 791717A NO 791717 A NO791717 A NO 791717A NO 791717 L NO791717 L NO 791717L
- Authority
- NO
- Norway
- Prior art keywords
- glycol
- mixture
- composition
- acid
- transesterified
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 18
- 229920006395 saturated elastomer Polymers 0.000 title claims description 7
- 239000000203 mixture Substances 0.000 claims description 49
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 239000002253 acid Substances 0.000 claims description 26
- 150000002334 glycols Chemical class 0.000 claims description 20
- 229920000728 polyester Polymers 0.000 claims description 19
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 7
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 5
- -1 polyethylene terephthalate Polymers 0.000 claims description 5
- 150000005846 sugar alcohols Polymers 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 4
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 238000005809 transesterification reaction Methods 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 150000005690 diesters Chemical class 0.000 claims 1
- 150000003504 terephthalic acids Chemical class 0.000 claims 1
- 238000009835 boiling Methods 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 7
- 150000008064 anhydrides Chemical class 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 238000005266 casting Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical class C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 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 1
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- SLGGJMDAZSEJNG-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;terephthalic acid Chemical compound OCCOCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 SLGGJMDAZSEJNG-UHFFFAOYSA-N 0.000 description 1
- 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
- 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 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Chemical class 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229940003585 ammens Drugs 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical class 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 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
- 238000004132 cross linking Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals 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
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical class CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical class CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical class C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Description
"Fremgangsmåte for fremstilling av umettede polyesterharpikser". "Process for the production of unsaturated polyester resins".
Foreliggende oppfinnelse vedrører en fremgangsmåte for fremstilling av umettede polyesterharpikser. The present invention relates to a method for the production of unsaturated polyester resins.
Fremstillingen av lineære polyestere av glykoler og tereftalsyre ved hjelp av esterutveksling og konvensering er vel kjent. Polyetylen-tereftalat og polybutylen-tereftalat er typiske produkter fra polyesterindustrien. Disse polyestere har funnet utstrakt anvendelse ved fremstilling av filmer, fibere og støpeblandinger. The production of linear polyesters from glycols and terephthalic acid by means of ester exchange and conventionation is well known. Polyethylene terephthalate and polybutylene terephthalate are typical products from the polyester industry. These polyesters have found extensive use in the production of films, fibers and molding compounds.
Fremgangsmåtene for fremstilling av lineære polyestere frem-bringer ofte en avfalls-strøm. De fleste fabrikanter fjerner etylenglykol fra disse strømmer og begraver eller brenner restene. I enkelte tilfeller er disse rester en blanding av glykoler og oligomerer. Oligomerer betegner i den foreliggende sammenheng en lavmolekylvekt polyester av tereftalsyre og en eller flere glykoler. Det er denne blanding som anvendes ved fremgangsmåten i henhold til oppfinnelsen for å fremstille de termoherdende umettede polyesterharpikser som ut-gjør det produkt som tilsiktes fremstilt. The processes for producing linear polyesters often produce a waste stream. Most manufacturers remove ethylene glycol from these streams and bury or burn the remains. In some cases, these residues are a mixture of glycols and oligomers. Oligomers in the present context denote a low molecular weight polyester of terephthalic acid and one or more glycols. It is this mixture that is used in the method according to the invention to produce the thermosetting unsaturated polyester resins which make up the intended product.
Det er vesentlig at egenskapene av polyestere er konstanteIt is essential that the properties of polyesters are constant
fra porsjon til porsjon. De avfalls-strømmer som anvendes ved fremgangsmåten i henhold til oppfinnelsen varierer imidlertid i sterk grad fra porsjon til porsjon og en inn- from portion to portion. The waste streams used in the method according to the invention, however, vary greatly from batch to batch and an in-
blanding av disse polyestere i uendret form i hovedkjeden av polyesterharpikser med høyere molekylvekt ville resultere i ønskede variasjoner i egenskapene. mixing these polyesters in unchanged form into the main chain of higher molecular weight polyester resins would result in desired variations in properties.
For å unngå dette fremstilles den termoherdende umettede polyester ved først å transforestre blandingen av glykoler og oligomerer. Dette gjøres ved oppvarming (første koking) To avoid this, the thermosetting unsaturated polyester is produced by first transesterifying the mixture of glycols and oligomers. This is done by heating (first boiling)
av blandingen av glykoler og oligomerer for å bryte opp oligomerene ved transforestring (depolymerisering). Til-setningen av etylenumettede dikarboksylsyrer eller deres anhydrider og en ytterligere koking følger den første koking. Ved å bryte opp oligomerene i den første koking nedsettes viskositetsvariasjoner i den resulterende umettede harpiks under lagring. of the mixture of glycols and oligomers to break up the oligomers by transesterification (depolymerization). The addition of ethylenically unsaturated dicarboxylic acids or their anhydrides and a further boiling follow the first boiling. By breaking up the oligomers in the first boil, viscosity variations in the resulting unsaturated resin are reduced during storage.
Den ytterligere glykol som anvendes ved fremgangsmåten i henhold til oppfinnelsen tilsettes til enten den første eller annen koking eller begge om nødvendig. Det samme gjelder den eller de umettede syrer som anvendes. The additional glycol used in the method according to the invention is added to either the first or second boiling or both if necessary. The same applies to the unsaturated acid(s) used.
Ved en ytterligere utførelsesform oppvarmes først avfalls-strømmen i den første koking for å transforestre oligomerene, ytterligere glykol tilsettes under en ytterligere koking og deretter følger tilsetning av umettet syre i en tredje koking. Også her kan det tilsettes ytterligere glykoler eller umettede syrer til hvilke som helst av de tre koketrinn. In a further embodiment, the waste stream is first heated in the first boiling to transesterify the oligomers, further glycol is added during a further boiling and then the addition of unsaturated acid follows in a third boiling. Here, too, additional glycols or unsaturated acids can be added to any of the three cooking stages.
Om ønsket kan katalysator tilsettes til det første trinn iIf desired, catalyst can be added to the first step i
både den to-trinns og tre-trinns kokeprosess. Det vesentlige trinn er at oligomerene brytes opp i transforestringstrinnet før den umettede syre tilsettes. both the two-stage and three-stage cooking process. The essential step is that the oligomers are broken up in the transesterification step before the unsaturated acid is added.
Blandingen av glykoler og oligomerer og hvilke som helst ytterligere umettede dikarboksylsyrer og glykoler føres inn i en reaktor og reaksjonen gjennomføres generelt ved en temperatur på fra 170 til 235°C ved et trykk på fra 0 til 4,2 kg/cm 2 og i en tid av fra 2 til 24 timer. Reaksjonen bør fortsette inntil utgangs-syretallet er i det minste halvert, The mixture of glycols and oligomers and any additional unsaturated dicarboxylic acids and glycols is introduced into a reactor and the reaction is generally carried out at a temperature of from 170 to 235°C at a pressure of from 0 to 4.2 kg/cm 2 and in a time off from 2 to 24 hours. The reaction should continue until the initial acid number is at least halved,
men foretrukket til et område fra 5 til 10.but preferably to a range of 5 to 10.
De etylenumettede dikarboksylsyrer føres så inn i reaktoren sammen med eventuelle ytterligere mettede syrer eller glykoler og reaksjonen gjennomføres ved en temperatur på The ethylenically unsaturated dicarboxylic acids are then fed into the reactor together with any further saturated acids or glycols and the reaction is carried out at a temperature of
fra 170 til 220°C og ved et trykk på fra 0 til 4,2 kg/cm<2>for den ytterligere tid som kreves for å redusere syretallet til under omtrent 35. from 170 to 220°C and at a pressure of from 0 to 4.2 kg/cm<2>for the additional time required to reduce the acid number to below about 35.
Blandingen av glykoler og glykol-tereftalsyre-polyester-oligomerer som med fordel anvendes for å fremstille de ønskede polyestere vil ha følgende analyse: The mixture of glycols and glycol terephthalic acid polyester oligomers which are advantageously used to produce the desired polyesters will have the following analysis:
S ammens etnii}2i_ vektprosent.S ammens etnii}2i_ weight percent.
Blandingen vil vanligvis ha et hydroksydtall i området fra omtrent 250 til omtrent 1000 idet et foretrukket område er fra omtrent 250 til omtrent 650. The mixture will usually have a hydroxide number in the range of from about 250 to about 1000, with a preferred range being from about 250 to about 650.
I den ovennevnte blanding kan glykoltereftalatet og høyere oligomerer antas å ha følgende formler: Etylenglykoltereftalatmonomer Dietylenglykoltereftalatmonorner Blandede glykoltereftalatmonomerer Høyere glykoltereftalat-oligomerer In the above mixture, the glycol terephthalate and higher oligomers can be assumed to have the following formulas: Ethylene glycol terephthalate monomer Diethylene glycol terephthalate monomers Mixed glycol terephthalate monomers Higher glycol terephthalate oligomers
hvori m generelt er større enn n og hvori summen av m + n er i området fra omtrent 2 til 4. wherein m is generally greater than n and wherein the sum of m + n is in the range of about 2 to 4.
Blandinger av glykoler og oligomerer som beskrevet ovenforMixtures of glycols and oligomers as described above
er kommersielt tilgjengelige som avfallsprodukt fra poly-alkylen-tereftalatproduksjon. are commercially available as a waste product from poly-alkylene terephthalate production.
Små mengder av forbindelser av uorganiske metaller som f.eks. titan, sink, bly, kalsium, antimon, mangan og lignende fore-ligger også i blandingen. Disse metallforbindelser er rester fra de katalysatorer som anvendes ved de forskjellige polyester prosesser. Small amounts of compounds of inorganic metals such as e.g. titanium, zinc, lead, calcium, antimony, manganese and the like are also present in the mixture. These metal compounds are residues from the catalysts used in the various polyester processes.
De mettede dikarboksylsyrer, flerverdige alkoholer og umettede dikarboksylsyrer som omsettes med denne blanding av glykoler og oligomerer for fremstilling av de ønskede umettede polyesterharpikser er i og for seg av kjent type. The saturated dicarboxylic acids, polyhydric alcohols and unsaturated dicarboxylic acids which are reacted with this mixture of glycols and oligomers to produce the desired unsaturated polyester resins are in and of themselves of a known type.
De karboksylsyrene, som er enten mettet eller bare aromatisk umettet, omfatter: ravsyre, adipinsyre, korksyre, azelainsyre, sebasinsyre, ftalsyre, isoftalsyre, tereftalsyre, tetraklorftalsyre, heksa-klorendometylentetrahydroftalsyre og lignende. The carboxylic acids, which are either saturated or only aromatically unsaturated, include: succinic acid, adipic acid, corkic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, hexachloroendomethylenetetrahydrophthalic acid and the like.
Anhydridene av disse syrer, hvor anhydrider forekommer, er selvfølgelig medomfattet da de polyestere som oppnås derfra er de samme. Videre er den aromatiske kjerne av disse syrer som f.eks. ftalsyre for oppfinnelsens formål generelt ansett som mettet da dobbeltbindingen ikke reagerer ved addisjon, The anhydrides of these acids, where anhydrides occur, are of course included as the polyesters obtained from them are the same. Furthermore, the aromatic core of these acids such as e.g. phthalic acid for the purposes of the invention is generally considered saturated as the double bond does not react upon addition,
i likhet med etylengrupper, ved fornettingsreaksjonene for de termoherdende polymerer. Hvor derfor betegnelsen "mettet dikarboksylsyre" anvender forstås det at betegnelsen omfatter også de aromatisk umettede dikarboksylsyrer. like ethylene groups, in the cross-linking reactions for the thermosetting polymers. Therefore, where the term "saturated dicarboxylic acid" is used, it is understood that the term also includes the aromatically unsaturated dicarboxylic acids.
De flerverdige alkoholer omfatter etylenglykol, dietylenglykol, trietylenglykol, polyetylenglykol, propylenglykol, dipropylenglykol, polypropylenglykol, glycerol, neopentylglykol, pentaerytritol, trimetylolpropan, trimetyloletan, 1,3-butylenglykol, 1,4-butylenglykol og lignende. The polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, glycerol, neopentyl glycol, pentaerythritol, trimethylolpropane, trimethylolethane, 1,3-butylene glycol, 1,4-butylene glycol and the like.
De etylenumettede dikarboksylsyrer omfatter syrer som f.eks. maleinsyre, fumarsyre, akonitinsyre, mesakonsyre, citrakon-syre, itakonsyre og halogenerte og alkylerte derivater av disse syrer og lignende, idet den foretrukne syre er maleinsyre. Anhydridene av disse syrer, hvor anhydrider forekommer, er selvfølgelig medomfattet da de polyestere som oppnås derfra hovedsakelig er de samme uansett om syren eller dens anhydrid anvendes. The ethylenically unsaturated dicarboxylic acids include acids such as maleic acid, fumaric acid, aconitic acid, mesaconic acid, citraconic acid, itaconic acid and halogenated and alkylated derivatives of these acids and the like, the preferred acid being maleic acid. The anhydrides of these acids, where anhydrides occur, are of course included as the polyesters obtained from them are essentially the same regardless of whether the acid or its anhydride is used.
Mengden av hvert material som eventuelt tilføres reaktorenThe amount of each material that may be fed to the reactor
er som følger basert på vektdeler:are as follows based on parts by weight:
Om ønsket kan etylenumettede monomerer som f.eks. vinylmonomerer innblandes etter at polyesteren er dannet. Eksempler på slike vinylmonomerer er styren, halogenerte styrener, vinyltoluen, divinylbenzen, oktylakrylat, oktylmetakrylat, diallylftalat og lignende. If desired, ethylenically unsaturated monomers such as e.g. vinyl monomers are mixed in after the polyester is formed. Examples of such vinyl monomers are styrene, halogenated styrenes, vinyltoluene, divinylbenzene, octyl acrylate, octyl methacrylate, diallyl phthalate and the like.
De forholdsvise mengder av de forskjellige materialer som tilføres styres av de egenskaper som kreves for den på-tenkte bruk av den endelige harpiks. Slike anvendelser omfatter bl.a. manuell opplegging, sprøyteopplegging, støpe-blandinger, ark-støpeblandinger og lignende. The relative amounts of the different materials supplied are controlled by the properties required for the intended use of the final resin. Such applications include e.g. manual application, spray application, casting mixes, sheet casting mixes and the like.
De følgende eksempler illustrerer oppfinnelsen.The following examples illustrate the invention.
EKSEMPEL 1.EXAMPLE 1.
Følgende bestanddeler ble ført inn i en reaktor:The following components were introduced into a reactor:
Blandingen ble oppvarmet ved en temperatur på 2 04°C i et tidsrom av 2 timer. Deretter ble 1,0 mol maleinsyreanhydrid ført inn i reaktoren og reaksjonen ble fortsatt i 5 timer ved en temperatur på 213°C. Syretallet ved slutten av kokingen var 19,6. The mixture was heated at a temperature of 204°C for a period of 2 hours. Then 1.0 mol of maleic anhydride was introduced into the reactor and the reaction was continued for 5 hours at a temperature of 213°C. The acid number at the end of boiling was 19.6.
Styren ble tilsatt til det resulterende material til å giStyrene was added to the resulting material to give
en initial viskositet på 395 eps. Etter 22 døgn var viskositeten 424 eps. Endringen i viskositet var således 1,3 eps pr. døgn. an initial viscosity of 395 eps. After 22 days the viscosity was 424 eps. The change in viscosity was thus 1.3 eps per day and night.
EKSEMPEL 2.EXAMPLE 2.
Følgende bestanddeler ble innført i en reaktor:The following components were introduced into a reactor:
Den oligomere-glykolblanding hadde samme sammensetning som blandingen anvendt i eksempel 1. The oligomeric glycol mixture had the same composition as the mixture used in example 1.
Blandingen ble oppvarmet ved en temperatur på 213°C i et tidsrom på 4 timer og 45 minutter. Syretallet ved slutten av kokingen var 19,7. The mixture was heated at a temperature of 213°C for a period of 4 hours and 45 minutes. The acid number at the end of boiling was 19.7.
Styren ble tilsatt til det resulterende material til å giStyrene was added to the resulting material to give
en initial viskositet på 370 eps. Etter 22 døgn var viskositeten 832 eps. Endringen i viskositet var 17 eps pr. døgn. an initial viscosity of 370 eps. After 22 days the viscosity was 832 eps. The change in viscosity was 17 eps per day and night.
Den eneste forskjell mellom eksemplene 1 og 2 er den to-trinns koking som ble foretatt i eksempel 1. Likevel er stabili-seringen av viskositeten i eksempel 1 påtagelig. Stabili-sering av viskositeten ved den to-trinns koking er meget fordelaktig for lagringsstabiliteten. The only difference between examples 1 and 2 is the two-stage boiling that was carried out in example 1. Nevertheless, the stabilization of the viscosity in example 1 is noticeable. Stabilization of the viscosity during the two-stage boiling is very beneficial for storage stability.
EKSEMPEL 3.EXAMPLE 3.
Følgende bestanddeler ble innført i en reaktor:The following components were introduced into a reactor:
Blandingen ble kokt i en lukket reaktor i 2 timer ved 232°C og deretter avkjølt til 93°C. The mixture was boiled in a closed reactor for 2 hours at 232°C and then cooled to 93°C.
Deretter ble følgende ytterligere blanding tilført reaktoren: Then the following additional mixture was added to the reactor:
Den annen koking varte så i 5 timer og 30 minutter ved 213°C inntil blandingen hadde et syretall på 26,9. Reaksjons-produktet ble avkjølt til 177°C og det ble sakte tilsatt 21,07 kg styren inneholdende 11,4 g toluhydrokinon. Den endelige harpiks hadde et syretall på 17,1 og en viskositet på 626 eps. The second boiling then lasted for 5 hours and 30 minutes at 213°C until the mixture had an acid number of 26.9. The reaction product was cooled to 177°C and 21.07 kg of styrene containing 11.4 g of toluhydroquinone was slowly added. The final resin had an acid number of 17.1 and a viscosity of 626 eps.
Dette eksempel viser fremstilling av en umettet polyester hvori blandingen av glykoler og oligomerer transforestres i nærvær av en ytterligere glykol og deretter omsettes med en umettet syre dg en mettet syre. This example shows the production of an unsaturated polyester in which the mixture of glycols and oligomers is transesterified in the presence of a further glycol and then reacted with an unsaturated acid and a saturated acid.
EKSEMPEL 4.EXAMPLE 4.
En typisk analyse av blandingen av glykoler og oligomerer som anvendes ved utøvelse av oppfinnelsen er: A typical analysis of the mixture of glycols and oligomers used in the practice of the invention is:
Den tilsynelatende molekylvekt av denne blanding eller hvilken som helst annen glykol-oligomerblanding som anvendes ved oppfinnelsen kan beregnes ved hjelp av den følgende formel: For å fremstille en termoherdende, umettet polyesterharpiks fra denne typiske blanding omsettes omtrent 5 6 vektdeler av blandingen med omtrent 5 vektdeler dipropylenglykol, omtrent 4 vektdeler propylenglykol, og omtrent 15 vektdeler isoftalsyre. 20 vektdeler maleinsyre tilsettes da under den annen koking. The apparent molecular weight of this mixture or any other glycol-oligomer mixture used in the invention can be calculated using the following formula: To prepare a thermosetting unsaturated polyester resin from this typical mixture, about 56 parts by weight of the mixture are reacted with about 5 parts by weight dipropylene glycol, about 4 parts by weight propylene glycol, and about 15 parts by weight isophthalic acid. 20 parts by weight of maleic acid are then added during the second boiling.
Mengden av glykoler og dikarboksylsyrer som tilsettes til den første koking avhenger av hydroksyltallet av avfalls-strømmen (blanding av oligomerer og glykoler) som anvendes, mens mengden av umettet dikarboksylsyre holdes konstant. Dette sikrer ensartede produktegenskaper til tross for variasjonene i sammensetningen av avfalls-strøm-glykol fra parti til parti. The amount of glycols and dicarboxylic acids added to the first boil depends on the hydroxyl number of the waste stream (mixture of oligomers and glycols) used, while the amount of unsaturated dicarboxylic acid is kept constant. This ensures uniform product properties despite the variations in the composition of waste stream glycol from batch to batch.
For å illustrere dette, hvis avfalls-strømmen hadde et hydroksyltall på 600, omsettes omtrent 49 vektdeler av avfalls-strømmen med omtrent 5,6 vektdeler dipropylenglykol, omtrent 4,4 vektdeler propylenglykol og omtrent 20 vektdeler isoftalsyre. 21 vektdeler maleinsyreanhydrid vil da bli tilsatt under den annen koking. To illustrate this, if the waste stream had a hydroxyl number of 600, about 49 parts by weight of the waste stream is reacted with about 5.6 parts by weight dipropylene glycol, about 4.4 parts by weight propylene glycol and about 20 parts by weight isophthalic acid. 21 parts by weight of maleic anhydride will then be added during the second boiling.
EKSEMPEL 5.EXAMPLE 5.
En umettet, termoherdende polyesterharpiks ble fremstilt i henhold til metoden fra eksempel 1 fra en blanding av oligomerer og glykoler hvori blandingen hadde et hydroksyltall på 529. Støpéstykker av denne harpiksfraksjon med 30 vektprosent styren ble fremstilt. An unsaturated, thermosetting polyester resin was prepared according to the method of Example 1 from a mixture of oligomers and glycols in which the mixture had a hydroxyl number of 529. Moldings of this resin fraction with 30% by weight styrene were prepared.
Støpestykkene ble testet for bøyemodul, bøyestyrke, strekk-styrke, strekkmodul, bruddforlengelse og varme-deformasjons-temperatur. The castings were tested for bending modulus, bending strength, tensile strength, tensile modulus, elongation at break and heat-deformation temperature.
Den samme fremgangsmåte ble gjennomført med en kommersielt tilgjengelig polyester-støpeblanding. Disse støpestykker ble også undersøkt med hensyn til egenskaper. I disse eksempler ble testene gjennomført i henhold til angitt ASTM-spesifikasjon. The same procedure was carried out with a commercially available polyester molding compound. These castings were also examined for properties. In these examples, the tests were carried out according to the stated ASTM specification.
De polyestere som således fremstilles ved fremgangsmåten i henhold til oppfinnelsen har fysikalske egenskaper som kan sammenlignes med eller i mange tilfeller er bedre enn egenskapene av kommersielt tilgjengelige polyestere. Likevel ble disse fremstilt fra avfalls-strømmer fra en polyester-fremstillingsprosess. Frembringelse av en brukbar polyester fra disse avfalls-strømmer gjør oppfinnelsen økologisk og økonomisk fordelaktig. The polyesters thus produced by the method according to the invention have physical properties which can be compared with or in many cases are better than the properties of commercially available polyesters. Nevertheless, these were produced from waste streams from a polyester manufacturing process. Production of a usable polyester from these waste streams makes the invention ecologically and economically advantageous.
Claims (6)
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