CN103665780B - Based on the fire-retardant combination of Poly(Trimethylene Terephthalate) - Google Patents
Based on the fire-retardant combination of Poly(Trimethylene Terephthalate) Download PDFInfo
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Abstract
The present invention relates to a kind of fire-retardant combination based on Poly(Trimethylene Terephthalate) (PTT), also relate to the fibre product obtained by described fire-retardant combination.Described fire-retardant combination comprises: the Poly(Trimethylene Terephthalate) of (a) 74 % by weight-99.4 % by weight; The poly-aryl phosphine acid esters of (b) 0.5 % by weight-10 % by weight; The alumina nanoparticles of (c) 0.1 % by weight-6 % by weight and/or kaolin nanoparticle; (d) additive of the optional existence of 0-10 % by weight.
Description
Technical field
The present invention relates to the fire-retardant combination based on Poly(Trimethylene Terephthalate) (PTT), particularly containing the fire-retardant combination based on PTT gathering aryl phosphine acid esters fire retardant and inorganic nano-particle.The invention still further relates to the goods comprising above-mentioned fire-retardant combination or obtained by above-mentioned fire-retardant combination, especially fibre product.
Background technology
Poly(Trimethylene Terephthalate) is (usually referred to as " PTT ", " PPT " or " 3GT ") generally by 1, ammediol and terephthalic acid or terephthalate polycondensation obtain, and are a kind of new polyesters after polyethylene terephthalate (being usually called for short " PET ") and polybutylene terephthalate (usually abbreviation " PBT ").PTT resin is more excellent than PET and PBT in mechanical characteristics, weathering resistance, heat-resistant aging and resistance to hydrolysis.
Ptt fiber combines the pollution resistance of the flexibility of nylon, the fluffiness of acrylic fibers and terylene, there is better colour fastness than nylon simultaneously, avoid the shortcoming of acrylic fibers balling-up easy to wear, have again reasonable feel, elasticity inherently very well and can normal temperature dyeing.
Due to the excellent properties of PTT, it can be widely used in the every field such as dress material, decoration and engineering plastics, particularly in carpet applications.But in some environments, PTT self flame retardance performance is inadequate, thus limits PTT application in these areas.
In order to improve the flame retardant resistance of PTT, attempt adding various flame-retardant additive.Such as, add the research of halogen-containing type fire retardant widely, but, halogen-containing type fire retardant manufacture, reclaim or discarded time all cause larger environmental pollution, and produce toxic and harmful when burning, therefore, its gradually substitute by non-halogen type fire retardant, non-halogen type fire retardant is the main development direction of present fire retardant.
As the mode of the flame retardant resistance of improvement PTT, mainly contain three kinds at present: one is post processing mode, use fire retardant dipping ptt fiber or fabric and obtained flame retardant resistance ptt fiber or fabric, the shortcoming of the method is that flame retardant resistance can not be lasting, and likely affects the outward appearance of fiber or fabric; Another kind be by fire retardant and PTT blended, obtain flame-retardant composition, then carry out follow-up molded or spinning with obtained fire-retardant fibre or fabric; Another is introduced in the macromolecular chain of PTT as copolymer composition by fire retardant, and copolymerization obtains flame retardant polyester, and the flame retardant resistance of the flame retardant polyester that the method obtains is lasting, but its shortcoming is other proper property changing PTT polyester.
Widely used in polyester especially trevira is phosphonium flame retardant, and it comprises response type phosphonium flame retardant and addition type phosphonium flame retardant.Response type phosphonium flame retardant due to be added into polyester molecular chain in therefore often change the thermal properties of polyester thus bring difficulty to spinning; And this often cannot produce on existing production platform, needs adjustment equipment or processing condition, thus adds production cost.
Patent application CN101532189A discloses a kind of flame retardant PTT polyester fiber and production method thereof, the method of copolymerization is wherein adopted to add in PTT polyester molecule chain by phosphonium flame retardant monomer (such as 2-propyloic alkyl phosphonic acid, 2-carboxyethyl phenyl phosphinic acid etc.), simultaneously, in copolymer reactant, add the inorganic nano-particle being selected from silicon-dioxide, calcium carbonate, magnesiumcarbonate and barium sulfate, obtain flame-retarding PTT polyester by copolymerization.This patent application relates to aforesaid reactive flame retardant.
Patent application CN101709137A discloses a kind of phosphorus-containing PTT/nano composite material and preparation method thereof, the method of copolymerization is wherein adopted to add in PTT polyester molecule chain by phosphonium flame retardant monomer (such as BHET, BHPPO, CEMPP etc.), simultaneously, in copolymer reactant, add the inorganic nano-particle being selected from barium sulfate, silicon-dioxide, titanium dioxide, zinc oxide etc., obtain flame-retarding PTT polyester by copolymerization.This patent application also relates to aforesaid reactive flame retardant.
Also composition fire retardant and PTT blended (i.e. aforementioned additive flame retardant) being obtained flame retardant properties and improve is had in prior art, such as, be disclose a kind of flame retardant polytrimethylene terephthalate in the application of CN101802075A in Chinese patent application publication No., wherein, by adding the melamine cyanurate as fire retardant in Poly(Trimethylene Terephthalate), then their melt blendings are obtained flame-retarding PTT composition.Be disclose a kind of flame retardant polytrimethylene terephthalate in the application of CN101802076A in Chinese patent application publication No., wherein, by adding the perfluorinated sulfonic acid as fire retardant in Poly(Trimethylene Terephthalate), then their melt blendings are obtained flame-retarding PTT composition.Only by adding fire retardant to improve the flame retardant resistance of PTT polyester in flame-retarding PTT composition disclosed in these two patent documentations, do not mention or relate to the use of inorganic nano-particle.
At present, still need to provide flame retardant properties to improve and the composition based on PTT of environmental protection.
Summary of the invention
The present inventor finds after deliberation, by by PTT and poly-aryl phosphine acid esters fire retardant and alumina nanoparticles and/or kaolin nanoparticle blended, flame retardant resistance can be obtained and improve and the fire-retardant combination based on PTT of satisfactory mechanical property.Particularly, contriver finds by adding a small amount of aluminum oxide and/or kaolin nanoparticle in the mixture of PTT and poly-aryl phosphine acid esters fire retardant, can improve the flame retardant effect of poly-aryl phosphine acid esters fire retardant synergistically.
Based on above-mentioned discovery, the present invention proposes a kind of fire-retardant combination, based on the gross weight of described fire-retardant combination, described fire-retardant combination comprises:
(a) about 74 % by weight Poly(Trimethylene Terephthalate) of-Yue 99.4 % by weight;
(b) about 0.5 % by weight poly-aryl phosphine acid esters of-Yue 10 % by weight;
(c) about 0.1 % by weight-Yue 6 % by weight alumina nanoparticles and/or kaolin nanoparticle; With
The additive of the optional existence of (d) 0-about 10 % by weight.
In an embodiment of the invention, in fire-retardant combination of the present invention, based on the gross weight of described fire-retardant combination, the content of described component (a) PTT is about 74 % by weight-Yue 99.4 % by weight, or is about 85 % by weight-Yue 95 % by weight.
In one embodiment, in fire-retardant combination of the present invention, based on the gross weight of described fire-retardant combination, the content of the poly-aryl phosphine acid esters of described component (b) is about 0.5 % by weight-Yue 10 % by weight, or is about 1 % by weight-Yue 6 % by weight.
In one embodiment, in fire-retardant combination of the present invention, based on the gross weight of described fire-retardant combination, the content of described composition (c) alumina nanoparticles and/or kaolin nanoparticle is about 0.1 % by weight to about 6 % by weight, or be about 0.2 % by weight to about 3 % by weight, or be about 0.5 % by weight to about 2 % by weight.
In one embodiment, in fire-retardant combination of the present invention, adopt the granularity of primary particle for about 100nm or less, or about 1nm to about 80nm, or be about 10nm to about 70nm, or the alumina nanoparticles being about 20nm extremely about 50nm.
In one embodiment, in fire-retardant combination of the present invention, adopt longitudinal thickness to be about 100nm or less, or about 1nm is to about 80nm, or be about 10nm to about 70nm, or is the kaolin nanoparticle of about 20nm extremely about 50nm.
In one embodiment, in fire-retardant combination of the present invention, its length-to-diameter ratio of the kaolin nanoparticle adopted is 1-1000, or is about 1-100, or is about 1-50, or is about 1-20, or is about 1-10.
In one embodiment, in fire-retardant combination of the present invention, based on the gross weight of described fire-retardant combination, the content of the additive that described composition (d) optionally exists is generally 0-about 10 % by weight, or be 0.01 % by weight to about 6 % by weight, or be 0.1 % by weight-2 % by weight.
In addition, the invention still further relates to the goods comprising above-mentioned fire-retardant combination or obtained by above-mentioned fire-retardant combination, especially fibre product, described fibre product can be long filament, fiber, yarn, fabric or carpet.
Embodiment
Unless otherwise indicated, all publication that the present invention mentions, patent application, patent and other reference are incorporated into herein all by reference in full, are equivalent to be presented in herein in full.
Unless otherwise defined, all technology used herein and scientific terminology have usual the understood same implication of one skilled in the art of the present invention.In case of conflict, comprise definition with this specification sheets to be as the criterion.
Unless otherwise indicated, all percentage ratio, number, ratio etc. are all by weight.
In time stating certain amount, concentration or other value or parameter with the form of scope, preferable range or preferred numerical upper limits and preferred numerical lower limits, be to be understood that and be equivalent to specifically disclose any scope by any pair range limit or preferred value being combined with any range lower limit or preferred value, and do not consider whether this scope specifically discloses.Unless otherwise noted, numerical range listed herein is intended to the end points comprising scope, and all integers within this scope and mark.
In this article, term " by ... formed " or " by ... form " be equal to " comprise/comprise ".Term used herein " comprises ", " comprising ", " having ", " having " " are contained " or their other variants any, is that intention comprises comprising of non-exclusionism.Such as, comprise the composition of a series of key element, process, method, product or equipment and might not be only limited to those key elements, but other key elements that clearly do not list or that these compositions, process, method, product or equipment are intrinsic can also be comprised.And, contrary unless expressly stated, otherwise "or" refers to and comprises "or" but not exclusive "or".Such as, any condition A or B:A that satisfy condition is true (or existence) and B is false (or not existing) below, A is false (or not existing) and B is true (or existence), and A and B is true (or existence).
In addition, not restricted for the quantity of word " one " to this key element or component before certain key element of the present invention or component.Therefore " one " is understood to include one or at least one, unless clear and definite quantity is odd number, otherwise the described key element of singulative or component also comprise the situation of plural number.
Unless otherwise indicated, material of the present invention, method and embodiment are only illustrative, and not restrictive.Although can adopt in enforcement of the present invention or test and be similar to or be equal to those methods as herein described and material, this specification sheets has hereafter described suitable method and material.
When using the end points of term " about " description value or scope, being appreciated that and comprising concrete value or involved end points.
Below fire-retardant combination of the present invention is described in detail.
component (a) PTT
Being applicable to PTT of the present invention can be PTT homopolymer, PTT multipolymer or PTT blend.Preferably PTT homopolymer.
Term " homopolymer " refers to the polymkeric substance only containing a kind of repeating unit.In the present invention, " PTT homopolymer " refers to the polymkeric substance obtained by the polycondensation of 1,3-PD and terephthalic acid or terephthalic acid equivalent.Wherein, " terephthalic acid equivalent " refers to and is showing substantially identical with terephthalic acid compound with in glycol reaction.For the object of the invention, terephthalic acid equivalent comprises the ester (such as dimethyl terephthalate (DMT)) of such as terephthalic acid and forms the derivative (such as carboxylic acid halides and acid anhydrides) of ester.Generally speaking, preferred terephthalic acid and terephthalate.
Term " multipolymer " refers to by the polymkeric substance of two or more monomer polymerizations, the polymkeric substance namely containing two or more repeating units.In the present invention, " PTT multipolymer " is preferably containing 80mol% or higher, or containing 90mol% or higher, or containing the propylene glycol ester terephthalate of 95mol% or higher, other parts are the polymkeric substance derived from the monomer (such as ethylene glycol, butyleneglycol etc.) except terephthalic acid and 1,3-PD.
Term " blend " refers to the mixture mixed by two or more components.In the present invention, " PTT blend " is by preparing PTT homopolymer or the mixing of PTT multipolymer; Preferably comprise the gross weight about 80 % by weight or higher based on PTT mixture, or containing 90 % by weight or higher, or contain PTT homopolymer or the PTT multipolymer of 95 % by weight or higher.
The preparation method being applicable to PTT homopolymer of the present invention, PTT multipolymer or PTT blend can adopt the known method of those skilled in the art, if U.S. Patent Application Publication No. is method described in the patent of US6281325 (B1).
Being applicable to PTT of the present invention also can be commercially available, and the commodity such as deriving from E.I.Du Pont Company are called
product, such as, being divided into according to its dulling agent content has greatly light, partly has the different sortses such as light, half delustring, full-dull; Each kind comprises again the PTT that several have different qualities viscosity (IV).
In fire-retardant combination of the present invention, based on the gross weight of described fire-retardant combination, the content of described component (a) PTT is about 74 % by weight-Yue 99.4 % by weight, or is about 85 % by weight-Yue 95 % by weight.
component (b) gathers aryl phosphine acid esters
The poly-aryl phosphine acid esters of the component (b) used in the present invention is the poly-aryl phosphine acid esters that following formula (1) represents:
Formula (1)
In formula, n is the integer within the scope of 10-35; And
Group listed below X is selected from;
In a preferred embodiment of the present invention, the poly-aryl phosphine acid esters of described component (b) is selected from: poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 3-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) oxygen base [1, 1 '-xenyl]-4, 4 '-two base], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene methylene radical-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene (1-methyl isophthalic acid, 1-ethylidene)-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene cyclohexylidene-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 5-naphthylidene], poly-[oxygen base (phenyl phosphinylidene) oxygen base-2, 6-naphthylidene], poly-[oxygen base (phenyl phosphinylidene) oxygen base-2, 7-naphthylidene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene-1, 2-diazenediyl-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene sulfenyl-1, 4-phenylene] and poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene alkylsulfonyl-1, 4-phenylene].
In another preferred embodiment of the present invention, the poly-aryl phosphine acid esters of described component (b) is selected from: poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 3-phenylene], poly-[oxygen base (phenyl phosphinylidene) oxygen base [1, 1 '-xenyl]-4, 4 '-two base], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene methylene radical-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene (1-methyl isophthalic acid, 1-ethylidene)-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) oxygen base-2, 6-naphthylidene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene sulfenyl-1, 4-phenylene] and poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene alkylsulfonyl-1, 4-phenylene].
In another preferred implementation of the present invention; the poly-aryl phosphine acid esters of described component (b) is selected from: poly-[oxygen base (phenyl phosphinylidene) Oxy-1; 4-phenylene (1-methyl isophthalic acid; 1-ethylidene)-1; 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) oxygen base-2; 6-naphthylidene] and poly-[oxygen base (phenyl phosphinylidene) Oxy-1,4-phenylene alkylsulfonyl-Isosorbide-5-Nitrae-phenylene].
Be applicable to the poly-aryl phosphine acid esters of component (b) of the present invention well known to a person skilled in the art that method is synthesized, such as, the melt-polycondensation disclosed in JP72-32299 to be adopted, phosphniline acyl chlorides and bisphenol compound are reacted and obtain; Also can be commercially available, such as poly-[oxygen base (phenyl phosphinylidene) Oxy-1,4-phenylene alkylsulfonyl-Isosorbide-5-Nitrae-phenylene] can purchased from Jinan Santai Fire Resistant Products Co., Ltd., and its commodity are called GP-77.
In fire-retardant combination of the present invention, based on the gross weight of described fire-retardant combination, the content of the poly-aryl phosphine acid esters of described component (b) is about 0.5 % by weight-Yue 10 % by weight, or is about 1 % by weight-Yue 6 % by weight.
When fire-retardant combination of the present invention is applied to spinning material, then under the general spinning temperature of PTT, should be liquid state for the poly-aryl phosphine acid esters of component (b) of the present invention, thus make the composition obtained can not block spinning die head under spinning temperature.In addition, the poly-aryl phosphine acid esters of the component (b) used in the present invention also should not be degraded under the general spinning temperature of PTT.The general spinning temperature of described PTT is between 240-280 ° of C.
composition (c) alumina nanoparticles and/or kaolin nanoparticle
In specification sheets of the present invention and/or claims, so-called " nanoparticle " is less than the particle of about 1 μm as long as to be the yardstick being defined as a dimension be widely.For the shape of described nano particle, can be spherical, needle-like, column, sheet or other are irregularly shaped.
When nanoparticle is nonspherical particle, the length of its maximum dimension, relative to the length ratio example of its smallest dimension, is length-to-diameter ratio (aspect ratio).
As long as in the range of definition of above-mentioned " nanoparticle ", the shape of the alumina nanoparticles used in the present invention and/or kaolin nanoparticle, size, be unimodal or bimodally all to have no particular limits with particle distribution curve.
The alumina nanoparticles used in the present invention generally has shape that is spherical or subglobular.Although only for the object of explanation, the granularity of the primary particle (i.e. non-agglomerated state) of the alumina nanoparticles used in the present invention is about 100nm or less, or be about 1nm to about 80nm, or be about 10nm to about 70nm, or be about 20nm to about 50nm.
The kaolin nanoparticle used in the present invention is generally sheet; The yardstick of described smallest dimension, is its longitudinal thickness (vertical thickness).Although only for the object of explanation, the longitudinal thickness of the kaolin nanoparticle used in the present invention is about 100nm or less, or is about 1nm to about 80nm, or is about 10nm to about 70nm, or is about 20nm to about 50nm.
In addition, the not special restriction of its length-to-diameter ratio of the kaolin nanoparticle adopted in the present invention, can be 1-1000, or be 1-100, or be 1-50, or be 1-20, and or be 1-10.
Component (c) alumina nanoparticles used in the present invention and/or kaolin nanoparticle, depending on its degree of scatter in polymeric substrate, can form aggregate (agglomerate), the granularity of usual formed aggregate is in the scope of about 50nm to about 300nm.
Granularity and the size distribution of this particle in polymeric substrate of nanoparticle can be determined by means of such as common focus point migration electron microscope (SEM).The description of the method can see " Confocaland Two-Photon Microscopy ", and Alberto Diaspro edits; I SBN 0-471-40920-0, Wiley-Liss, John Wiley & Sons, Inc. publish, the 2nd chapter, 19-38 page, and wherein quoted document.In addition, the granularity of nanoparticle and the size-grade distribution in polymeric substrate also can be passed through transmission electron microscope (TEM) and determine.
Be applicable to alumina nanoparticles of the present invention and/or all commercially available acquisition of kaolin nanoparticle; Such as, Hangzhou Wanjing New Material Co., Ltd. provides various different grain size and surface-treated commodity to be called the alumina nanoparticles of nano aluminium oxide; The commodity that emerging new high-tech material company limited of Zaozhuang City three provides are called the kaolin nanoparticle of nano kaoline.
In fire-retardant combination of the present invention, based on the gross weight of described fire-retardant combination, the content of described component (c) alumina nanoparticles and/or kaolin nanoparticle is about 0.1 % by weight to about 6 % by weight, or be about 0.2 % by weight to about 3 % by weight, or be about 0.5 % by weight to about 2 % by weight.
the additive that composition (d) optionally exists
Optionally can add in fire-retardant combination of the present invention and be selected from following additive: antioxidant, tinting material (comprising pigment and dyestuff), hydrolysis-resisting agent, lubricant, nucleator, coupling agent, thermo-stabilizer, antistatic agent and ultra-violet stabilizer.The additive used in the present invention has no particular limits, and can use kind conventional in this area, those skilled in the art can carry out selecting and adding according to purposes and actual needs.
As the example of above-mentioned various additive, can be listed below, but, it will be appreciated by those skilled in the art that the concrete kind that may be used for additive of the present invention is not limited to following example.
Described antioxidant such as hindered phenol anti-oxidants.Described tinting material is generally dry powder form and gives the material of color to composition or goods (such as fiber), and it can be inorganic or organic, natural or synthesis; In general, tinting material is inertia (is such as electroneutral and not with polymer reaction).Described hydrolysis-resisting agent is Carbodiimides hydrolysis-resisting agent such as.Described lubricant is TAF lubricant such as.Described nucleator can be inorganic or organic, such as nano silicon, organic carboxylate or organic phosphonate etc.Described coupling agent is as silicane and titante coupling agent.Described thermo-stabilizer is macromole hindered amines, phosphoric acid ester and copper halide type thermal stabilizing agent such as.Described ultra-violet stabilizer such as Benzotriazole Ultraviolet Stabilizer and benzophenone ultraviolet absorption agent.Described antistatic agent is included in five kinds of conventional antistatic agents of fiber industry, i.e. the derivative of amine, quaternary ammonium salt, the derivative of sulfuric ester, phosphoric acid ester and polyoxyethylene glycol.
In fire-retardant combination of the present invention, based on the gross weight of described fire-retardant combination, the content of the additive that described composition (d) optionally exists is generally 0-about 10 % by weight, or be 0.01 % by weight to about 6 % by weight, or be 0.1 % by weight-2 % by weight, as long as they do not deviate from essential property and the novel characteristics of described fire-retardant combination, and do not produce remarkable adverse influence to the performance of described fire-retardant combination.
the preparation of fire-retardant combination of the present invention and purposes
Fire-retardant combination of the present invention is prepared by conventional blending techniques well known to those skilled in the art, described component (a)-(c) and the optional additive (d) existed are at room temperature powder or particle form usually, blend composition can be formed in a number of different manners, such as, can heat simultaneously mix with molten state, also pre-mixing in a separate device (as dry type mixing) then can heat, or first heat remix separately.Above-mentioned mixing and heating can be carried out in this area conventional equipment such as forcing machine, Banbury mixer etc.Specifically; by above-mentioned component (a)-(c) in powder or particle form and the optional additive (d) existed; be enough at the temperature forming melt blended material, heating mixing is also extruded in a continuous manner and is cut into as pill or other suitable shapes.Term " pill " is broadly used, although sometimes also its shape is called " fragment ", " thin slice " etc. at this.
Of the present invention one preferred embodiment in, fire-retardant combination of the present invention is by said components (a)-(c) and the optional additive (d) existed being obtained with melt-blending process preparation.In addition, fire-retardant combination of the present invention can use conventional mold apparatus to prepare becomes moulded product; Also can use easily conventional throwing equipment by the pill made again melt-spinning become silk, redraw and become long filament, or directly use spinning/drawing process and make long filament.
Described mixing temperature should higher than the melting temperature of each component, but also need lower than the lowest decomposition temperature of its each composition, so PTT contained by fire-retardant combination and component (b), component (c) and/or component (d) mixing temperature must be regulated.Depend on each component used in the present invention, described mixing temperature is generally about 180 DEG C to about 290 DEG C, and preferred minimum temperature is about 220 DEG C, and top temperature is about 280 DEG C.
When component (b), component (c) and/or component (d) are evenly dispersed in the PTT base material of described component (a) substantially, fire-retardant combination of the present invention can form nano composite structure, and by electron microscope as transmission electron microscope (TEM) and scanning electronic microscope (SEM) confirm its nano composite structure.
Fire-retardant combination based on PTT of the present invention can prepare the fibre product, film, moulded product and other moulded products that become multiple different shape and form.For purposes of the present invention, term " fibre product ", be not specifically limited, it comprises long filament (filament), fiber (ber), short fiber (staplefiber), yarn (yarn), fabric (fabric), carpet or other weaving finished products, and it can be used for clothes, home decoration, carpet and other consumer's goods.
Fire-retardant combination of the present invention can be prepared into the long filament of various shape and thickness, and described long filament becomes fiber or yarn by steps such as doubling, twisting, plying, or is cut off and become short fiber.Then, by described long filament, fiber, short fiber, yarn for the preparation of fabric, carpet or other weaving finished product.Fabric of the present invention can be " knitting ", " weaving " or " non-woven " fabric.Described supatex fabric, also known as non-woven fabrics, typically refers to by applying heat, entanglement and/or pressure and long filament or short fiber is combined the fibrous reticulum or fibrefill made.
Described long filament can be circular or have other shapes, as octagon, trilateral, Radiation (also referred to as sol), scalloped ellipse (scalloped oval), trilobal, four tubular (also referred to as quatra-channel), scalloped band shape, band shape, T_Starburst etc.They can be solid, hollow or porous, and preferably solid.And be applicable to the stock size of most of purposes as the long filament of fabric and carpet and be at least about 0.5dpf (filament denier), and up to about 35dpf.Monofilament is thicker, can be about 10dpf to about 2000dpf.
Fire-retardant combination based on PTT of the present invention is preferred for preparing fibre product, and wherein particularly preferred fibre product comprises long filament, fiber, short fiber, yarn, fabric and carpet.
In an embodiment of the invention, fire-retardant combination of the present invention is for the preparation of fibre product, film or moulded product.In yet another embodiment of the present invention, fire-retardant combination of the present invention is for the preparation of fibre product, and wherein said fibre product comprises long filament, fiber, short fiber, yarn, fabric or carpet.
By using above-mentioned poly-aryl phosphine acid esters fire retardant (b) and above-mentioned inorganic nano-particle (c), the fire-retardant combination based on PTT that flame retardant resistance significantly improves can be obtained.Simultaneously, fire-retardant combination of the present invention because of comprised poly-aryl phosphine acid esters fire retardant (b) and inorganic nano-particle (c) be evenly dispersed in the base material of PTT (a), so can successfully carry out spinning and not block spinning die head, namely there is excellent spinning property.In addition, the mechanical property not obvious negative impact of the fibre product obtained prepared by this flame retardant combination.Compared with the ptt fiber goods not adding fire retardant, the physical strength of the fibre product that the fire-retardant combination obtained by the present invention is made obviously does not become bad, is sometimes even improved.
Embodiment
Below by specific embodiment, exemplary explanation is carried out to the present invention, but scope of the present invention is not by the restriction of these embodiments.
material
(a) PTT: be that E.I.DuPont de Nemours and Company (E.I.Du Pont Company) commodity are called
the Poly(Trimethylene Terephthalate) of half level of extinction (semidull grade), its IV is 1.02.
B () gathers aryl phosphine acid esters: poly-[oxygen base (phenyl phosphinylidene) Oxy-1; 4-phenylene alkylsulfonyl-1; 4-phenylene] (being also called " polyphenylene phosphonic acids sulfobenzide ester " or " PSPPP "); purchased from Jinan Santai Fire Resistant Products Co., Ltd., marque: GP-77.
(c1) alumina nanoparticles: purchased from Hangzhou Wanjing New Material Co., Ltd., trade(brand)name: nano aluminium oxide, surface via 2% silane coupler modified, particle size is 30-50nm, is to be recorded by transmission electron microscope.
(c2) kaolin nanoparticle: purchased from emerging new high-tech material company limited of Zaozhuang City three, trade(brand)name: nano kaoline, longitudinal thickness is 20-50nm, and lamella is of a size of 300-500nm, is to be recorded by transmission electron microscope.
the preparation of fire-retardant combination and test sample
1. melting mixing
Before mixing, PTT pill is placed in forced air circulation baking oven, 120 DEG C of dryings about 8 hours.
Each component of each embodiment and comparative example (is referred to table 1) in proportion and sends into twin screw extruder (kebeilong Co., Ltd ZSK-26MC), blended granulation is with obtained corresponding fire-retardant combination.For the forcing machine comprising 10 heating zone structures, the temperature of forcing machine is set in 180/240/240/240/240/240/240/240/240/230 ° of C, die head temperature is 230 ° of C, and screw speed is 300rpm, and work output is 20 kgs/hr.
2. molding
After molding, the pill extruded is dried to moisture content and is less than 40ppm.For flame retardant properties test, on Sumitomo 100 tons of mould machines, prepare test bars according to GB/T 2406.2-2009 molding, the screw diameter of mould machine is 32 millimeters, and nozzle diameter is 5 millimeters.Barrel temperature is set in 240 ° of C, and die temperature is 80 ° of C.
Basic configuration for the molding batten of test mechanical performance is dumb-bell shape batten, long 150 millimeters, and centre portions is of a size of wide 10 millimeters × thick 4 millimeters × long 80 millimeters.
Being then microscler batten for testing the molding batten of flame retardant resistance (LOI), being of a size of wide 10 millimeters × thick 4 millimeters × long 80 millimeters.
3. the preparation of fiber sample
The FDY spinning-drawing machine using Shanghai Jwell Chemical Fiber Machinery Co., Ltd to produce obtains fiber base material of the present invention (i.e. yarn).Before spinning, by the fire-retardant combination pill that obtains from above-mentioned melting mixing process under 120 ° of C dry 8 hours, then under suitable spinning temperature (250 ° of C-270 ° of C), by pill with the speed of 27 ml/min from 72 hole spinning nozzle (bore dia 25 millimeters, length/diameter equals 3) melt extrude, the long filament extruded is through two hot-rollings (temperature is respectively 68 ° of C and 135 ° C) drawing-off, and final winding obtains fully drawn yarn (FDY).Use identical parameter that the pill of other embodiment and comparative example is carried out melt-spinning, to assess the spinning property of this group combustion composition.And obtained long filament (i.e. fully drawn yarn) can be carried out measuring mechanical property, to assess breaking tenacity and the elongation at break of this long filament.
The hosiery machine that the model using Wuxi Zhen Rong Electrical Appliances Co., Ltd to manufacture obtained long filament is KU482, needle gage is 0.08mm, be made into the stocking leg, then a rectangle is cut off into, the rectangle cloth being of a size of 150 millimeters × 58 millimeters is cut into, to assess the flame retardant properties of this fabric according to GB/T 5454-1997 textiles limiting oxygen index(LOI) test request.
flame retardant resistance is tested
The flame retardant resistance of obtained fire-retardant combination is assessed by the limiting oxygen index(LOI) (LOI) testing sample.Basic LOI testing method and mechanism are: be placed on by sample to be tested in the transparent cylinder of the oriented nitrogen of upper flowing and the gas mixture of oxygen, light sample top and observe combustion processes, by the continuous burning time with burning length compared with the judging criterion in relevant criterion.By a series of test under different oxygen concentrations, judge the minimum oxygen concentration needed for burning.
1. the LOI test of moulded product: in the present invention, the LOI test of moulded product is carried out according to standard GB/T 2406.2-2009, equipment used is that concrete steps are as follows from Shandong Textile Research Institute (the automatic oxygen index tester of model JF-3LSY-605):
Within the time being no more than 30 seconds, light molding batten top, if batten can not be lighted, then represent that oxygen concentration used is too low.Continue to increase oxygen concentration until this batten is lighted, and observe its combustion time and burning length.If its combustion time is greater than 180 seconds, or its burning length is greater than 50 millimeters, then judge that oxygen concentration used is the minimum oxygen concentration of lighting this batten.
2. the LOI test of textiles: by rectangular fabric batten, carry out testing for the LOI of fabric according to standard GB/T 5454-1997, equipment used is that concrete steps are as follows from Shandong Textile Research Institute (the automatic oxygen index tester of model JF-3LSY-605):
Within the time of 10-15 second, put combustible fabric batten top, if batten can not be lighted, then oxygen concentration is too low.If lighted, record its time of glowing, after flame time and burning length.If it glows, the summation of time, after flame time or glow time and after flame time is greater than 2 minutes, or burning length is greater than 40 millimeters, then judge that oxygen concentration used is the minimum oxygen concentration of lighting this batten.
fibre breakage intensity and elongation at break test
Fiber test sample preparation: the long filament adopted obtained by above-mentioned spinning technique and spinning condition is used electronics single yarn tester test (Electronic Instrument, Limited of Laizhou City, YG061FQ type), at 20 ° of C, the test environment of 65% humidity, measure breaking tenacity and the elongation at break of this long filament, testing and getting its mean value for 30 times is test result.
Embodiment 1
According to preceding method, the fire-retardant combination of preparation comparative example 1-10 and embodiment 1-8, and prepare it and test sample (molding batten) accordingly and test for the LOI of moulded product, its test result is in table 1, and wherein listed LOI result is repeatedly prepare the test result mean value of flame retardant combination matter sample.
Table 1: the composition of fire-retardant combination and LOI test result
By the result of table 1, be apparent to draw a conclusion.
Can be seen by comparative example 2-6, when only using poly-aryl phosphine acid esters (b) (i.e. PSPPP), along with the content of poly-aryl phosphine acid esters increases (such as, content is 1 % by weight and 10 % by weight), the flame retardant properties of said composition increases (such as, LOI is 23.5 and 27.0).Can be seen by comparative example 7-10, when only using nanoparticle (c), the content of alumina nanoparticles (c1) or kaolin nanoparticle (c2) (such as, 0.5 % by weight and 2 % by weight) on the flame retardant properties impact little (such as, LOI is 23.0 and 23.5) of said composition.
Can be seen by embodiment 1-8, when to use poly-aryl phosphine acid esters (b) and alumina nanoparticles (c1) or kaolin nanoparticle (c2) simultaneously, when the poly-arylphosphonic acid ester content of identical component (b), add the flame retardant properties that a small amount of component (c) nanoparticle can significantly improve obtained fire-retardant combination, that is, the nanoparticle of component (c) improves the flame retardant effect of the poly-aryl phosphine acid esters of component (b) synergistically.
According to method described above, the long filament obtained by the composition by PTT (comparative example 1), embodiment 3 and embodiment 4 is woven into fabric, tests the flame retardant properties LOI of these fabrics, and test result is listed in table 2.
Table 2: the flame retardant properties of fabric
| Use composition | The LOI of fabric |
| PTT (comparative example 1) | 24.1 (warp-wises), 24.2 (broadwises) |
| Embodiment 3 | 26.1 (warp-wises), 26.3 (broadwises) |
| Embodiment 4 | 27.1 (warp-wises), 27.3 (broadwises) |
As can be seen from Table 2, the flame retardant properties of the fabric obtained by the fire-retardant combination based on PTT of the present invention significantly improves.
The breaking tenacity of the long filament of test obtained by the fire-retardant combination of comparative example 1, embodiment 4 and embodiment 7 and elongation at break, its result is as shown in table 3.
Table 3: the mechanical property of fiber
Even if the physical strength of the long filament shown obtained by fire-retardant combination of the present invention by the result of table 3 reduces a little, still in the acceptable scope in this area (reducing amount is not more than 20%), or even increase.
In present specification in conjunction with specific embodiments to invention has been detailed description, but to those skilled in the art, obviously can to make various changes and modifications it without departing from the case in the spirit of the invention.All this type of change and modification should think the claims all falling into the application scope within.
Claims (9)
1. fire-retardant combination, based on the gross weight of described fire-retardant combination, described fire-retardant combination comprises:
The Poly(Trimethylene Terephthalate) of (a) 74 % by weight-99.4 % by weight;
The poly-aryl phosphine acid esters of (b) 0.5 % by weight-10 % by weight;
The alumina nanoparticles of (c) 0.1 % by weight-6 % by weight and/or kaolin nanoparticle; With
The additive of the optional existence of (d) 0-10 % by weight.
2. fire-retardant combination according to claim 1, wherein, described poly-aryl phosphine acid esters is selected from: poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 3-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) oxygen base [1, 1 '-xenyl]-4, 4 '-two base], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene methylene radical-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene (1-methyl isophthalic acid, 1-ethylidene)-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene cyclohexylidene-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 5-naphthylidene], poly-[oxygen base (phenyl phosphinylidene) oxygen base-2, 6-naphthylidene], poly-[oxygen base (phenyl phosphinylidene) oxygen base-2, 7-naphthylidene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene-1, 2-diazenediyl-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene sulfenyl-1, 4-phenylene], with poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene alkylsulfonyl-1, 4-phenylene].
3. fire-retardant combination according to claim 2, wherein, described poly-aryl phosphine acid esters is selected from: poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 3-phenylene], poly-[oxygen base (phenyl phosphinylidene) oxygen base [1, 1 '-xenyl]-4, 4 '-two base], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene methylene radical-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene (1-methyl isophthalic acid, 1-ethylidene)-1, 4-phenylene], poly-[oxygen base (phenyl phosphinylidene) oxygen base-2, 6-naphthylidene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene sulfenyl-1, 4-phenylene], with poly-[oxygen base (phenyl phosphinylidene) Oxy-1, 4-phenylene alkylsulfonyl-1, 4-phenylene].
4. fire-retardant combination according to claim 3; wherein; described poly-aryl phosphine acid esters is selected from: poly-[oxygen base (phenyl phosphinylidene) Oxy-1; 4-phenylene (1-methyl isophthalic acid; 1-ethylidene)-Isosorbide-5-Nitrae-phenylene], poly-[oxygen base (phenyl phosphinylidene) oxygen base-2,6-naphthylidene], poly-[oxygen base (phenyl phosphinylidene) Oxy-1; 4-phenylene alkylsulfonyl-Isosorbide-5-Nitrae-phenylene].
5. fire-retardant combination according to claim 1, wherein, the content of described alumina nanoparticles and/or kaolin nanoparticle is 0.2 % by weight-3 % by weight.
6. fire-retardant combination according to claim 1, wherein, the additive of described optional existence is selected from: antioxidant, the tinting material comprising pigment and dyestuff, hydrolysis-resisting agent, lubricant, nucleator, coupling agent, thermo-stabilizer, antistatic agent and ultra-violet stabilizer.
7. goods, comprise fire-retardant combination according to claim 1 or are obtained by fire-retardant combination according to claim 1.
8. goods according to claim 7, wherein said goods are fibre products.
9. goods according to claim 8, wherein said fibre product is long filament, fiber, short fiber, yarn, fabric or carpet.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3928283A (en) * | 1970-03-09 | 1975-12-23 | Toyo Boseki | Fireproof, thermoplastic polyester composition |
| CN1732232A (en) * | 2002-12-27 | 2006-02-08 | 宝理塑料株式会社 | Flame-retardant resin composition |
| CN102504500A (en) * | 2011-10-26 | 2012-06-20 | 惠州市沃特新材料有限公司 | PET (polyethylene terephthalate) engineering plastic and preparation method and application thereof |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3928283A (en) * | 1970-03-09 | 1975-12-23 | Toyo Boseki | Fireproof, thermoplastic polyester composition |
| CN1732232A (en) * | 2002-12-27 | 2006-02-08 | 宝理塑料株式会社 | Flame-retardant resin composition |
| CN102504500A (en) * | 2011-10-26 | 2012-06-20 | 惠州市沃特新材料有限公司 | PET (polyethylene terephthalate) engineering plastic and preparation method and application thereof |
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