TR201821369A2 - HALOGEN-FREE POLYAMIDE-BASED COMPOSITE MATERIAL - Google Patents
HALOGEN-FREE POLYAMIDE-BASED COMPOSITE MATERIAL Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 67
- 229920002647 polyamide Polymers 0.000 title claims abstract description 42
- 239000003063 flame retardant Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 25
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 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 abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910021539 ulexite Inorganic materials 0.000 claims abstract description 9
- 229910021540 colemanite Inorganic materials 0.000 claims abstract description 7
- 239000004952 Polyamide Substances 0.000 claims description 22
- 239000000779 smoke Substances 0.000 claims description 17
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229920002292 Nylon 6 Polymers 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- 239000003517 fume Substances 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000007493 shaping process Methods 0.000 claims 1
- 239000000654 additive Substances 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 4
- 150000001638 boron Chemical class 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- HQURVGSRQBOZEX-UHFFFAOYSA-N 3,5-diamino-2-hydroxybenzoic acid Chemical compound NC1=CC(N)=C(O)C(C(O)=O)=C1 HQURVGSRQBOZEX-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000004614 Process Aid Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000017168 chlorine Nutrition 0.000 description 1
- 125000001309 chloro group Chemical class Cl* 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- KTLIMPGQZDZPSB-UHFFFAOYSA-N diethylphosphinic acid Chemical compound CCP(O)(=O)CC KTLIMPGQZDZPSB-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 108010038270 melain Proteins 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000015927 pasta Nutrition 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
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- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
Abstract
Mevcut buluş, halojen içermeyen ve alev geciktiricili poliamid bazlı kompozit malzeme, belirli bir oranda fosfor içeren organik fosfinat ile birlikte ağırlıkça %1-15 oranında kolemanit, çinko borat, boraks dekahidrat ve uleksit arasından seçilen bir veya daha bazla bor türevi malzeme ihtiva etmektedir.The present invention includes a halogen-free and flame retardant polyamide-based composite material, organic phosphinate containing a certain proportion of phosphorus, as well as 1-15% by weight of colemanite, zinc borate, borax decahydrate and ulexite with one or more bases and boron-derived materials.
Description
TARIFNAME HALOJEN IÇERMEYEN POLIAMID BAZLI KOMPOZIT MALZEME Teknik Alan Bulus, halojen içermeyen poliamid bazli bir kompozit malzeme ile ilgilidir. DESCRIPTION HALOGEN-FREE POLYAMIDE BASED COMPOSITE MATERIAL Technical Area The invention relates to a halogen-free polyamide-based composite material.
Bulus özellikle, demiryolu tasit içi ve disi uygulamalarinda kullanim için halojen içermeyen ve alev geciktiricili poliamid bazli bir kompozit malzeme ile ilgilidir. In particular, the invention is halogen-free for use in railway vehicle interior and exterior applications. and a flame retardant polyamide-based composite material.
Teknigin Bilinen Durumu Günümüzde, sentetik polimerler arasinda termoplastiklerin kullanim orani %65 seviyesine ulasmistir. Polimerler çogunlukla bina ve konstrüksiyon, ulastirma, elektrik ve elektronik, mobilya ve ev esyasi, paketleme sektörlerinde kullanilmaktadir. Ozellikle poliamid (PA) bazli malzemelerin son yillarda ulasim sektöründe fren hortumlari, priz kutulari, batarya kutulari, yag kartelleri, dügme ve tutacaklar gibi parçalarda kullanimi artmaktadir. State of the Art Today, the rate of use of thermoplastics among synthetic polymers reaches 65%. has reached. Polymers are mostly used in building and construction, transportation, electrical and electronics, It is used in furniture and household goods, packaging sectors. Especially polyamide (PA) based materials in the transportation sector in recent years, brake hoses, socket boxes, batteries Its use in parts such as boxes, oil cartridges, knobs and handles is increasing.
Ancak, poliamid kolaylikla yanabilen bir malzemedir. Poliamid yüksek sicakliklarda pirolize olur ve poliamid pirolize sicakligi kritik olarak oksijen konsantrasyonuna baglidir. Poliamid malzemeden imal ürünlerin alev geciktirici özellik tasimasi önem arz etmektedir. Bu nedenle poliamid malzemelerin kolay bir sekilde yanmasini önlemek için alev geciktirici katkilarin eklenmesi gereklidir. However, polyamide is an easily combustible material. Polyamide is pyrolyzed at high temperatures and the polyamide pyrolysis temperature is critically dependent on the oxygen concentration. Polyamide It is important that the products made of materials have flame retardant properties. This Therefore, it is flame retardant to prevent polyamide materials from burning easily. additives must be added.
Alüminyum hidroksit, magnezyum hidroksit, bromlular, orgona fosforlar, antinomioksit, klorlular alev geciktirici malzemelerdir. Asyada en çok bromlular kullanilmakta iken, Avrupa ve Amerika'da halojen içermeyen katkilar kullanilmaktadir. Halojenli bilesikler insanlar, hayvanlar ve çevre için çok tehlikelidir. Halojenli alev geciktiriciler kullanildiginda yangin durumunda tehlikeli ürünler örnegin, dioksin gazi çikarirlar ve bu gaz toksik bir gazdir. Birçok ülkede yasal düzenlemeler yapilarak bu ürünlerin kullanimina sinirlar getirilmektedir. Bu nedenle halojensiz alev geciktiricilere olan talep gün geçtikçe artmaktadir. Aluminum hydroxide, magnesium hydroxide, brominates, orgona phosphors, antinomioxide, Chlorines are flame retardant materials. While brominated is used most in Asia, Halogen-free additives are used in Europe and America. Halogenated compounds It is very dangerous for people, animals and the environment. When using halogenated flame retardants In case of fire they emit dangerous products eg dioxin gas which is a toxic gas. is gas. In many countries, legal regulations have been made to limit the use of these products. is brought. Therefore, the demand for halogen-free flame retardants is increasing day by day. increasing.
Poliamid 6 (PAB), otomotiv, demiryolu, tekstil, insaat ve elektrik- elekronik sektörleri gibi birçok alanda uygulamasi olan termoplastiklerden biridir. PA6 nispeten yüksek mekanik dayanim, kolay islenebilirlik, yüksek termal dayanim, iyi kimyasal direnç, iyi asinma ve düsük sürtünme katsayisi gibi özelliklere sahiptir, Bununla birlikte, PAG'Iarin yüksek nem emiciligi, düsük boyutsal kararlilik, düsük sicaklik darbe mukavemeti ve kolay alevlenebilirlik gibi bazi dezavantajlari vardir. Dolayisiyla, saf PAG'nin özelliklerini iyilestirici bazi katkilar kullanilarak bu dezavantajlari ortadan kaldirmak mümkündür. Polyamide 6 (PAB), such as automotive, railway, textile, construction and electric-electronic sectors It is one of the thermoplastics that has applications in many areas. PA6 relatively high mechanical strength, easy workability, high thermal resistance, good chemical resistance, good abrasion and It has features such as low coefficient of friction, However, PAGs have high humidity absorbency, low dimensional stability, low temperature impact strength and easy It has some disadvantages such as flammability. Therefore, the properties of pure PAG It is possible to eliminate these disadvantages by using some healing additives.
Ozellikle, PAB çabuk alevlenebilen ve kisitlayici oksijen indeksi (LOI) düsük olan termoplastik malzemelerden birisidir. In particular, PAB is flammable and has a low restrictive oxygen index (LOI). It is one of the thermoplastic materials.
Demiryolu araçlarinin yangindan korunmasi için çesitli standartlar bulunmaktadir. Ornegin EN 45545-2 standardina göre farkli HL1, HL2 ve HL3 tehlike düzeyinde demiryolu tasit içi/disi uygulamalarinda kullanilabilecek halojen içermeyen alev geciktirici özellige sahip malzemelerin standartlari tanimlanmistir. HL3 tehlike düzeyinde kullanilabilecek malzemenin UL94 yanma standardina göre V-O, EN ISO 4589-2: LOI standardina göre kisitlayici oksijen indeksinin (LOI) 32%'den büyük olmasi, EN ISO 5659-3 standardina göre duman yogunlugunun 150'den küçük olmasi ve NF X70-100-1 standardina göre duman toksisitesinin 0,75'den küçük olmasi gerekmektedir. There are various standards for fire protection of railway vehicles. For example Railway vehicles with different HL1, HL2 and HL3 hazard levels according to EN 45545-2 standard It has a halogen-free flame retardant feature that can be used in indoor/outdoor applications. standards of materials are defined. Can be used at HL3 hazard level material according to UL94 combustion standard V-O, EN ISO 4589-2: according to LOI standard A restrictive oxygen index (LOI) greater than 32% conforms to EN ISO 5659-3. According to the NF X70-100-1 standard, the smoke density should be less than 150 smoke toxicity should be less than 0.75.
Teknigin bilinen durumunda alev geciktirici olarak kullanilan fosfor bazli malzemeler açiklanmaktadir. bazli bir kompozit malzeme açiklanmaktadir. Bahsedilen dokümanda alev geciktirici olarak bir ya da daha fazla fosfinat ve polimer yapilarinin kombinasyonlari açiklanmaktadir. bazli alev geciktirici katki içeren bir kompozisyon açiklanmaktadir. Phosphorus-based materials used as flame retardants in the state of the art is explained. based composite material is described. Flame retardant in the mentioned document combinations of one or more phosphinate and polymer structures is explained. Disclosed is a composition containing a flame retardant additive.
Bahsedilen kompozit malzemeler, özellikle demiryolu tasitlarinda kullanim için gereken yüksek standartlari saglamakta yetersiz kalmaktadir. Said composite materials are especially needed for use in railway vehicles. falls short of meeting high standards.
Sonuç olarak yukarida anlatilan olumsuzluklardan dolayi ve mevcut çözümlerin konu hakkindaki yetersizligi nedeniyle ilgili teknik alanda bir gelistirme yapilmasi gerekli kilinmistir. As a result, due to the above-mentioned negativities and existing solutions It is necessary to make an improvement in the relevant technical field due to the inadequacy of the is locked.
Bulusun Kisa Açiklamasi Mevcut bulus, yukarida bahsedilen gereksinimleri karsilayan, tüm dezavantajlari ortadan kaldiran ve ilave bazi avantajlar getiren halojen içermeyen ve alev geciktiricili poliamid bazli bir kompozit malzeme ile ilgilidir. Brief Description of the Invention The present invention satisfies the above-mentioned requirements, eliminates all disadvantages. halogen-free and flame-retardant polyamide based on a composite material.
Bulusun öncelikli amaci, demiryolu tasit içi/disi uygulamalarinda kullanilabilecek, halojen içermeyen ve alev geciktiricili özellige sahip poliamid bazli bir kompozit malzeme temin etmektir. The primary aim of the invention is to use halogen, which can be used in rail vehicle interior/exterior applications. providing a polyamide-based composite material that does not contain flame retardants is to do.
Bulusun bir amaci yüksek mekanik dayanim, kolay islenebilirlik, yüksek termal dayanim, iyi kimyasal direnç, iyi asinma ve düsük sürtünme katsayisi özelliklerine sahip, halojen içermeyen ve alev geciktiricili özellige sahip poliamid bazli bir kompozit malzeme temin etmektir. An object of the invention is high mechanical strength, easy workability, high thermal resistance, halogen with good chemical resistance, good wear and low coefficient of friction providing a polyamide-based composite material that does not contain flame retardants is to do.
Bulusun bir amaci, demiryolu tasit içi/disi uygulamalarinda EN 45545-2 standardina göre HL3 tehlike düzeyinde kullanabilecek poliamid bazli bir kompozit malzeme temin etmektir. One object of the invention is to use in/out of rail vehicle applications according to EN 45545-2 standard. To provide a polyamide-based composite material that can be used at the HL3 hazard level.
Bulusun bir diger amaci, UL94 yanma standardina göre V-O sinifina giren poliamid bazli bir kompozit malzeme temin etmektir. Another object of the invention is to produce polyamide based polyamides, which are in the V-O class according to the UL94 combustion standard. to provide a composite material.
Bulusun bir diger amaci, EN ISO 4589-2 standardina göre kisitlayici oksijen indeksi 32%'den büyük olan poliamid bazli bir kompozit malzeme temin etmektir. Another object of the invention is the restrictive oxygen index according to the EN ISO 4589-2 standard. is to provide a polyamide-based composite material greater than 32%.
Bulusun bir baska amaci, EN ISO 5659-3 standardina göre duman yogunlu 150'den küçük olan poliamid bazli bir kompozit malzeme temin etmektir. It is another object of the invention to make more than 150 smoke-dense products according to the EN ISO 5659-3 standard. small is to provide a polyamide-based composite material.
Bulusun bir baska amaci, NF X70-100-1 standardina göre duman toksisitesi 0.75'den küçük olan poliamid bazli bir kompozit malzeme temin etmektir. Another object of the invention is that the smoke toxicity is less than 0.75 according to the NF X70-100-1 standard. small is to provide a polyamide-based composite material.
Bulus, ayrica demiryolu tasit içi/disi uygulamalarinda kullanilabilecek, halojen içermeyen ve alev geciktiricili özellige poliamid bazli bir kompozit malzeme hazirlamak için bir yöntem temin etmeyi amaçlamaktadir. The invention is also halogen-free, which can be used in rail vehicle interior/exterior applications. and a flame retardant property to prepare a polyamide-based composite material. method aims to provide
Yukarida anlatilan amaçlarin yerine getirilmesi için, halojen içermeyen ve alev geciktiricili poliamid bazli kompozit malzeme, belirli bir oranda fosfor içeren organik fosfinat ile birlikte agirlikça %1-15 oraninda kolemanit, çinko borat, boraks dekahidrat ve uleksit arasindan seçilen bir veya daha bazla bor türevi malzeme ihtiva etmektedir. To fulfill the above-described purposes, halogen-free and flame-retardant polyamide-based composite material, together with organic phosphinate containing a certain amount of phosphorus 1-15% by weight of colemanite, zinc borate, borax decahydrate and ulexite. containing one or more selected bases of boron-derived material.
Bulus ayrica yukarida bahsedilen gereksinimleri karsilayan, tüm dezavantajlari ortadan kaldiran ve ilave bazi avantajlar getiren, demiryolu tasitinin içinde veya disinda, halojen içermeyen ve alev geciktiricili bir parça ile ilgilidir. The invention also eliminates all disadvantages, meeting the above-mentioned requirements. halogen, inside or outside of the railway vehicle, which lifts and brings some additional advantages It relates to a part that does not contain a flame retardant.
Yukarida anlatilan amaçlarin yerine getirilmesi için, bahsedilen parça halojen içermeyen ve alev geciktiricili poliamid bazli bir kompozit malzeme içermektedir. Bahsedilen kompozit malzeme belirli bir oranda fosfor içeren organik fosfinat ile birlikte agirlikça %1-15 oraninda kolemanit, çinko borat, boraks dekahidrat ve uleksit arasindan seçilen bir veya daha bazla bor türevi malzeme içermektedir. To fulfill the above-described purposes, said part is halogen-free. and a flame retardant polyamide-based composite material. The said composite material with a certain proportion of phosphorus-containing organic phosphinate 1-15% by weight one or more of a mixture of colemanite, zinc borate, borax decahydrate and ulexite. contains more boron-derived material.
Bulus ayrica yukarida bahsedilen gereksinimleri karsilayan, tüm dezavantajlari ortadan kaldiran ve ilave bazi avantajlar getiren, halojen içermeyen ve alev geciktiricili poliamid bazli bir kompozit malzemenin hazirlanmasi için bir yöntem ile ilgilidir. The invention also eliminates all disadvantages, meeting the above-mentioned requirements. halogen-free and flame-retardant polyamide relates to a method for preparing a composite material based on
Yukarida anlatilan amaçlarin yerine getirilmesi için, bahsedilen yöntem eriyik haldeki poliamide diger bilesenlerin karistirilmasi ve kompozit malzemenin belirli bir sicaklikta ekstr'üde edilerek grani'il hale getirilmesi adimlarini içermektedir. In order to fulfill the above-described purposes, said method is mixing the other components of the polyamide and mixing the composite material at a certain temperature. It includes the steps of extrusion and granulation.
Bulusun yapisal ve karakteristik özellikleri ve tüm avantajlari asagida verilen detayli açiklama sayesinde daha net olarak anlasilacaktir ve bu nedenle degerlendirmenin de bu detayli açiklama göz önüne alinarak yapilmasi gerekmektedir. The structural and characteristic features of the invention and all its advantages are detailed below. will be more clearly understood by the explanation and therefore this should be made taking into account the detailed explanation.
Bulusun Detayli Açiklamasi Bu detayli açiklamada bulus konusu kompozit malzeme sadece konunun daha iyi anlasilmasina yönelik olarak ve hiçbir sinirlayici etki olusturmayacak sekilde açiklanmaktadir. Detailed Description of the Invention In this detailed description, the composite material of the invention is only better than the subject. for understanding and without any limiting effect is explained.
Bulus, halojen içermeyen ve alev geciktirici özellige sahip poliamid bazli bir kompozit malzemeyi açiklamaktadir. The invention is a halogen-free and flame retardant polyamide-based composite. explains the material.
Demiryolu tasitlarinda yangindan korunma gereklilikleri iç yüzeyler pencere çerçeveleri, yolcu koltugu kaplamalari, iç ve dis kablo tasima kanallari, iç ve dis giydirmeler gibi demiryolu tasit içi ve tasit disi parçalarda kullanilan malzemelerin özelliklerine kisitlama getirmektedir. Bulus, malzeme bahsedilen demiryolu tasitlarinda kullanim için gereken özellikleri saglayan poliamid bazli bir kompozit malzemeyi açiklamaktadir. Fire protection requirements in railway vehicles interior surfaces window frames, such as passenger seat covers, inner and outer cable trays, inner and outer claddings. Limiting the properties of materials used in railway vehicle interior and exterior parts brings. The invention is the material required for use in the mentioned railway vehicles. describes a polyamide-based composite material that provides
Bulus konusu kompozit malzeme ana bilesen olarak poliamid içermektedir. Poliamid termoplastik özellikli bir malzemedir. Poliamidin kisitlayici oksijen indeksi (LOI) düsük oldugu için kolaylikla yanabilen bir malzemedir. Söz konusu kompozit malzeme, tercihen poliamid 6 ve/veya poliamid 6.6 içermektedir. Poliamid 6 vei'veya poliamid 6.6'nin tercih edilmesinin sebebi poliamid 6 ve poliamid 6.6'nin nispeten yüksek mekanik dayanim, kolay islenebilirlik, yüksek termal dayanim, iyi kimyasal direnç, iyi asinma ve düsük sürtünme katsayisi gibi özelliklere sahip olmasidir. The composite material of the invention contains polyamide as a main component. Polyamide It is a thermoplastic material. The restrictive oxygen index (LOI) of polyamide is low It is an easily combustible material. The composite material in question is preferably polyamide 6 and/or polyamide 6.6. Polyamide 6 and polyamide 6.6 are preferred. The reason why polyamide 6 and polyamide 6.6 are relatively high mechanical strength, easy workability, high thermal resistance, good chemical resistance, good corrosion and low It has properties such as coefficient of friction.
Bulus konusu kompozit malzeme alev geciktirici katki içermektedir. Bulusta alev geciktirici olarak organik fosfinat kullanilmaktadir. Tercih edilen organik fosfinatlar arasinda dietil fosfinik asit, alüminyum dietil-fosfinat ve çinko fosfinat bulunmaktadir. Organik fosfinatlar ile birlikte melain polifosfat ve türevleri birlikte kullanilabilir. &'3er sicakliga karsi dirençli bir tabaka olusturularak koruma saglanmaktadir. Kullanilan organik fosfinat degisen oranlarda fosfor içerebilir. Böylece ihtiyaç duyulan aktif fosfor katkinin miktarina göre uygun bir organik fosfinat seçilmektedir. Örnegin, kompozit malzeme agirlikça %15-25 oraninda fosfor içeren organik fosfinat içerebilir. Kompozit malzeme tercihen, agirlikça organik fosfinat ve agirlikça %23-24 oraninda fosfor içeren organik fosfinat arasindan seçilen bir ya da daha fazla organik fosfinat içermektedir. Fosfor orani performansi etkiledigi için karisimin tüm içerigini dikkate alarak belirlenmesi gerekmektedir. The composite material which is the subject of the invention contains a flame retardant additive. Flame retardant in the invention organic phosphinate is used. Among the preferred organic phosphinates, diethyl phosphinic acid, aluminum diethyl-phosphinate and zinc phosphinate. Organic phosphinates together with melain polyphosphate and its derivatives can be used together. &'3 temperature resistant Protection is provided by forming a layer. The organic phosphinate used may contain phosphorus. Thus, depending on the amount of active phosphorus additive needed. a suitable organic phosphinate is selected. For example, 15-25% by weight of composite material It may contain organic phosphinate containing phosphorus in the ratio. Composite material preferably by weight organic phosphinate and organic phosphinate containing 23-24% phosphorus by weight. contains one or more selected organic phosphinates. Phosphorus ratio performance It must be determined by taking into account all the contents of the mixture.
Söz konusu kompozit malzeme, hem pahali oldugu için hem de mekanik ve fiziksel gibi bazi özellikleri bozabildigi için mümkün oldugunca düsük oranda organik fosfinat içermektedir. Ayrica, ektrüzyon ve enjeksiyon gibi proses edilme zorluklari da ortaya çikabilmektedir. Yani yüksek LOI degerleri elde edebilmek için daha yüksek fosfor oranlari kullanildiginda mekanik 'Özellkleri çok bozulmus ve proses edilme zorlugu olan bir ürünün ortaya çikmasi uygulanabilirligi düsürebilmektedir. Bu nedenlerle, kullanilan organik fosfinat miktari istenilen performansi gösterecek ve fosfor orani en uygun olan organik fosfinata göre belirlenmektedir. The composite material in question is both expensive and mechanically and physically demanding. organic phosphinate as low as possible, as it may impair some properties contains. Processing difficulties such as extrusion and injection also arise. can come out. In other words, higher phosphorus ratios to obtain higher LOI values. When used, the mechanical properties of a product that is very deteriorated and difficult to process. emergence may reduce the applicability. For these reasons, the organic The amount of phosphinate will show the desired performance and the organic matter with the most suitable phosphorus ratio. determined by phosphinate.
Kompozit malzeme tercihen, agirlikça %19-20 oraninda fosfor içeren organik fosfinat, agirlikça %21-22 oraninda fosfor içeren organik fosfinat ve agirlikça %23-24 oraninda fosfor içeren organik fosfinat arasindan seçilen bir ya da daha fazla organik fosfinat içermektedir, kullanilan organik fosfinatin tercihen toplam agirlikça orani %10-20'dir . Çogunlukla tekstil, cam elyafi, tarim ve deterjan Üretiminde kullanilan bor ürünleri ayrica, çati kaplama malzemeleri, selülozik izolasyon malzemeleri, çimento katki maddesi olarak da kullanilmaktadir. Bulus konusu kompozit malzeme alev geciktirici katki olarak bor türevi velveya koleminat (Ca286011.5H20) içermektedir. Bor türevi malzeme çinko borat velveya koleminat yerine veya koleminat vei'veya çinko borat ile birlikte boraks dekahidrat, üleksit gibi baska bir veya daha fazla bor türevi malzeme de içerebilir. Mevcut bulus ile mineral bakimindan oldukça zengin bor çesitlerinden olan koleminat veya çinko borat veya boraks dekahidrat veya üleksit veya bir baska bor türevi malzemenin organik fosfinat ile kombinasyon halinde kullanilmasiyla bulus konusu kompozit malzemenin alev geciktiricilik özelliklerinin ve kisitlayici oksijen indeksinin sinerjik bir biçimde daha da arttigi bulunmustur. Söz konusu kompozit malzeme, tercihen toplam agirlikça %0,1-15 oraninda kolemanit ve agirlikça %0,1-15 çinko borat, uleksit, boraks dekahidrattan birini veya Bulus konusu kompozit malzeme ayrica duman baskilayici dolgulardan bir ya da daha fazlasini içerebilir. Tercih edilen duman baskilayicilar siloksan bazli duman baskilayicilardir. Tercih edilen siloksan bazli duman baskilayicilar arasinda dumani hapsedip disari salinimini azaltma performansi bakimindan polipropilen (PP) tasiyicili yüksek molekül agirlikli siloksan bulunmaktadir. Söz konusu kompozit malzeme, toplam agirlikça %1-5 oraninda siloksan bazli duman baskilayici içermektedir. Tercihen siloksan bazli duman baskilayicinin orani toplam agirlikça %1-3, daha fazla tercihen toplam agirlikça %1, 3 veya 5'tir. Siloksan bazli duman baskilayicinin orani belirtilen oranlardan fazla oldugun kompozit malzemenin yanma ve diger özellikleri bozulabilmektedir. The composite material is preferably organic phosphinate containing 19-20% by weight phosphorus, Organic phosphinate containing 21-22% by weight phosphorus and 23-24% by weight one or more organic phosphinates selected from phosphorus-containing organic phosphinates The organic phosphinate used is preferably 10-20% by weight. Boron products, which are mostly used in textile, glass fiber, agriculture and detergent production, as roofing materials, cellulosic insulation materials, cement additives is also used. Boron derivative as flame retardant additive in composite material which is the subject of the invention velor coleminate (Ca286011.5H20). Boron derivative material zinc borate borax decahydrate instead of velor or coleminate or in combination with coleminate vei or zinc borate, It may also contain one or more other boron-derived materials such as ulexite. With the present invention Coleminate or zinc borate, which is one of the boron varieties rich in minerals or organic phosphinate of borax decahydrate or ulexite or another boron-derived material Invented composite material is used in combination with flame retardant. The retardation properties and the restrictive oxygen index were further increased synergistically. has been found. The said composite material is preferably 0.1-15% by total weight. colemanite and 0.1-15% by weight zinc borate, ulexite, borax decahydrate, or The composite material of the invention may also contain one or more of the smoke suppressant fillers. may contain more. Preferred smoke suppressants are siloxane-based fume are suppressors. Among the preferred siloxane-based smoke suppressants with polypropylene (PP) carrier for its performance to trap and reduce its release high molecular weight siloxane. The composite material in question is a total It contains 1-5% by weight of siloxane-based smoke suppressant. Preferably siloxane based smoke suppressor ratio 1-3% by total weight, more preferably total 1, 3 or 5% by weight. The ratio of the siloxane-based fume suppressant is higher than the specified ratios. Combustion and other properties of the composite material that you have in excess may deteriorate.
Bulus konusu kompozit malzeme baska alev geciktirici katkilar ve duman baskilayici katkilar içerebilir. Bahsedilen kompozit malzeme tercihen magnezyum hidroksit ve/veya b'ohmit içermektedir. Düsük oranda kullanilan magnezyum hidroksit duman baskilayici islevi gbrmektedir. Bulus konusu kompozit malzemede magnezyum hidroksit tercihen duman baskilayici olarak kullanilmaktadir. The composite material of the invention contains other flame retardant additives and smoke suppressant. may contain additives. Said composite material is preferably magnesium hydroxide and/or Contains b'ohmide. Low use magnesium hydroxide fume suppressant performs its function. In the composite material of the invention, magnesium hydroxide is preferably It is used as a smoke suppressant.
Bulus konusu kompozit malzemede kullanilan bilesenlerin sinerjik etki yaratarak poliamid malzemenin alev geciktiricilik degerini yükselttigi, kisitlayici oksijen indeksi (LOI) degerini arttirdigi, duman yogunlugunu ve duman toksisitesini düsürdügü bulunmustur. Organik fosfinat ile beraber kolemanit, çinko borat, üleksit. boraks dekahidrat gibi bor türevi malzemelerden bir ya da daha fazlasi ve duman baskilayici kullanilmasi sayesinde HL3 tehlike düzeyinde kullanilabilecek, yani UL94 yanma standardina göre V-O, EN ISO 4589- 2: LOI standardina göre kisitlayici oksijen indeksinin %32'den büyük oldugu, EN ISO standardina göre duman toksisitesinin 0,75'den küçük oldugu poliamid bazli bir kompozit malzeme elde edilmektedir. Ayrica elde edilen kompozit malzemenin mekanik özelliklerinin, ham polimerin mekanik özelliklerine göre kötülesmedigi bulunmustur. By creating a synergistic effect of the components used in the composite material of the invention, polyamide the restrictive oxygen index (LOI) value, which increases the flame retardancy value of the material. It was found that it increased the smoke density and decreased the smoke toxicity. Organic colemanite, zinc borate, ulexite with phosphinate. boron derivative such as borax decahydrate HL3 thanks to the use of one or more of the materials and a smoke suppressor that can be used at the level of danger, ie V-O according to UL94 combustion standard, EN ISO 4589- 2: According to the LOI standard, the restrictive oxygen index is greater than 32%, EN ISO A polyamide-based composite with a smoke toxicity of less than 0.75 according to the standard material is obtained. In addition, the mechanical properties of the obtained composite material It was found that the properties of the raw polymer did not deteriorate compared to the mechanical properties of the raw polymer.
Bulus konusu kompozit malzeme ayrica takviye olarak cam fiberi/elyafi içerebilir. Takviye olarak cam fiber bulus konusu kompozit malzemenin çekme ve egilme dayanimi gibi mekanik özelliklerinin iyilesmesini ve malzemenin yumusama sicakliginin yükselmesini saglamaktadir. Bahsedilen kompozit malzemeye takviye olarak cam fiber eklenmesi kompozit malzemenin yanmazlik özelliklerini etkilemektedir. Bu nedenle eklenen cam fiberin miktarini diger bilesenlerin oranlarina göre optimize etmek gerekmektedir. The composite material of the invention may further comprise glass fiber/fiber as reinforcement. Reinforcement such as the tensile and bending strength of the composite material, which is the subject of the invention of glass fiber. improve the mechanical properties and increase the softening temperature of the material. it provides. Adding glass fiber as reinforcement to the said composite material affects the flammability properties of the composite material. Therefore, the added glass It is necessary to optimize the amount of fiber according to the ratios of other components.
Kompozit malzeme toplam agirlikça %10-40 oraninda cam fiberi içermektedir. Composite material contains 10-40% glass fiber by total weight.
Bulus konusu kompozit malzeme üretilirken çift vidali ekstruder kullanilmaktadir. Twin screw extruder is used while producing the composite material which is the subject of the invention.
Bahsedilen ekstruderda dört adet gravimetrik besleyici bulunmaktadir. Uretim asamasinda bir no'lu besleyiciden poliamid verilmektedir. Iki no'lu besleyiciden ise gerektigi durumda proses yardimcilari örnegin, iç ve dis kaydirici verilmektedir. Uç no'lu besleyiciden ise organik fosfinat, kolemanit, çinko borat, üleksit, boraks dekahidrat gibi bor türevi malzemeler, magnezyum hidroksit ve siloksan bazli duman baskilayici eklenmektedir. There are four gravimetric feeders in the said extruder. During production polyamide is given from feeder no. If necessary from the feeder number two Process aids, for example, internal and external slider are provided. If from the feeder no. boron derivative such as organic phosphinate, colemanite, zinc borate, ulexite, borax decahydrate materials, magnesium hydroxide and siloxane-based smoke suppressant are added.
Bahsedilen katkilarin polimer içerisine homojen bir sekilde dagitilabilmesi için besleme noktalari degistirilebilmektedir. Drnegin, bahsedilen katkilar iki no'lu vei'veya dört no'lu besleyiciden de verilebilmektedir. In order to distribute the said additives homogeneously into the polymer, the feeding points can be changed. Drnegin, the contributions mentioned are no. two vei' or four. It can also be given from the feeder.
Dört no'lu besleyiciden ise takviyeli kompozit üretimi sirasinda cam fiber beslenmektedir. Glass fiber is fed from the feeder number four during the production of reinforced composite.
Katki ve takviyeler ekstruder prosesinde homojen karismayabilmektedir. Buna göre ekstruderin vida tasariminda yenilik yapilarak bu problem çözülebilmektedir. Ayrica, homojen dagilimin saglanmasi amaciyla poliamid için vaks miktari, örnegin %1 oranina yükseltilebilmektedir. Ayrica, elde edilen kompozit malzeme enjeksiyon kaliplama yöntemine uygun olmadigi durumda poliamid viskozitesini düsürmek için ortama zincir kiricilar eklenebilmektedir. Ektruderden çikan örnegin, 3 mm çapindaki makarnalar strand tipi pellet makinasinda kesilerek granül hale getirilmektedir. Additives and supplements may not mix homogeneously in the extruder process. According to this This problem can be solved by innovating the screw design of the extruder. Moreover, In order to ensure homogeneous distribution, the amount of wax for polyamide, for example 1% can be upgraded. In addition, the resulting composite material injection molding In case it is not suitable for the method of breakers can be added. For example, 3 mm diameter pasta coming out of the extruder is stranded. It is cut into granules in a type pellet machine.
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| PCT/TR2019/050879 WO2020142029A1 (en) | 2018-12-31 | 2019-10-18 | Polyamide-based halogen free composite material |
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