CN103897353A - Flame retardant composition based on polytrimethylene terephthalate - Google Patents
Flame retardant composition based on polytrimethylene terephthalate Download PDFInfo
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- CN103897353A CN103897353A CN201210567564.4A CN201210567564A CN103897353A CN 103897353 A CN103897353 A CN 103897353A CN 201210567564 A CN201210567564 A CN 201210567564A CN 103897353 A CN103897353 A CN 103897353A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/14—Macromolecular materials
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- 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
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
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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
- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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'
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
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- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a flame retardant composition based on polytrimethylene terephthalate (PTT), also relates to fiber products prepared from the flame retardant composition. The flame retardant composition comprises: (a) 74 wt%-99.4 wt% of polytrimethylene terephthalate; (b) 0.5 wt%-10 wt% of a flame retardant, which is the phosphorus-containing polyester shown in the formula 1, wherein n is an integer from 22 to 150; (c) 0.1 wt%-6 wt% of alumina nanoparticles; and (d) 0-10 wt% of an optional existing additive. The weight percentage is based on the total weight of the flame retardant composition. (img file='DDA00002640851200011.TIF' wi = '1012' he = '609' /).
Description
Technical field
The present invention relates to the fire-retardant combination based on Poly(Trimethylene Terephthalate) (PTT), particularly contain the fire-retardant combination based on PTT of phosphorus-containing polyester fire retardant agent and inorganic nano-particle.The invention still further relates to the goods, the especially fibre product that comprise above-mentioned fire-retardant combination or made by above-mentioned fire-retardant combination.
Background technology
Poly(Trimethylene Terephthalate) is (conventionally referred to as " PTT ", " PPT " or " 3GT ") generally by 1, ammediol and terephthalic acid or 1, ammediol and terephthalate polycondensation make, and are a kind of new aromatic polyester after polyethylene terephthalate (being conventionally called for short " PET ") and polybutylene terephthalate (being conventionally called for short " PBT ").PTT resin is more excellent than PET and PBT aspect mechanical characteristics, weathering resistance, heat-resistant aging and resistance to hydrolysis.
Flexibility, the fluffiness of acrylic fibers and the pollution resistance of terylene that ptt fiber combines nylon are, there is better colour fastness than nylon simultaneously, the shortcoming of having avoided acrylic fibers balling-ups easy to wear, has again reasonable feel, and intrinsic elasticity itself is fine 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 under some environment, PTT self flame retardant properties is good not, thereby limit the application of PTT in these fields.
Improve the mode of the flame retardant resistance of PTT, mainly contain at present three kinds: one is post processing mode, use fire retardant dipping ptt fiber or fabric and make flame retardant resistance ptt fiber or fabric, the shortcoming of the method is that flame retardant resistance can not be lasting, and likely affect the outward appearance of fiber or fabric, be not suitable for the application of engineering plastics yet; Another kind is copolymerization formula,, introduces in the macromolecular chain of PTT and makes flame-retarding PTT as one of comonomer by fire retardant, and the flame retardant resistance of the flame-retarding PTT that the method obtains is lasting, but its shortcoming is other inherent nature that has also simultaneously changed PTT polyester; Another is blend formula, by fire retardant and PTT blend, obtains flame-retardant composition, then carries out follow-up molding or spinning to make fire-retardant fibre or fabric.Although the fire-retardant PTT of commixed type is compared with copolymerization formula flame-retarding PTT, there are simple process, advantage with low cost manufacturing to produce, but the fire retardant adding must can be uniformly dispersed in matrix resin, and also can not produce the phenomenons such as migration, frosting, in order to avoid cause the flame retardant resistance of PTT blend decline or lost efficacy.
The research of adding halogen-containing type fire retardant in polyester is very extensive, but halogen-containing type fire retardant all can cause larger environmental pollution in manufacture, recovery or when discarded, and produces toxic and harmful in the time of burning, therefore, it is substituted by non-halogen-type fire retardant gradually.No-halogen type fire retardant, especially phosphonium flame retardant have been widely used in polyester, especially in trevira.Described phosphonium flame retardant comprises response type phosphonium flame retardant and addition type phosphonium flame retardant.Response type phosphonium flame retardant, owing to being added in the molecular chain of polyester, therefore tends to change the thermal properties of this flame retardant polyester, thereby brings difficulty to follow-up spinning; And this often cannot produce on existing production platform, need to adjust equipment or processing condition, thereby has increased production cost.
Patent application CN101532189A discloses a kind of flame retardant PTT polyester fiber and production method thereof, wherein adopt the method for copolymerization that phosphonium flame retardant monomer (such as 2-propyloic alkyl phosphonic acid, 2-carboxyethyl phenyl phosphinic acid etc.) is added in PTT polyester molecule chain, simultaneously, in copolyreaction thing, add the inorganic nano-particle that is selected from silicon-dioxide, calcium carbonate, magnesiumcarbonate and barium sulfate, obtain flame-retarding PTT polyester by copolymerization.This patent application relates to aforesaid response type phosphonium flame retardant.
Patent application CN101709137A discloses a kind of phosphorus-containing PTT/nano composite material and preparation method thereof, wherein adopt the method for copolymerization that phosphonium flame retardant monomer (such as BHET, BHPPO, CEMPP, DDP etc.) is added in PTT polyester molecule chain, simultaneously, in copolyreaction thing, add the inorganic nano-particle that is 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 response type phosphonium flame retardant.
In prior art, also there is the composition (being aforementioned additive flame retardant) that fire retardant and polyester blend are improved to obtain flame retardant properties, for example, patent application JP2006-144184A discloses a kind of flame retardant polyester composition for artificial hair, described composition is that polyester (for example, PET) and flame retardant polyester are copolymer blended and obtain.Wherein, described flame retardant polyester multipolymer is the multipolymer being made by terephthalic acid, alkyl diol and phosphorous or brominated compound copolymerization.
Patent application JP2007-112875A discloses a kind of fire-retadant polyester resin composition, the organic phosphorus flame retardant of its polyester that comprises 100 weight parts, 10-80 weight part and the mineral compound of 10-100 weight part, obtain fire-retadant polyester resin composition through melt blending.The main application of described fire-retadant polyester resin composition is automobile, household electrical appliances, electric etc. molded parts, be to increase its physical strength and rigidity, and its consumption is at least 10 weight parts so add the object of mineral compound (as mica, talcum powder etc.).Described organic phosphorus flame retardant is the homopolymer suc as formula A:
Wherein, n is the integer of 2-20.
At present, still need to provide flame retardant properties to improve and the composition based on PTT of environmental protection, and its application is not limited only to engineering plastics, also can comprises that fibre product is as fields such as garment material, family's spun articles and carpets.
Summary of the invention
The present inventor finds after deliberation, by by PTT and phosphorous-containing polyester blend as shown in Equation 1, can obtain the fire-retardant combination that flame retardant resistance improves.Particularly, contriver finds, by add a small amount of aluminium oxide nano particle in the mixture of the phosphorous-containing polyester of PTT and formula 1, can improve synergistically the flame retardant effect of the phosphorous-containing polyester of formula 1.
Based on above-mentioned discovery, the invention provides a kind of fire-retardant combination, it comprises:
(a) Poly(Trimethylene Terephthalate) of approximately 74 % by weight-Yue 99.4 % by weight;
(b) fire retardant of approximately 0.5 % by weight-Yue 10 % by weight, it is phosphorous-containing polyester as shown in Equation 1:
(c) the aluminium oxide nano particle of approximately 0.1 % by weight-Yue 6 % by weight; With
(d) additive of the optional existence of 0-approximately 10 % by weight;
Wherein
N is the integer of scope at 22-150; And
Described % by weight is the gross weight based on described fire-retardant combination.
In an embodiment of the invention, in fire-retardant combination of the present invention, described Poly(Trimethylene Terephthalate) (a) is Poly(Trimethylene Terephthalate) homopolymer, Poly(Trimethylene Terephthalate) multipolymer or its any blend, and the propylene glycol ester terephthalate that wherein said Poly(Trimethylene Terephthalate) multipolymer comprises 70mol% is at least as main copolymerization units.
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 Poly(Trimethylene Terephthalate) (a) is approximately 74 % by weight-Yue 99.4 % by weight, or is approximately 85 % by weight-Yue 95 % by weight.
In an embodiment of the invention, in fire-retardant combination of the present invention, described fire retardant (b), the number-average molecular weight of the phosphorous-containing polyester of formula 1 is 9,000-approximately 50,000.
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 fire retardant (b) is approximately 0.5 % by weight-Yue 10 % by weight, or is approximately 1 % by weight-Yue 6 % by weight.
In one embodiment, in fire-retardant combination of the present invention, the granularity of the primary particle of described aluminium oxide nano particle (c) is about 100nm or less, or is that about 1nm is to about 80nm, or be extremely about 70nm of about 10nm, or be that about 20nm is to about 50nm.
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 aluminium oxide nano particle (c) is that approximately 0.1 % by weight is to approximately 6 % by weight, or be extremely approximately 4 % by weight of approximately 0.2 % by weight, or be that approximately 0.3 % by weight is to approximately 2 % by weight.
In one embodiment, in fire-retardant combination of the present invention, the additive of described optional existence (d) is selected from: antioxidant, the tinting material that comprises pigment and dyestuff, hydrolysis-resisting agent, lubricant, nucleator, coupling agent, thermo-stabilizer, antistatic agent and UV light stabilizing agent.
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 of described optional existence (d) is generally 0-approximately 10 % by weight, or be extremely approximately 6 % by weight of 0.01 % by weight, or be 0.1 % by weight-2 % by weight.
In addition, the invention still further relates to the goods that comprise above-mentioned fire-retardant combination or made by above-mentioned fire-retardant combination, especially fibre product, described fibre product can be long filament (filament), fiber (fiber), short fiber (staple fiber), yarn (yarn), fabric (fabric) or carpet.
Embodiment
Unless otherwise indicated, all publications, patent application, patent and other reference that the present invention mentions is all incorporated into herein by reference in full, is equivalent to be presented in full herein.
Unless otherwise defined, all technology used herein and scientific terminology have common the understood same implication of one skilled in the art of the present invention.In the situation that conflicting, comprise that with this specification sheets definition is as the criterion.
Unless otherwise indicated, all percentage ratio, umber, ratio etc. are all by weight.
" mol% " refers to molar percentage.
In the time explaining 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 any scope that is equivalent to specifically to have disclosed by any a pair of range limit or preferred value and any range lower limit or preferred value are combined, and do not consider whether this scope specifically discloses.Unless otherwise noted, numerical range listed herein is intended to comprise the end points of scope, and all integers and mark within this scope.
In this article, term " by ... form " or " by ... form " be equal to " comprise/comprise ".Term used herein " comprises ", " comprising ", " having ", " having " " are contained " or their any other variants, is that intention comprises comprising of non-exclusionism.For example, the composition, process, method, product or the equipment that comprise a series of key elements might not be only limited to those key elements, but can also comprise other key elements of clearly not listing or these compositions, process, method, product or equipment are intrinsic.And, unless clearly represent contrary, "or" refers to and comprises "or" but not exclusive "or".For example, satisfy condition A or B:A of any condition is that true (or existence) and B are false (or not existing) below, A is that false (or not existing) and B are true (or existence), and A and B are true (or existence).
In addition, do not have restricted for the word " one " before certain key element of the present invention or component to the quantity of this key element 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 plural situation.
Unless there is other explanation, material of the present invention, method and embodiment are only illustrative, and not restrictive.Although can adopt and be similar to or be equal to those methods as herein described and material in enforcement of the present invention or test, this specification sheets has below been described suitable method and material.
In the time using the end points of term " about " description value or scope, be appreciated that and comprise concrete value or related end points.
Below fire-retardant combination of the present invention is described in detail.
(a)PTT
Being applicable to PTT of the present invention can be PTT homopolymer, PTT multipolymer or any blend of PTT.Preferably PTT homopolymer.
Term " homopolymer " refers to the polymkeric substance that only contains a kind of repeating unit.In the present invention, " PTT homopolymer " refers to the polymkeric substance being obtained by the polycondensation of 1,3-PD and terephthalic acid or terephthalic acid equivalent.Wherein, " terephthalic acid equivalent " refers to and aspect reacting with glycol, showing substantially and the compound of terephthalic acid same nature.For the object of the invention, terephthalic acid equivalent comprises the ester (for example dimethyl terephthalate (DMT)) of for example terephthalic acid and forms the derivative (for example carboxylic acid halides and acid anhydrides) of ester.Generally speaking, preferred terephthalic acid and terephthalate.
Term " multipolymer " refers to the polymkeric substance being formed by two or more monomer polymerizations, contains the polymkeric substance of two or more repeating units.In the present invention, " PTT multipolymer " is preferably containing 70mol% or higher or containing 80mol% or higher or containing 90mol% or higher or containing 95mol% or higher propylene glycol ester terephthalate, other parts are such as, polymkeric substance derived from the monomer except terephthalic acid and 1,3-PD (ethylene glycol, butyleneglycol etc.).
Term " blend " refers to the mixture being mixed by two or more components.In the present invention, " PTT blend " can be by mixing PTT homopolymer or PTT multipolymer to prepare; Preferably comprise gross weight approximately 80 % by weight based on PTT blend or higher or containing 90 % by weight or higher or containing 95 % by weight or higher PTT homopolymer or PTT multipolymer.
The preparation method who is 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 that for example derive from E.I.Du Pont Company are by name
product, for example, be divided into according to its dulling agent content and have greatly light, partly have the different sortses such as light, half delustring, full-dull; Each kind comprises again several and has the PTT of 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 PTT (a) is approximately 74 % by weight-Yue 99.4 % by weight, or is approximately 85 % by weight-Yue 95 % by weight.
(b
) fire retardant
The fire retardant (b) using in the present invention is as shown in the formula the phosphorous-containing polyester shown in 1:
Formula 1
Wherein
N is from 22 to 150 integer.
In the situation that fire-retardant combination of the present invention is applied to spinning material, be applicable to fire retardant of the present invention (b), be the phosphorous-containing polyester of formula 1, under the general spinning temperature of PTT, should be molten state, thereby make the composition obtaining under spinning temperature, can not block spinning die head.The phosphorous-containing polyester (b) of the formula 1 using in the present invention in addition, also should not be degraded under the general spinning temperature of PTT.The general spinning temperature of described PTT is between 240-290 ° of C.
From the viewpoint of flame retardant resistance, there is no particular restriction for the molecular weight of the phosphorous-containing polyester (b) to formula 1, because its phosphorus content (is not about 7.8-8.3%) along with the increase of n value changes too much, so only need regulate its consumption while use.But, after the phosphorous-containing polyester (b) of consideration formula 1 and PTT (a) blend, do not have phenomenon and the thermostabilitys thereof such as migration, frosting, the number-average molecular weight of the phosphorous-containing polyester (b) of preferred described formula 1 is at least approximately 9,000; Or be 9,500; Or be 10,000.On the other hand, the difficulty of obtaining from material and melt temperature consideration thereof, the number-average molecular weight of the phosphorous-containing polyester of preferred described formula 1 (b) mostly is approximately 50,000 most; Or be 40,000; Or be 30,000; Or be 20,000.The number-average molecular weight of described formula 1 phosphorous-containing polyester (b) can be measured with gel permeation chromatography (GPC), referring to US2006/025824A1.
In an embodiment of the invention, in fire-retardant combination of the present invention, described fire retardant (b), the number-average molecular weight of the phosphorous-containing polyester of formula 1 is approximately 9,000-approximately 50,000; Or be approximately 9,500-approximately 40,000; Or be approximately 10,000-approximately 30,000.
Be applicable to fire retardant of the present invention (b), it is the phosphorous-containing polyester of formula 1, can be synthetic well known to a person skilled in the art method, for example, adopt the disclosed condensation methods of patent application JP2007-112875A, by 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO, CAS 35848-25-5), methylene-succinic acid (CAS 2170-03-8) and ethylene glycol and suitable catalyzer direct reaction and make.In addition, also can adopt the disclosed condensation methods of patent application US2006/025824A1, use by the phosphorus ester glycol of DOPO, methylene-succinic acid and ethylene glycol pre-polymerization gained (suc as formula 2 compound) and suitable catalyzer, under the condition of high-temperature pressure-reduction, the length by controlling the reaction times is to obtain number-average molecular weight different phosphorous-containing polyester homopolymer.
In addition, the phosphorous-containing polyester of formula 1 also can be commercially available, and for example three wide trade Co., Ltds (Sanko Co.Ltd.) of Japan sell, the phosphorous-containing polyester homopolymer of commodity ME-P8 by name.
In fire-retardant combination of the present invention, based on the gross weight of described fire-retardant combination, the content of the phosphorous-containing polyester of described formula 1 (b) is approximately 0.5 % by weight-Yue 10 % by weight, or is approximately 1 % by weight-Yue 6 % by weight.
(c) aluminium oxide nano particle
In specification sheets of the present invention and/or claims, so-called " nanoparticle " is as long as be that the yardstick that is defined as widely a dimension is the particle that is less than approximately 1 μ m.For the shape of described nano particle, can be spherical, needle-like, column, sheet or other are irregularly shaped.
In the time that nanoparticle is nonspherical particle, the length of its maximum dimension, with respect 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 aluminium oxide nano particle (c) using in the present invention, size, be unimodal or bimodally all to have no particular limits with particle distribution curve.
The aluminium oxide nano particle (c) using in the present invention generally has the shape of spherical or subglobular.Although only for the object of explanation, the granularity of the primary particle (being non-reunion state) of the aluminium oxide nano particle (c) using in the present invention is about 100nm or less, or be extremely about 80nm of about 1nm, or be extremely about 70nm of about 10nm, or be that about 20nm is to about 50nm.
The aluminium oxide nano particle (c) using in the present invention, degree of scatter depending on it in polymeric substrate, can form aggregate (agglomerate), the granularity of common formed aggregate is in the scope of about 300nm at about 50nm.
The granularity of nanoparticle and the size distribution of this particle in polymeric substrate can be determined by means of for example confocal laser scanning electronic microscope (SEM).The description of the method can be referring to " Confocal and Two-Photon Microscopy ", and Alberto Diaspro edits; ISBN0-471-40920-0, Wiley-Liss, John Wiley & Sons, Inc. publishes, the 2nd chapter, 19-38 page, and the document wherein quoted.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 the commercially available acquisition of aluminium oxide nano particle of the present invention (c); For example, Hangzhou ten thousand scape novel material company limiteds provide the aluminium oxide nano particle of various different grain sizes and surface-treated commodity nano aluminium oxide by name.
In fire-retardant combination of the present invention, based on the gross weight of described fire-retardant combination, the content of described aluminium oxide nano particle (c) is extremely approximately 6 % by weight of approximately 0.1 % by weight, or is extremely approximately 4 % by weight of approximately 0.2 % by weight, or is that approximately 0.3 % by weight is to approximately 2 % by weight.
(d) the optional additive existing
In fire-retardant combination of the present invention, can optionally add 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 UV light stabilizing agent.The additive using in the present invention has no particular limits, and can use kind conventional in this area, and those skilled in the art can select and add according to purposes and actual needs.
As the example of above-mentioned various additives, can be listed below, still, it will be appreciated by those skilled in the art that and can be not limited to following example for the concrete kind of additive of the present invention.
Such as hindered phenol anti-oxidants of described antioxidant.Described tinting material is generally dry powder form and for example, gives the material of color to composition or goods (fiber), and it can be inorganic or organic, natural or synthetic; In general, tinting material be inertia (be for example electroneutral and not with polymer reaction).Described hydrolysis-resisting agent is Carbodiimides hydrolysis-resisting agent for example.Described lubricant is TAF lubricant for example.Described nucleator can be inorganic or organic, such as nano silicon, organic carboxylate or organic phosphonate etc.For example silicane of described coupling agent and titante coupling agent.Described thermo-stabilizer is macromole hindered amines, phosphoric acid ester and copper halide type thermal stabilizing agent for example.For example benzotriazole category ultraviolet absorbers of described UV light stabilizing agent and benzophenone ultraviolet absorbers.Described antistatic agent is included in five kinds of antistatic agents that fiber industry is conventional, the i.e. 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 (d) of described optional existence is generally 0-approximately 10 % by weight, or be that 0.01 % by weight is to approximately 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 the performance of described fire-retardant combination is not produced to remarkable adverse influence.
the preparation of fire-retardant combination of the present invention and purposes
Fire-retardant combination of the present invention can be prepared by conventional blending technology well known to those skilled in the art, described component (a)-(c) and the optional additive (d) existing are at room temperature powder or particle form conventionally, can multiple different mode form blend composition, for example, can heat with molten state and mix simultaneously, also can pre-mixing in independent equipment (as dry type is mixed) then heat, or first heat separately remix.Above-mentioned mixing and heating can be carried out in this area conventional equipment such as forcing machine, Banbury mixer etc.Specifically, by the above-mentioned component (a) that is powder or particle form-(c) and the optional additive (d) existing, at the temperature that is enough to form melt blended material, heating mixes, and extrudes in a continuous manner and be cut into as pellet or other suitable shapes.Broadly use term " pellet " at this, although sometimes also its shape is called to " smear metal ", " sheet stock " etc.
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) existing are obtained with melt-blending process preparation.In addition, fire-retardant combination of the present invention can use conventional mold apparatus preparation to become moulded product; Also can use conventional spinning equipment well known to those skilled in the art by the pellet of making again melt spun make silk, redraw and become long filament, or directly use spin/draw technique and make long filament.
Described mixing temperature should be higher than the melting temperature of each component, but also need be lower than the lowest decomposition temperature of its each composition, so must regulate mixing temperature according to the contained PTT of fire-retardant combination and component (b), component (c) and/or component (d).Depend on each component used in the present invention, described mixing temperature is generally approximately 180 ℃ to approximately 290 ℃, and preferred minimum temperature is approximately 220 ℃, and top temperature is approximately 280 ℃.
Component (b), component (c) and/or component (d) can be evenly dispersed in the PTT base material of described component (a) by melt blending substantially, and the structure of prepared fire-retardant combination of the present invention can be confirmed as transmission electron microscope (TEM) and scanning electronic microscope (SEM) by electron microscope.
Fire-retardant combination based on PTT of the present invention can be prepared becomes the fibre product of multiple different shape and form, film, moulded product and other moulded products.For purposes of the present invention, term " fibre product ", is not specifically limited, and it comprises long filament, fiber, short fiber, yarn, 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 can become fiber or yarn by steps such as doubling, twisting, plying, or its cut-out is become to 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 claims again non-woven fabrics, typically refers to by applying heat, entanglement and/or pressure long filament or short fiber in conjunction with fibrous reticulum or the 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.Be at least about 0.5dpf (filament denier) and be applicable to most of purposes as the stock size of the long filament of fabric and carpet, and up to about 35dpf.Monofilament can be thicker, and it can be that about 10dpf is 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 can be used for preparing fibre product, film or moulded product.In yet another embodiment of the present invention, fire-retardant combination of the present invention can be used for preparing fibre product, and wherein said fibre product comprises long filament, fiber, short fiber, yarn, fabric or carpet.
By using above-mentioned phosphorous-containing polyester as shown in Equation 1 (b) and above-mentioned aluminium oxide nano particle (c), can obtain the fire-retardant combination based on PTT that flame retardant resistance obviously improves.Simultaneously, fire-retardant combination of the present invention is because of comprised fire retardant (b), it is the phosphorous-containing polyester of formula 1, and aluminium oxide nano particle (c) is to be evenly dispersed in the base material of PTT (a), do not block spinning die head so can successfully carry out spinning, there is good spinning property.In addition, prepared by this flame retardant combination and the mechanical property of fibre product do not have obvious negative impact.Compared with not adding the ptt fiber goods of fire retardant, it is bad that the physical strength of the fibre product that the fire-retardant combination being obtained by the present invention is made does not obviously become, and is sometimes even improved.
Embodiment
Below by specific embodiment, the present invention is carried out to exemplary explanation, but scope of the present invention is not subject to the restriction of these embodiment.
material
(a) PTT: be that E.I.DuPont de Nemours and Company (E.I.Du Pont Company) commodity are by name
the Poly(Trimethylene Terephthalate) of half level of extinction (semidull grade), its IV is 1.02.
(b) ME-P8: being the phosphorous-containing polyester of formula 1, is for No. CAS 403614-60-8, purchased from three wide trade Co., Ltds of Japan, number-average molecular weight is approximately 10,000, phosphorus content is 7.8-8.2%.
(c) aluminium oxide nano particle: purchased from Hangzhou ten thousand scape novel material company limiteds, 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.
(d)
1010: be antioxidant, four (methylene radical-3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester) methane (being for No. CAS 6683-19-8), phenol type antioxidant, purchased from BASF.
the preparation of fire-retardant combination and test sample
1. melting mixing
Before mixing, PTT pellet is placed in to forced air circulation baking oven, be dried approximately 8 hours at 120 ℃.
Each component of each embodiment and comparative example (is referred to table 1) in proportion and send into twin screw extruder (ZSK-26MC of kebeilong Co., Ltd) in batches, blend granulation is to make corresponding fire-retardant combination.For the forcing machine that comprises 10 heating zone structures, by the Temperature Setting of forcing machine, at 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.The charging total amount of every batch is approximately 4 kilograms (moulded parts) or 10 kilograms (fibre product); In addition, also, by charging total amount, add in addition approximately 0.2% antioxidant.
2. the preparation of molding sample
Before molding, the pellet of extruding is dried to moisture content and is less than 40ppm.For flame retardant properties test, on Sumitomo100 ton mould machine, prepare test bars according to GB/T2406.2-2009 molding, the screw diameter of mould machine is 32 millimeters, nozzle diameter is 5 millimeters.Barrel temperature is set in 240 ° of C, and die temperature is 80 ° of C.
The basic configuration that is used for the molding batten of test mechanical performance is dumb-bell shape batten, and long 150 millimeters, centre portions is of a size of wide 10 millimeters × thick 4 millimeters × long 80 millimeters.
The molding batten that is used for testing flame retardant resistance (LOI) is microscler batten, is of a size of wide 10 millimeters × thick 4 millimeters × long 80 millimeters.
3. the preparation of fiber sample
Before melt-spinning, the pellet of extruding is dried to 8 hours at 120 ° of C in baking oven, then dry pellet is metered in single screw extrusion machine (Fuji E0200), under suitable spinning temperature (250 ° of C-270 ° of C), by using Fuji melting-Spinning machine (ABE type), it is equipped with diameter to be 100 millimeters is the spinning nozzle in 36 holes, it is 2 that each hole has diameter and the length/diameter ratio of 0.3 millimeter, extrudes fiber with the speed of 27 ml/min.The fiber of extruding is that 65 ° of C, hot plate temperature are that (Suzhou is special sends out company limited dynamo-electric for the drawing-off crimping machine of 135 ° of C by using heat roller temperature again, VC403-0111), with the speed drawing-off of 800 ms/min, its drafting multiple is about 1.8, and final coiling obtains partially oriented fiber (POY).
Use identical parameter that the pellet of other embodiment and comparative example is carried out to melt-spinning, to assess the spinning property of this group combustion composition.And prepared fiber can be carried out to measuring mechanical property, to assess breaking tenacity and the elongation at break of this fiber.
The hosiery machine that the model that uses Wuxi Zhen Rong Electrical Appliances Co., Ltd to manufacture the fiber making is KU482, needle gage is 0.08mm, be made into the stocking leg, then cut off into a rectangle, be cut into according to GB/T5454-1997 textiles limiting oxygen index(LOI) test request the rectangle cloth that is of a size of 150 millimeters × 58 millimeters, to assess the flame retardant properties of this fabric.
flame retardant resistance test
Assess the flame retardant resistance of obtained fire-retardant combination by the limiting oxygen index(LOI) (LOI) of test sample.Basic LOI testing method and mechanism are: sample to be tested is placed in the transparent cylinder of gas mixture of oriented mobile nitrogen and oxygen, light sample top and observe combustion processes, continuous burning time and burning length are compared with the judging criterion in relevant criterion.By a series of test under different oxygen concentrations, the minimum oxygen concentration that judgement burning is required.
1. the LOI of moulded product test: in the present invention, carry out the LOI test of moulded product according to standard GB/T2406.2-2009, 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 that is no more than 30 seconds, light molding batten top, if batten can not be lighted, represent that oxygen concentration used is too low.Continuing increases oxygen concentration until this batten is lighted, and observes its combustion time and burning length.If be greater than 180 seconds its combustion time, or its burning length is greater than 50 millimeters, judges that oxygen concentration used is the minimum oxygen concentration of lighting this batten.
2. the LOI of textiles test: rectangular fabric batten is carried out to the LOI test for fabric according to standard GB/T5454-1997, 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 10-15 time of second, put combustible fabric batten top, if batten can not be lighted, 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, judges 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: will adopt the prepared fiber of above-mentioned spinning technique and spinning condition to use electronics single yarn tester test (Japanese Shimadzu company, AG-X PLUS type), at the test environment of 20 ° of C, 65% humidity, measure breaking tenacity and the elongation at break of this fiber, test 20 times, getting its mean value is test result.
According to preceding method, the fire-retardant combination of preparation comparative example 1-8 and embodiment 1-6, and prepare its corresponding test sample (molding batten) and test for the LOI of moulded product, its test result is in table 1, and wherein listed LOI result is the mean value of the test result of 2-4 preparation flame retardant combination matter sample.
Table 1: the composition of fire-retardant combination and LOI test result
* listed each weight percentages of components, disregards the antioxidant of 0.2 % by weight adding in the time of melting mixing.
By the result of table 1, be apparent to draw a conclusion.
Can see by comparative example 2-6, in the time only using the phosphorous-containing polyester (b) (being ME-P8) of formula 1, for example, along with the content of the phosphorous-containing polyester (b) of formula 1 (increases, content is 1 % by weight and 10 % by weight), the flame retardant properties of said composition increases (for example, LOI is 23.0 and 27.5).Can see by comparative example 7-8, in the time only using aluminium oxide nano particle (c), the content of aluminium oxide nano particle (c) (for example, 0.5 % by weight and 2 % by weight) flame retardant properties of said composition is affected to little (for example, LOI is 23.0 and 23.5).
Can see by embodiment 1-6, in the time using the phosphorous-containing polyester (b) of formula 1 and aluminium oxide nano particle (c) simultaneously, in the case of phosphorous-containing polyester (b) content of identical formula 1, add a small amount of aluminium oxide nano particle (c) can obviously improve the flame retardant properties of obtained fire-retardant combination, that is to say, aluminium oxide nano particle (c) has improved the flame retardant effect of the phosphorous-containing polyester (b) of formula 1 synergistically.
According to as preceding method, the prepared fibrage of composition by comparative example 9, embodiment 7 and embodiment 8 is become to fabric, test the flame retardant properties LOI of these fabrics, and test result is listed in to table 2.
Table 2: the flame retardant properties of fabric
* listed each weight percentages of components, disregards the antioxidant of 0.2 % by weight adding in the time of melting mixing.
As can be seen from Table 2, obviously improved by the flame retardant properties of the prepared fabric of fiber that contains the fire-retardant combination based on PTT of the present invention.
Test is by breaking tenacity and the elongation at break of the prepared fiber of fire-retardant combination of comparative example 9, embodiment 7 and embodiment 8, and its result is as shown in table 3.
Table 3: the mechanical property of fiber
For example, even by the physical strength slight reduction of the prepared fiber of fire-retardant combination of the present invention (shown by the result of table 3, embodiment 8), still in the acceptable scope in this area (reducing amount is not more than 15%), or (for example, embodiment 7) even increases.
In present specification, in conjunction with specific embodiments, the present invention is described in detail, but to those skilled in the art, obviously can makes various changes and modifications it without departing from the case in the spirit of the invention.All this type of changes and modification should be thought within the scope of claims of all falling into the application.
Claims (10)
1. fire-retardant combination, it comprises:
(a) Poly(Trimethylene Terephthalate) of 74 % by weight-99.4 % by weight;
(b) fire retardant of 0.5 % by weight-10 % by weight, it is phosphorous-containing polyester as shown in Equation 1:
(c) the aluminium oxide nano particle of 0.1 % by weight-6 % by weight; With
(d) additive of the optional existence of 0-10 % by weight;
Wherein
N is the integer of scope at 22-150; And
Described % by weight is the gross weight based on described fire-retardant combination.
2. fire-retardant combination claimed in claim 1, wherein, described Poly(Trimethylene Terephthalate) (a) is Poly(Trimethylene Terephthalate) homopolymer, Poly(Trimethylene Terephthalate) multipolymer or its any blend, and the propylene glycol ester terephthalate that wherein said Poly(Trimethylene Terephthalate) multipolymer comprises 70mol% is at least as main copolymerization units.
3. fire-retardant combination claimed in claim 1, wherein, the number-average molecular weight of the phosphorous-containing polyester of described formula 1 (b) is 9,000-approximately 50,000.
4. fire-retardant combination claimed in claim 1, wherein, the content of the phosphorous-containing polyester of described formula 1 (b) is 1 % by weight-6 % by weight, and described % by weight is the gross weight based on described fire-retardant combination.
5. fire-retardant combination claimed in claim 1, wherein, the granularity of the primary particle of described aluminium oxide nano particle (c) is about 100nm or less.
6. fire-retardant combination claimed in claim 1, wherein, the content of described aluminium oxide nano particle (c) is 0.2 % by weight-4 % by weight, and described % by weight is the gross weight based on described fire-retardant combination.
7. fire-retardant combination claimed in claim 1, wherein, the additive of described optional existence (d) is selected from: antioxidant, the tinting material that comprises pigment and dyestuff, hydrolysis-resisting agent, lubricant, nucleator, coupling agent, thermo-stabilizer, antistatic agent and UV light stabilizing agent.
8. goods, it comprises fire-retardant combination claimed in claim 1, or is made by fire-retardant combination claimed in claim 1, and wherein said goods comprise fibre product, film or moulded product.
9. goods claimed in claim 8, wherein said goods are fibre products.
10. goods claimed in claim 9, wherein said fibre product is long filament, fiber, short fiber, yarn, fabric or carpet.
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| PCT/US2013/076794 WO2014105669A1 (en) | 2012-12-24 | 2013-12-20 | Polytrimethylene terephthalate-based flame retardant compositions |
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| CN105755616A (en) * | 2016-04-15 | 2016-07-13 | 安踏（中国）有限公司 | Double-component biomass yarn, shell fabric and clothes |
| CN107739433A (en) * | 2017-09-21 | 2018-02-27 | 四川大学 | A kind of terminal hydroxy group phosphorous-containing polyester, preparation method and application and a kind of halogen-free flameproof activeness and quietness epoxy composite material |
| CN111615529A (en) * | 2018-01-16 | 2020-09-01 | 赢创运营有限公司 | Composition containing nanoparticles |
| CN112410921A (en) * | 2020-11-19 | 2021-02-26 | 湖州欣缘纺织有限公司 | Preparation method of anti-static polyester filament yarn with flame-retardant function |
| JP2022044836A (en) * | 2017-12-26 | 2022-03-17 | 三菱ケミカル株式会社 | Method for producing polyester film |
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| US10633591B2 (en) | 2017-10-05 | 2020-04-28 | International Business Machines Corporation | Flame retardant itaconic acid-based compounds |
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