EP3765550A1 - Flammhemmender masterbatch für polyamid 6 und daraus hergestellte fasern - Google Patents
Flammhemmender masterbatch für polyamid 6 und daraus hergestellte fasernInfo
- Publication number
- EP3765550A1 EP3765550A1 EP19716785.1A EP19716785A EP3765550A1 EP 3765550 A1 EP3765550 A1 EP 3765550A1 EP 19716785 A EP19716785 A EP 19716785A EP 3765550 A1 EP3765550 A1 EP 3765550A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- master batch
- flame retardant
- base polymer
- polyamide
- flame
- 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.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 78
- 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 title claims abstract description 70
- 229920002292 Nylon 6 Polymers 0.000 title claims abstract description 66
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 47
- 239000000835 fiber Substances 0.000 title claims description 46
- 238000000034 method Methods 0.000 claims abstract description 46
- 229920005601 base polymer Polymers 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 238000013329 compounding Methods 0.000 claims abstract description 16
- 238000010128 melt processing Methods 0.000 claims abstract description 10
- 239000004033 plastic Substances 0.000 claims abstract description 7
- 229920003023 plastic Polymers 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- ZVNLUXZZYVQUTE-UHFFFAOYSA-N (6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)methanol Chemical compound C1=CC=C2P(CO)(=O)OC3=CC=CC=C3C2=C1 ZVNLUXZZYVQUTE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005469 granulation Methods 0.000 claims abstract description 3
- 230000003179 granulation Effects 0.000 claims abstract description 3
- 229920006018 co-polyamide Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 239000004753 textile Substances 0.000 claims description 7
- 239000010408 film Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 18
- 230000000996 additive effect Effects 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 9
- 238000009987 spinning Methods 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 230000009970 fire resistant effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- -1 bicyclic phosphates Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- AIXMJTYHQHQJLU-UHFFFAOYSA-N chembl210858 Chemical compound O1C(CC(=O)OC)CC(C=2C=CC(O)=CC=2)=N1 AIXMJTYHQHQJLU-UHFFFAOYSA-N 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007380 fibre production Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- LNEUSAPFBRDCPM-UHFFFAOYSA-N carbamimidoylazanium;sulfamate Chemical compound NC(N)=N.NS(O)(=O)=O LNEUSAPFBRDCPM-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000739 chaotic effect Effects 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KZRJKMZQXATVEB-UHFFFAOYSA-N chlorophosphinous acid Chemical class OPCl KZRJKMZQXATVEB-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920005622 compatible polymer blend Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- OYIKARCXOQLFHF-UHFFFAOYSA-N isoxaflutole Chemical compound CS(=O)(=O)C1=CC(C(F)(F)F)=CC=C1C(=O)C1=C(C2CC2)ON=C1 OYIKARCXOQLFHF-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229960003903 oxygen Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
Definitions
- the present invention generally relates to a flame-retardant polymer master batch and to a method of producing the same. Moreover, the invention relates to a method of producing a product with flame retardant properties, and to such a product.
- Fibers of polyamide 6 are preferred fibers in technical applications where high mechanical strength (high tenacity and elongation at break) is needed.
- the PA6 polymer being aliphatic, it is very flammable and produces a large amount of toxic gases like HCN and CO. Therefore, a suitable flame-retardant modifica tion of PA6 fibers is needed for fire safe application.
- the polyam ides can be flame retarded by incorporating halogenated flame retardants, however their use is not preferred due to toxicity and environmental reasons [3,4]
- Flame retardant PA6 fibers can also be prepared by incorporating meltable [5] and non-meltable halogen free additives [6] or combination of both kinds of additives [7] in the fiber spinning process. Textiles produced from these fibers have shown to have excellent flame-retardant be havior; however, they have very poor mechanical properties. In some cases, only small lab scale trials were performed without any industrial upscaling or feasibility study. Non meltable additives like melamine cyanurate [8] and clays [9] have also been used to pre pare flame retardant PA6 fibers. The actual manufacturing process for producing these flame-retardant fibers is quite complex (cleaning after in situ polymerization) and such fibers have inferior mechanical properties and are thus not suitable for industrial applica- tions.
- DOPO based compounds are established as flame retardant additives for high temperature polyesters because of their excellent thermal stability [10].
- DOPO derivatives with varying thermal stabilities and compatibility in PA6 are known in the literature. However, there is limited reference or no reference on the use DOPO- derivatives to produce flame retardant PA6 fibers via the melt spinning route. Some DOPO derivatives have been shown to be suitable for PA6 engineering plastics [10], but their use for making PA6 fibers has not been reported.
- a flame retardant polymer master batch which comprises an admixture of 8 to 70 wt.% of a flame retard ant consisting of 6-(hydroxymethyl)dibenzo[c,e] [1,2]oxaphosphinine 6-oxide, with the remainder essentially consisting of a base polymer, said base polymer being either poly amide or co-polyamide compatible with polyamide 6.
- the master batch is in a granular form.
- granular form generally denotes a non-powdery form consisting of particles shaped as chips, flakes, pellets or granules and having a size of the order of a few mm, typically about 2 to 8 mm.
- master batch shall be understood in a broad sense meaning that the master batch is suitable for use in a melt compounding process with predefined amounts of (i) a main polymeric species, which is often a neat or “virgin” polymer, and (ii) of the master batch. However, this terminology does not exclude suitability of the master batch for di rect melt processing.
- the expression "essentially consisting of a base polymer” shall be understood as equivalent to “consisting of a base polymer plus any impurities and other substances that are inevitably present in the base polymer”.
- co-polyamide shall be understood in the sense corresponding to the defini tion of "co-polymer”, i.e. as a polyamide derived from more than one monomeric spe cies.
- polyamide or co-polyamide compatible with polyamide-6 shall be under stood as a a polyamide or co-polyamide that can be melt processed together with poly amide 6 without adverse effect on thermomechanical properties.
- the statemtent "polymer A is compatible with B” is generally accepted in the sense of being suitable to form a compatible polymer blend.
- a definition for the latter term is found in the IUPAC Compendium of Chemical Terminolo gy (doi:10.1351/goldbook.CT07581).
- Various types of co-polyamides tailored to different types of application can be obtained commercially.
- Co-polyamides considered as useful for the present invention would gen erally be selected from those having a melting range of 1 10-200 °C.
- HMDOPO has the following structure:
- HMDOPO 6-(hydroxymethyl)dibenzo[c,e][1 ,2]oxaphosphinine 6-oxide
- HMDOPO is known in the literature as flame retardant for various polymers [1 1 -49] but has never been described to produce PA6 master batch and/or PA 6 fibers made thereof.
- the use of HMDOPO as a reactive flame retardant for epoxy and other polymers has been reported in the literature [1 1 -48]. Few reports also outline its possible use in PET fi bers as flame retardant additive [41 ,49]. However, there is no report of use of HMDOPO as flame retardant additive for melt-spun PA 6 fibers.
- HMDOPO has a melting point -170 °C and a decomposition temperature slightly greater than 200 °C, and it is likely that it starts to volatilize above this temperature.
- HMDOPO is compatible with PA6 processing. This finding was particularly unexpected in view of the presence of a reactive hydroxyl group. As will be discussed further below, fibers with satisfactory mechanical performance were produced even when spun with 30 wt.% HMDOPO. An admixture of 5-10 wt. %
- a method of producing a master batch as defined above comprises the steps of supplying appropriate amounts of the base poly mer in granular form and of said flame retardant in powder form to a compounding ex truder followed by melt compounding at a temperature of 200 to 260°C and granulation to form said master batch in granular form.
- a method of producing a product with flame retardant properties comprises the steps of either
- the above method exploits the main finding of the present invention, i.e. the favorable flame-retardant effect obtainable by incorporating HMDOPO into PA6.
- the method can be carried out according to option (a), which means directly melt processing a master batch, preferably in granular form, comprising 8 to 70 wt.% HMDOPO with the remainder essentially consisting of base polymer.
- the method can be car ried out according to option (b), in which case virgin base polymer (i.e. base polymer without flame retardant) in granular form and flame retardant in neat granular form (i.e. without base polymer) are melt processed together.
- a product with flame retardant proper ties obtainable with the above defined method comprises at least one region formed of said base polymer containing an admixture of 8 to 40 wt.%, particularly 15 to 30 wt.%, of said flame retardant.
- the relative amount of the flame-retardant admixture can be selected in broad range and will generally depend on how the master batch is used further.
- the admixture is 10 to 50 wt.%, particularly 10 to 40 wt.%, more particularly 15 to 30 wt.%.
- the base polymer is polyamide 6. Advan tageously, the base polymer has a comparatively high relative viscosity, which improves stability after addition of the flame retardant. Therefore, according to one embodiment, the relative viscosity is at least about 2.7.
- a step (a) of melt processing a master batch is carried out using a granular mixture of the master batch and a further polymer that is compatible with the base polymer.
- the term "granular mixture” shall be understood to mean that both the base polymer and the further polymer are supplied in granular form.
- the product being formed is a film, membrane or solid body, whereas according to a further embodiment (claim 9) the product is a melt spun fiber.
- the product being formed is a melt spun fiber comprising a core section and a sheath section, the sheath section being formed of the base polymer and an admixture of 10 to 40 wt.%, particularly 15 to 30 wt.% of the flame retardant, and the core section being formed of a further polymer compatible with the base polymer.
- the base polymer is polyamide 6 with a rela tive viscosity of at least about 2.7 and the further polymer is polyamide 6 with a relative viscosity of about 2.4, i.e. in the range of 2.3 to 2.5.
- the method further comprises the step of making a textile from said melt spun fiber.
- the textile has flame retardant properties characterized by a limiting oxygen index of at least 25%, preferably at least 30%.
- a limiting oxygen index is the minimum concentration of oxygen, expressed as a percentage, that will support combustion of a polymer. Noting that air has an oxy- gen content of about 21%, any LOI values that are higher than 21 % are indicative of a flame-retardant effect.
- LOI values for different plastics materials are deter mined by standardized tests such as the ISO 4589 and ASTM D2863 tests. BRIEF DESCRIPTION OF THE DRAWING
- Fig. 1 shows a diagram of the melt flow ratio obtained for the master batch using
- PA6 RV2.4 (circles, blue curve) and PA6 RV2.7 (squares, red curve) as a func tion of HMDOPO concentration expressed in wt.%.
- the master batch/ compound production was performed using a polyamide 6 with a rel- ative viscosity of 2,7 and HMDOPO.
- twin screw compound ing lines with 21 mm, 25 L/D (MB No. 1 -3), and 16 mm, 36 L/D (MB No. 4), respectively, were used.
- the screw configuration was set up to obtain a homogeneous compound. Chaotic mixing elements were used on the screw configuration allowing the use of lower temperatures, pressure and torque. The following were the processing conditions for manufacturing the master batch.
- PA6 RV 2.7 Using a PA6 RV 2.7 it was possible to achieve 40% additive concentration; however, the process becomes instable, showing a behavior similar to the observed when processing 30 % of additive using PA6 RV 2.4. As conclusion, it is possi ble to say that the use a PA6 RV 2.7 allows to introduce 10% more additive into the compounding than using PA6 RV2.4. With a stable process was possible to reach 30% of FR additive. Pa6 with higher relative viscosity (greater than 2.7) may be suitable to pro prise master batch with higher additive HMDOPO concentration (>40%).
- a mas ter batch with 50% HMDOPO concentration (master batch no. 4) could be produced in a stable process (PA6 with RV 2.6). Characterization of the master batch
- Melt flow index (MFI) tests were carried out to deduce the material behavior during the spinning trials. As reference values between 10 g/10min and 50 g/10min (under a 2,16 kg load) should be obtained for a stable spinning process. These values are only indica tive, since they are based in stable processes previously achieved using materials with melt flows rate out of this range. Others parameters, such as melt strength, should be taken in account. However, considering this test, its observations, and the observations from previous compounding step, it will be possible to deduce about the relevance of performing a melt spinning trial using the master batch with a higher amount of FR ad ditive. The MFI tests were performed using a load of 2,16 kg at 230 °C. All the samples were previous dried 4 hours at 80°C.
- DSC data of the master batch were obtained as per the standards ISO 1 1357-1 :1997 Plastics - Differential scanning calorimetry (DSC) - Part 1 : General principles" and ISO 1 1357-2:1999 "Plastics - Differential scanning calorimetry (DSC) - Part 2: Determination of glass transition temperature".
- the data for respective PA6 are pre sented in the tables given below:
- Table 2 DSC data for master batch obtained from PA6 with relative viscosity of 2.4.
- Table 3 DSC data for master batch obtained from PA6 with relative viscosity of 2.7.
- the fiber production was conducted using virgin PA6 and the master batch (PA6 - 2.7 viscosity with 30 % of HMDOPO additive).
- An initial approach of bi-component fiber with a sheath-core geometry was followed.
- the FR compound was placed in the sheath side (extruder A, with a pump capacity of 0.6 cc/rot) and its final percentage in the fibers was controlled by the direct mixture of pellets of the 30% FR compound and virgin PA6 (with relative viscosity of 2.7).
- a virgin PA6 with relative viscosity of 2.4 was used in the core (extruder C, with a pump capacity of 2.9cc/rot) in order to improve process stability while ensuring similar melt flow rates of the different materials throughout the spinneret.
- the fibers thus produced were converted into knitted fabric in a laboratory scale circular loom from Sodemat.
- the fire tests on the fabrics were conducted in accordance to a method based on ISO 3795, which consists of placing a flame at 2cm of the sample (in the middle) during 2 second, remove the flame and wait until the fire extinguishes. The time till the fire extinguishes (no flame spread) from the start of the test was recorded for each specimen.
- the blank fabric without HMDOPO had a time of burning of 25 sec. Significant flame retardancy was observed for fabrics with HMDOPO concentration greater than 8 %. In this case the time till the fire extinguishes was less than 7 secs, clear ly demonstrating the flame-retardant efficacy of the HMDOPO containing fibers.
- LOI limiting oxygen index
- Co-polyamides suitable for the present invention can be obtained, for example, from Ems-Chemie AG, Domat/Ems, Switzerland. A selection of such co-polyamides and key properties is given in Table below. Table 9: Co-polyamides and selected properties thereof
- thermoplastic elastomer material for electric wire/cable and preparation method there of. CN 105623180A, 2016.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP18162392.7A EP3540000A1 (de) | 2018-03-16 | 2018-03-16 | Flammhemmendes polyamid 6-masterbatch und daraus hergestellte fasern |
| PCT/EP2019/056616 WO2019175421A1 (en) | 2018-03-16 | 2019-03-15 | Flame retardant master batch for polyamide 6 and fibers made thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP3765550A1 true EP3765550A1 (de) | 2021-01-20 |
Family
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Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP18162392.7A Withdrawn EP3540000A1 (de) | 2018-03-16 | 2018-03-16 | Flammhemmendes polyamid 6-masterbatch und daraus hergestellte fasern |
| EP19716785.1A Pending EP3765550A1 (de) | 2018-03-16 | 2019-03-15 | Flammhemmender masterbatch für polyamid 6 und daraus hergestellte fasern |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP18162392.7A Withdrawn EP3540000A1 (de) | 2018-03-16 | 2018-03-16 | Flammhemmendes polyamid 6-masterbatch und daraus hergestellte fasern |
Country Status (2)
| Country | Link |
|---|---|
| EP (2) | EP3540000A1 (de) |
| WO (1) | WO2019175421A1 (de) |
Families Citing this family (4)
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|---|---|---|---|---|
| KR102255957B1 (ko) * | 2019-09-09 | 2021-05-25 | 한밭대학교 산학협력단 | 신규한 디벤조옥사포스피닌 옥사이드 유도체 화합물 및 이를 포함하는 퇴행성 질환의 예방 또는 치료용 약제학적 조성물 |
| CN111171521A (zh) * | 2020-02-27 | 2020-05-19 | 贵州民族大学 | 一种环氧树脂与磷杂菲和聚磷腈双基协效的阻燃复合材料及其制备方法与应用 |
| CN111363219A (zh) * | 2020-02-29 | 2020-07-03 | 贵州民族大学 | 一种聚乙烯与磷杂菲和聚磷腈双基协效阻燃复合材料及其制备方法和应用 |
| CN111286173A (zh) * | 2020-02-29 | 2020-06-16 | 贵州民族大学 | 一种磷杂菲和聚磷腈双基协效阻燃pla复合材料及其制备方法和应用 |
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-
2018
- 2018-03-16 EP EP18162392.7A patent/EP3540000A1/de not_active Withdrawn
-
2019
- 2019-03-15 WO PCT/EP2019/056616 patent/WO2019175421A1/en unknown
- 2019-03-15 EP EP19716785.1A patent/EP3765550A1/de active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP3540000A1 (de) | 2019-09-18 |
| WO2019175421A1 (en) | 2019-09-19 |
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