DE4325849A1 - Flameproofed polylactide and copolylactide - Google Patents
Flameproofed polylactide and copolylactideInfo
- Publication number
- DE4325849A1 DE4325849A1 DE19934325849 DE4325849A DE4325849A1 DE 4325849 A1 DE4325849 A1 DE 4325849A1 DE 19934325849 DE19934325849 DE 19934325849 DE 4325849 A DE4325849 A DE 4325849A DE 4325849 A1 DE4325849 A1 DE 4325849A1
- Authority
- DE
- Germany
- Prior art keywords
- polylactide
- lactide
- flameproofed
- poly
- copolylactide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 18
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical class NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- 239000003063 flame retardant Substances 0.000 claims description 10
- 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 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 5
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 5
- -1 cyclic Lactones Chemical class 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920001432 poly(L-lactide) Polymers 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009264 composting Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- VPVXHAANQNHFSF-UHFFFAOYSA-N 1,4-dioxan-2-one Chemical compound O=C1COCCO1 VPVXHAANQNHFSF-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Polymers OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229920001244 Poly(D,L-lactide) Polymers 0.000 description 1
- 229920000954 Polyglycolide Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 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
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- CJFCGSLFEZPBNJ-UHFFFAOYSA-N carbamimidoylazanium;phosphate Chemical compound NC([NH3+])=N.NC([NH3+])=N.NC([NH3+])=N.[O-]P([O-])([O-])=O CJFCGSLFEZPBNJ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- UOCIZHQMWNPGEN-UHFFFAOYSA-N dialuminum;oxygen(2-);trihydrate Chemical compound O.O.O.[O-2].[O-2].[O-2].[Al+3].[Al+3] UOCIZHQMWNPGEN-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- UYAKTBUPMOOXNW-UHFFFAOYSA-N guanidine;sulfuric acid Chemical compound NC(N)=N.NC(N)=N.OS(O)(=O)=O UYAKTBUPMOOXNW-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012549 training Methods 0.000 description 1
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical class O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Polylactid wird durch ringöffnende Polymerisation des cyclischen Lactids hergestellt. Ausgehend von L-Lactid, D-Lactid oder DL-Lactid erhält man Poly-L-Lactid, Poly-D-Lactid oder Poly-DL- Lactid. Während der Polymerisation kommt es nicht zu einer In version am optisch aktiven C-Atom, wodurch die Taktizität er halten bleibt. Poly-L- und Poly-D-Lactid können unter entspre chenden Verarbeitungsbedingungen, speziell durch kurzes Halten im Temperaturbereich von 100-200°C als teilkristalline Polymere mit einer Glaserweichungstemperatur von 50-55°C und einem Kristallitschmelzpunkt von 175°C erhalten werden. Durch Zumischen von DL- oder DD-Lactid oder von DL- oder LL-Lactid zu D-Lactid werden durch die ringöffnende Polymerisation Copolymere mit erniedrigter Kristallisationsgeschwindigkeit und erniedrigtem kristallinen Anteil erhalten. Der Schmelzpunkt sinkt ab, die Glaserweichungstemperatur bleibt jedoch erhalten. Möchte man jedoch die Glaserweichungstemperatur absenken, so führt man eine Copolymerisation mit dem cyclischen Glykolid durch. Das homopoly mere Polyglykolid weist eine Glaserweichungstemperatur von 20- 25°C auf. Durch Copolymerisation entsprechender Anteile von Lactid und Glykolid läßt sich die Glastemperatur des Copolymeren demnach zwischen 20-25°C bis 50-55°C einstellen.Polylactide is obtained by ring-opening polymerization of the cyclic Lactids manufactured. Starting from L-lactide, D-lactide or DL-lactide gives poly-L-lactide, poly-D-lactide or poly-DL- Lactide. In does not occur during the polymerization version on the optically active carbon atom, which increases the tacticity lasts. Poly-L- and poly-D-lactide can correspond to appropriate processing conditions, especially by briefly holding in Temperature range from 100-200 ° C as semi-crystalline polymers with a glass softening temperature of 50-55 ° C and one Crystallite melting point of 175 ° C can be obtained. By adding from DL or DD lactide or from DL or LL lactide to D lactide are copolymers with the ring-opening polymerization decreased crystallization rate and decreased obtained crystalline portion. The melting point drops that However, the glass softening temperature is retained. Would you like to however, lower the glass softening temperature, so you do one Copolymerization with the cyclic glycolide. The homopoly mere polyglycolide has a glass softening temperature of 20- 25 ° C. By copolymerizing appropriate proportions of lactide and glycolide the glass transition temperature of the copolymer accordingly Set between 20-25 ° C to 50-55 ° C.
Durch Blockcopolymerisation mit längerkettigen cyclischen Lactonen, insbesondere epsilon-Caprolacton erhält man sehr zähe, schlagfeste Lactidcopolymere, die sich durch einen kaum erniedrigten Schmelzbereich auszeichnen.By block copolymerization with longer chain cyclic Lactones, especially epsilon-caprolactone, are obtained in very tough form, impact-resistant lactide copolymers, which hardly differ distinguish reduced melting range.
Aufgrund der ausgezeichneten mechanischen Eigenschaften, der Ressourceschonung, der Kompostierbarkeit sowie der hohen Hydrolysestabilität unterhalb 50°C hat Polylactid ein hohes Anwen dungspotential. Es läßt sich überall dort einsetzen, wo bereits bisher technische Kunststoffe angewendet werden, z. B. für Gehäuse oder als Funktionsteile in Maschinenbau, Apparatebau, Elektro technik, Elektronik und Konsumgüterindustrie. Die Anwendung wird nur eingeschränkt durch die schlechtere Bewitterungsbeständig keit. Überall dort jedoch, wo Außenbewitterung oder UV-Licht kein Problem darstellt, sind die Teile dauerbeständig. Ein weiterer Vorteil von Polylactid ist seine ausgezeichnete Kriechstrom festigkeit, die darin begründet ist, daß bei thermischer Belastung keine nichtflüchtigen aromatischen, die elektrische Leitfähigkeit reduzierenden Abbauprodukte gebildet werden. Due to the excellent mechanical properties, the Conservation of resources, compostability and high Hydrolysis stability below 50 ° C has a high application potential. It can be used wherever it already is previously used engineering plastics, e.g. B. for housing or as functional parts in mechanical engineering, apparatus engineering, electronics technology, electronics and consumer goods industry. The application will only limited by the poorer weather resistance speed. However, wherever outdoor weathering or UV light does not occur The problem is, the parts are durable. Another The advantage of polylactide is its excellent leakage current strength, which is due to the fact that thermal No non-volatile aromatic, electrical pollution Conductivity-reducing degradation products are formed.
Bereits nicht ausgerüstetes Polylactid zeigt im Vergleich zu üblichen technischen Kunststoffen vorteilhafte Eigenschaften im Brandfall: Aufgrund des hohen Sauerstoffgehalts (ca. 44%) ist die Verbrennungswärme nahezu um die Hälfte geringer als bei üblichen Kunststoffen. Polylactid brennt deshalb mit niedrigerer Flammtemperatur als andere Kunststoffe. Die Flamme ist kaum sichtbar. Polylactid brennt auch ohne Rauchbildung und entwickelt keine hustenreizenden Brandgase. Bis zur Ausbildung einer selbst ändig brennenden Flamme muß wesentlich länger beflammt werden als beispielsweise im Falle von Polypropylen oder Polystyrol.Already not equipped polylactide shows in comparison to usual engineering plastics advantageous properties in Fire event: Due to the high oxygen content (approx. 44%) the heat of combustion is almost half that of usual plastics. Polylactide therefore burns at a lower rate Flame temperature than other plastics. The flame is barely there visible. Polylactide burns even without smoke and develops no coughing fumes. Until training yourself Constantly burning flame must be flamed much longer than for example in the case of polypropylene or polystyrene.
Aufgabe der Erfindung war es, die an sich schon günstigen Brand eigenschaften durch den Einsatz flammhemmender Additive soweit zu verbessern, daß derart ausgerüstetes Polylactid nach dem Brand verhalten nach UL 94-VO eingestuft werden kann.The object of the invention was to create the already inexpensive fire properties through the use of flame retardant additives improve that so treated polylactide after the fire behavior can be classified according to UL 94-VO.
Selbstverständlich steht zur Lösung dieser Aufgabe eine große Anzahl kommerzieller Flammschutzmittel wie halogenierte länger kettige Alkane, halogenierte cycloaliphatische Verbindungen, bromierte Diphenyle und Diphenylether, bromierte Polycarbonate, aliphatische und aromatische Phosphorverbindungen zur Verfügung. Unter der Voraussetzung der Entsorgung durch Kompostierung ver bietet sich jedoch der Einsatz derartiger Flammschutzmittel.Of course there is a big one to solve this task Number of commercial flame retardants such as halogenated longer chain alkanes, halogenated cycloaliphatic compounds, brominated diphenyls and diphenyl ethers, brominated polycarbonates, aliphatic and aromatic phosphorus compounds are available. Under the condition of disposal by composting ver however, the use of such flame retardants is appropriate.
Es wurde nun gefunden, daß sich Polylactid in der gewünschten Weise flammhemmend ausrüsten läßt, wenn jeweils 100 Gewichtsteile Polylactid mit 5 bis 100 Gewicht steilen eines Metalloxids oder -hydrats wie Aluminiumoxidtrihydrat (oder Aluminiumhydroxid), Magnesiumhydroxid oder eines Phosphats wie Ammoniumpolyphosphat vermischt werden.It has now been found that polylactide is in the desired Can be equipped flame retardant if 100 parts by weight each Polylactide with 5 to 100 parts by weight of a metal oxide or hydrate such as aluminum oxide trihydrate (or aluminum hydroxide), Magnesium hydroxide or a phosphate such as ammonium polyphosphate be mixed.
Als flammhemmende Mittel sind außerdem Guanidiniumsalze geeignet wie Guanidiniumphosphat, Guanidiniumsulfat oder Guanidinium carbonat. Der Guanidinanteil zerfällt während der Kompostierung in Ammoniak und Harnstoff, die weiter bakteriell abgebaut werden. Es können beliebige Mischungen der genannten flammhemmenden Mittel eingesetzt werden.Guanidinium salts are also suitable as flame retardants such as guanidinium phosphate, guanidinium sulfate or guanidinium carbonate. The guanidine fraction disintegrates during composting in ammonia and urea, which are further broken down bacterially. Any mixtures of the flame retardants mentioned can be used Means are used.
Die Korngröße der flammhemmenden Mittel sollte z. B. bei 0,5 bis 100 µm, vorzugsweise 2 bis 20 µm liegen. Vor dem Einmischen werden die Mittel zur Entfernung von anhaftendem Wasser zweckmäßig bei bis zu 180°C und eventuell vermindertem Druck (also unter 1 bar absolut) getrocknet. Die Einarbeitung in das Polylactid erfolgt nach üblichen Verfahren. So ist es günstig, das oder die flamm hemmenden Mittel in eine Schmelze des Polylactids einzumischen, wobei einem Extruder zunächst trockenes Polylactid, gegebenen falls unter Argon, bei 190 bis 210°C zugeführt wird und strom abwärts über eine weitere Öffnung im Extrudergehäuse das flamm hemmende Mittel zudosiert wird. Dabei hat es sich als vorteilhaft erwiesen, eine starke Abkühlung der Schmelze dadurch zu ver meiden, daß die anorganischen Pulver, beispielsweise mittels eines geheizten Förderaggregats, auf Temperaturen von 150 bis 180°C vorgeheizt werden.The grain size of the flame retardant should, for. B. at 0.5 to 100 microns, preferably 2 to 20 microns. Before being mixed in the means for removing adhering water expediently up to 180 ° C and possibly reduced pressure (i.e. under 1 bar absolutely) dried. The incorporation into the polylactide takes place according to usual procedures. So it is cheap, the flame inhibiting agents in a melt of the polylactide, with an extruder first given dry polylactide if supplied under argon, at 190 to 210 ° C and current down the flame through another opening in the extruder housing inhibiting agent is added. It has proven to be beneficial proven to thereby strongly cool the melt avoid that the inorganic powder, for example by means of a heated conveyor, at temperatures from 150 to Be preheated to 180 ° C.
Zur Herstellung kleinerer Mengen flammwidrig ausgerüsteten Poly lactids, z. B. für Prüfzwecke ist es auch möglich, Polylactid im 2- bis 10fachen ihres Volumens in Chloroform bei Raumtemperatur zu lösen, die gewünschte Menge an Flammschutzmittel in die Lösung einzumischen und sodann das Lösungsmittel durch Verdampfen, beispielsweise mittels eines Rotationsverdampfers zu entfernen.For the production of small quantities of flame retardant poly lactids, e.g. B. for testing purposes, it is also possible to use polylactide 2 to 10 times their volume in chloroform at room temperature to dissolve the desired amount of flame retardant in the solution mix in and then evaporate the solvent, for example by means of a rotary evaporator.
Bei den eingesetzten Polylactiden handelt es sich vorzugsweise um Poly-L-Lactid oder Poly-D-Lactid. Copolymere Lactide sind nur insoweit von Interesse, wenn sie noch Schmelzpunkte oberhalb 150°C aufweisen, also nur bis ca. 5 Mol.-% Comonomereinheiten. Comono mere sind 1,3-Dioxan-2-one der StrukturThe polylactides used are preferably Poly-L-lactide or poly-D-lactide. Copolymers are lactides only of interest if they still have melting points above 150 ° C have, ie only up to about 5 mol .-% comonomer units. Comono mers are 1,3-dioxan-2-ones of the structure
1,4-Dioxan-2-one der Struktur1,4-dioxan-2-one of the structure
weitere Lactide der Strukturfurther lactides of the structure
oder Lactone der Strukturor lactones of the structure
In den angeführten Strukturformeln können die Reste R¹ bis R⁶ gleich oder verschieden sein und Wasserstoff, eine verzweigte oder unverzweigte Alkyl-, Alkylen- oder Alkingruppe mit 1 bis 12, bevorzugt 1 bis 4 Kohlenstoffatomen enthalten, die gegebenenfalls durch Halogene, Hydroxigruppen, Alkoxygruppen, Formylgruppen, Acrylgruppen, Amino, Alkylamino, Dialkylamino oder Cycloalkyl gruppen substituiert sind.In the structural formulas mentioned, the radicals R¹ to R⁶ be the same or different and hydrogen, a branched or unbranched alkyl, alkylene or alkyne group with 1 to 12, preferably contain 1 to 4 carbon atoms, optionally by halogens, hydroxyl groups, alkoxy groups, formyl groups, Acrylic groups, amino, alkylamino, dialkylamino or cycloalkyl groups are substituted.
Die homo- oder copolymeren Lactide werden nach dem Stand der Technik ringöffnend ausgehend von der Monomerschmelze bei Tempe raturen von 180°C bis 230°C hergestellt. Als Polymerisationskata lysatoren sind BF3-Etherat, Titanalkoholate sowie weitere Man gan-, Zink-, Zinn-, Blei-Antimon oder Aluminiumverbindungen ein setzbar. Am häufigsten werden Zinn-II-Verbindungen als carbon saure Salze verwendet. Bevorzugt werden Zinn-II-octoat oder Zinn- II-ethyl-2-hexanoat in Konzentrationen von 10-6 bis 10-3 Mol pro Mol Monomermischung eingesetzt.The homo- or copolymeric lactides are ring-opening according to the prior art based on the monomer melt at temperatures from 180 ° C to 230 ° C produced. BF3 etherate, titanium alcoholates and other man, zinc, tin, lead antimony or aluminum compounds can be used as polymerization catalysts. Tin-II compounds are most commonly used as carboxylic acid salts. Tin-II-octoate or tin-II-ethyl-2-hexanoate is preferably used in concentrations of 10 -6 to 10 -3 moles per mole of monomer mixture.
Zur Demonstration der Wirkung wird Poly-L-Lactid mit einer in härenten Viskosität von 1,59 (100 ml/g), gemessen als 0,1%ige Lösung in Chloroform bei 25°C, eingesetzt. Die flammhemmenden Mittel werden eingemischt, indem jeweils 50 g Additiv in 300 ml Chloroform bei 25 bis 50°C suspendiert werden und in dieser Suspe nsion 75 bis 100 g Poly-L-Lactid gelöst werden. Danach wird das Chloroform soweit in einem Rotationsverdampfer abgezogen, bis die Masse gerade noch fließfähig ist. Sie wird sodann in eine mit Polytetrafluorethylen beschichtete Schale gegossen und das rest liche Chloroform bei Temperaturen bis 100°C in einem Vakuum trockenschrank abgezogen. Das Material wird mit Trockeneis abge kühlt und in einer Messermühle granuliert, getrocknet und mittels einer Matrize in einer Presse bei 200°C Prüfstäbe der Abmessungen 1,58 mm (1/16 Zoll) × 12,7 mm × 127 mm hergestellt. Die Prüfstäbe werden senkrecht eingespannt und nach der Vorschrift UL 94 der Underwriter′s Laboratories geprüft und eingestuft. To demonstrate the effect, poly-L-lactide is treated with an in inherent viscosity of 1.59 (100 ml / g) measured as 0.1% Solution in chloroform at 25 ° C, used. The flame retardant Agents are mixed in by adding 50 g of additive in 300 ml Chloroform are suspended at 25 to 50 ° C and in this Suspe nsion 75 to 100 g of poly-L-lactide can be dissolved. After that it will Withdraw the chloroform in a rotary evaporator until the Mass is just still flowable. You will then be in a Poured polytetrafluoroethylene coated shell and the rest Chloroform at temperatures up to 100 ° C in a vacuum deducted drying cabinet. The material is removed with dry ice cools and granulated in a knife mill, dried and dried a die in a press at 200 ° C test rods of dimensions 1.58 mm (1/16 inch) x 12.7 mm x 127 mm. The test bars are clamped vertically and according to UL 94 of the Underwriter’s Laboratories tested and classified.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934325849 DE4325849A1 (en) | 1993-07-31 | 1993-07-31 | Flameproofed polylactide and copolylactide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19934325849 DE4325849A1 (en) | 1993-07-31 | 1993-07-31 | Flameproofed polylactide and copolylactide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE4325849A1 true DE4325849A1 (en) | 1995-02-02 |
Family
ID=6494244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19934325849 Withdrawn DE4325849A1 (en) | 1993-07-31 | 1993-07-31 | Flameproofed polylactide and copolylactide |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE4325849A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005028558A1 (en) | 2003-09-22 | 2005-03-31 | Matsushita Electric Industrial Co., Ltd. | Flame-retardant resin composition, process for producing the same, and method of molding the same |
| WO2005105775A1 (en) * | 2004-04-30 | 2005-11-10 | Kyushu Institute Of Technology | Method of recovering lactide from polylactic acid or derivative thereof |
| EP1609820A4 (en) * | 2003-04-02 | 2006-04-12 | Mitsubishi Plastics Inc | OBJECT MOLDED BY INJECTION |
| CN100436524C (en) * | 2003-09-22 | 2008-11-26 | 松下电器产业株式会社 | Flame-retardant resin composition, its production method, and its molding method |
-
1993
- 1993-07-31 DE DE19934325849 patent/DE4325849A1/en not_active Withdrawn
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1609820A4 (en) * | 2003-04-02 | 2006-04-12 | Mitsubishi Plastics Inc | OBJECT MOLDED BY INJECTION |
| US8349935B2 (en) | 2003-04-02 | 2013-01-08 | Mitsubishi Plastics, Inc. | Polylactic acid resin article comprising grains of metal-hydroxide particles |
| WO2005028558A1 (en) | 2003-09-22 | 2005-03-31 | Matsushita Electric Industrial Co., Ltd. | Flame-retardant resin composition, process for producing the same, and method of molding the same |
| EP1669409A4 (en) * | 2003-09-22 | 2006-09-27 | Matsushita Electric Industrial Co Ltd | NON-FLAMMABLE RESIN COMPOSITION, PROCESS FOR PRODUCING THE SAME, AND METHOD OF MOLDING THE COMPOSITION |
| CN100436524C (en) * | 2003-09-22 | 2008-11-26 | 松下电器产业株式会社 | Flame-retardant resin composition, its production method, and its molding method |
| US7750069B2 (en) | 2003-09-22 | 2010-07-06 | Panasonic Corporation | Flame-retardant resin composition, production method of the same and molding method of the same |
| WO2005105775A1 (en) * | 2004-04-30 | 2005-11-10 | Kyushu Institute Of Technology | Method of recovering lactide from polylactic acid or derivative thereof |
| JPWO2005105775A1 (en) * | 2004-04-30 | 2008-03-13 | 国立大学法人九州工業大学 | Method for recovering lactide from polylactic acid or its derivatives |
| KR100830022B1 (en) * | 2004-04-30 | 2008-05-15 | 고쿠리츠 다이가쿠 호진 큐슈 코교 다이가쿠 | Mehtod of recovering lactide from polylactic acid or derivative thereof |
| US7557224B2 (en) | 2004-04-30 | 2009-07-07 | Kyushu Institute Of Technology | Method for recovering lactide from polylactic acid or derivative thereof |
| JP4517069B2 (en) * | 2004-04-30 | 2010-08-04 | 国立大学法人九州工業大学 | Method for recovering lactide from polylactic acid or its derivatives |
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