WO2014105669A1 - Compositions retardatrices de flamme à base de poly(téréphtalate de triméthylène) - Google Patents

Compositions retardatrices de flamme à base de poly(téréphtalate de triméthylène) Download PDF

Info

Publication number
WO2014105669A1
WO2014105669A1 PCT/US2013/076794 US2013076794W WO2014105669A1 WO 2014105669 A1 WO2014105669 A1 WO 2014105669A1 US 2013076794 W US2013076794 W US 2013076794W WO 2014105669 A1 WO2014105669 A1 WO 2014105669A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
flame retardant
retardant composition
article
polytrimethylene terephthalate
Prior art date
Application number
PCT/US2013/076794
Other languages
English (en)
Inventor
Ting Yu
Xin Lv
Yi Zhang
Original Assignee
E. I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Publication of WO2014105669A1 publication Critical patent/WO2014105669A1/fr

Links

Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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'
    • 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

Definitions

  • This invention relates to polytrimethylene terephthalate-based flame retardant compositions, particularly relates to polytrimethylene terephthalate-based flame retardant compositions comprising phosphorous containing polyester flame retardants and inorganic nanoparticles.
  • the invention also relates to articles comprising or prepared from the present flame retardant compositions, especially to fibrous articles.
  • Polytrimethylene terephthalate (commonly referred to as "PTT”, “PPT” or “3GT”) is generally prepared by the condensation polymerization of 1,3 -propanediol and terephthalic acid or 1,3 -propanediol and terephthalate ester, and is a new class of aromatic polyester after polyethylene terephthalate (commonly abbreviated to "PET”) and polybutylene terephthalate (commonly abbreviated to "PBT”).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PTT resin has better performance in mechanical properties, weather resistance, heat aging resistance and hydrolysis resistance as compared to that of PET and PBT.
  • PTT fibers combines the softness of nylon fibers, the fluffiness of acrylic fibers and the stain resistance of PBT fibers; meanwhile, it has better color fastness than nylon fibers, and avoids the pilling shortcoming of acrylic fibers, and it also has better hand feel, good inherent elasticity and dyeability at room temperature. Since PTT resin has the excellent performance, it is commonly used in applications such as textile, upholstery, and engineering plastics, especially carpets. However, in some environment, the inherent flame retardancy of PTT resin is insufficient, as a result, it limits the applications of PTT resin in some area.
  • one method is the post-treatment, in which PTT fibers or fabrics are impregnated with flame retardants to form flame retardant PTT fibers or fabrics, the disadvantage of this method is that flame retardancy cannot be sustained, and the appearance of the fibers or fabrics may be negatively affected, this method is also not suitable for engineering plastics;
  • another method is copolymerization, i.e., introducing the flame retardant as commoner into the PTT macromolecular chains to obtain a flame retardant PTT resin, the PTT resin prepared by this method has sustainable flame retardancy, but also has other inherent properties changed at the same time;
  • yet another method is blending, i.e., blending the flame retardant with PTT resin to obtain flame retardant composition, which is subsequently molded or spun into flame retardant fibers or fabrics.
  • the PPT resin prepared by blending has advantages such as simple process and low cost than the PPT resin prepared by copolymerization, the added flame retardants must be uniformly dispersed in the resin matrix without migration, frosting, etc., so as to avoid the flame retandancy of PTT blends decreases or diminishes.
  • halogenated flame retardants cause environmental pollution during manufacturing, recycling and disposing, and generate toxic and harmful gases during burning, therefore, halogenated flame retardants are gradually replaced by halogen-free flame retardants.
  • Halogen-free flame retardants, especially phosphorus containing flame retardants have been widely used in polyesters, especially in polyester fibers.
  • Phosphorus containing flame retardants include reactive type and additive type. When introduced into polyester molecular chains, the reactive type of phosphorus containing flame retardants generally alter the thermal property of the resulting flame retardant polyester and subsequently cause spinning difficulty; moreover, its processing cannot be done on the existing manufacture platform, and requires adjusting equipment or process parameters, thus increases the production cost.
  • Patent application CN101532189A discloses flame retardant PTT fibers and preparation method thereof, which includes a copolymerization method to incorporate flame retardant phosphorus containing monomers (e.g., 2-carboxyethyl alkyl phosphonic acid, 2-phenyl carboxyethyl phosphinic acid and the like) into the molecular chains of PTT polyester, meanwhile, adding inorganic nanoparticles selected from silicon oxide, calcium carbonate, magnesium carbonate and barium sulfate into the copolymerization reactants to obtain the flame retardant PTT polyesters.
  • flame retardant phosphorus containing monomers e.g., 2-carboxyethyl alkyl phosphonic acid, 2-phenyl carboxyethyl phosphinic acid and the like
  • inorganic nanoparticles selected from silicon oxide, calcium carbonate, magnesium carbonate and barium sulfate into the copolymerization reactants to obtain the flame retardant PTT polyesters.
  • Patent application CN101709137A discloses a phosphorus containing flame retardant polyethylene terephthalate copolyester/nanocomposition and preparation method thereof, which includes a copolymerization method to add flame retardant phosphorus containing monomers (e.g., BHET, BHPPO, CEMPP, DDP and the like) to the molecular chains of PTT polyester, simultaneously, adding inorganic nanoparticles selected from barium sulfate, silicon oxide, titanium oxide, zinc oxide and the like to obtain flame retardant PTT polyesters.
  • This patent application also relates to the aforementioned reactive type of phosphorus containing flame retardant.
  • Prior art also discloses blending flame retardants and polyester resin to obtain compositions with improved flame retardancy (i.e., the aforementioned additive type flame retardant), for example, patent application JP2006-144184A discloses a flame retardant polyester composition for artificial hair, that the composition is the blends of a polyester (e.g., PET) and a flame retardant polyester copolymer.
  • the flame retardant polyester copolymer is prepared by copolymerization terephthalic acid, alkylene glycols and phosphorus or bromine containing compound.
  • Patent application JP2007-112875 A discloses a flame retardant polyester resin composition which is prepared by melt mixing 100 parts by weight of polyesters, 10-80 parts by weight of organic phosphorus flame retardants and 10-100 parts by weight of inorganic compounds.
  • the main application of flame retardant polyester resin composition is the molded parts of automobiles, household appliances, electronics, etc., thus inorganic compounds (e.g. mica, talc, etc.) are introduced to increase the mechanical strength and rigidity, and the amount of inorganic compounds is at least 10 parts by weight.
  • the organic phosphorus containing flame retardant is a homopolymer of Formula A:
  • n is an integer in the range of 2-20.
  • PTT compositions that not only have improved flame retardancy and are environmental friendly, and the applications of such compositions include, not limit to engineering plastic, but also fibrous articles such as textiles, upholstery and carpets.
  • the inventors of the present invention found that flame retardant compositions obtained by blending phosphorous containing polyester of Formula 1 and PTT provided improved flame retardancy.
  • the inventors found that adding a small amount of aluminum oxide nanoparticles to the blends of PTT and the phosphorous containing polyester of Formula 1 (b) synergistically improves the flame retardancy of the phosphorous containing polyester of Formula 1 (b) .
  • the present invention provides a flame retardant composition
  • a flame retardant composition comprising:
  • n is an integer ranging from 22 to 150;
  • the weight percent is based on the total weight of the flame retardant composition.
  • the polytrimethylene terephthalate (a) is a polytrimethylene terephthalate homopolymer, a polytrimethylene terephthalate copolymer, or blends thereof, wherein the polytrimethylene terephthalate copolymer contains at least 70 mol % of trimethylene terephthalate as the major copolymerized unit.
  • the amount of the polytrimethylene terephthalate (a) is about 74 weight % to about 99.4 weight %, or about 85 weight % to about 95 weight %, based on the total weight of the flame retardant composition.
  • the average number molecular weight of the flame retardant (b), i.e., the phosphorus containing polyester of Formula 1, is from 9,000 to about 50,000.
  • the amount of the flame retardant (b) is about 0.5 weight % to about 10 weight %, or about 1 weight % to about 6 weight %, based on the total weight of the flame retardant composition.
  • the primary particle size of the alumina oxide nanoparticles (c) is about 100 nm or less, or from about 1 nm to about 80 nm, or from about 10 nm to about 70 nm, or from about 20 nm to about 50 nm.
  • the amount of the aluminum oxide nanoparticles (c) is from about 0.1 weight % to about 6 weight %, or from about 0.2 weight % to about 4 weight %, or from about 0.3 weight % to about 2 weight %, based on the total weight of the flame retardant composition.
  • the optional additive (d) is selected from the group consisting of antioxidants, colorants including dyes and pigments, hydrolysis resistants, lubricants, nucleating agents, coupling agents, thermal stabilizers, anti-static agents and ultraviolet light stabilizers.
  • the amount of the optional additive (d) is typically from 0 to about 10 weight %, or from about 0.01 weight % to about 6 weight %, or from about 0.1 weight % to about 2 weight %, based on the total weight of the flame retardant composition.
  • the invention also relates to an article comprising or produced from the flame retardant compositions mentioned above, especially to a fibrous article, wherein the fibrous article is filaments, fibers, staple fibers, yarns, fabrics, or carpets.
  • mol % refers to mole percent
  • the term “produced from” is synonymous to "comprising”.
  • the terms “includes”, “including”, “comprises”, “comprising”, “has”, “having”, “contains” or “containing”, or any other variation thereof are intended to cover a nonexclusive inclusion.
  • a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • “or” refers to an inclusive “or” and not to an exclusive “or”. For example, a condition A “or” B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • Suitable PTT resin for the present invention is a PTT homopolymer, a PTT copolymer or blends thereof.
  • the preferred PTT resin is a PTT homopolymer.
  • terephthalic acid equivalent refers to the compound having essentially the same properties as terephthalic acid in the reactions with diol.
  • terephthalic acid equivalents include esters of terephthalic acid (e.g., dimethyl terephthalate) and derivatives of ester precursor of other (e.g., acid halides and acid anhydrides).
  • esters of terephthalic acid e.g., dimethyl terephthalate
  • ester precursor of other e.g., acid halides and acid anhydrides.
  • terephthalic acid equivalent is terephthalic acid and dimethyl terephthalate are preferred.
  • copolymer refers to polymers copolymerized from two or more comonomers, i.e., polymers comprising two or more species of repeating units.
  • PTT copolymer preferably contains 70 mol% or more, or 80 mol% or more, or 90 mol% or more, or 95 mol% or more of polytrimethylene terephthalate, and the rest are the derivatives from the monomers excluding terephthalic acid and 1,3- propanediol (such as glycol, butanediol, etc.).
  • blends means a mixture of two or more components.
  • PTT blends can be prepared by blending PTT homopolymers or PTT copolymers; the PPT blends preferably contain about 80 weight % or more, or about 90 weight % or more, or about 95 weight % or more of PTT homopolymers or PTT copolymers, based on the total weight of the PTT blends.
  • Suitable PTT resin for the present invention is commercially available, Sorona ® from DuPont, for example, in accordance with matting agent content, there are various classes including bright, semi-bright, semi-dull and dull, and each class further includes several types of PTT resins having different intrinsic viscosity (IV).
  • the amount of PTT resin in the flame retardant composition of the present invention, the amount of PTT resin
  • (a) is from about 74 weight % to about 99.4 weight %, or from about 85 weight % to about 95 weight %, based on the total weight of the flame retardant composition.
  • the flame retardant (b) employed in the present invention is a phosphorus containing polyester of Formula 1:
  • n is an integer ranging from 22 to 150.
  • suitable flame retardant (b) of the present invention i.e., a phosphorus containing polyester of Formula 1
  • PTT resin i.e., PTT resin
  • the phosphorus containing polyester of Formula 1 of the present invention should not degrade at the typical spinning temperature of PTT.
  • Typical spinning temperature of PTT is between 240 °C and 290 °C.
  • the average number molecular weight of the phosphorus containing polyester of Formula 1 (b) preferably is at least about 9,000; or about 9,500; or about 10,000.
  • the average number molecular weight of the phosphorus containing polyester of Formula 1 (b) preferably is no more than about 50,000; or 40,000; or 30,000; or 20,000.
  • the average number molecular weight of the phosphorus containing polyester of Formula 1 (b) can be measured by gel permeation chromatography (GPC), see US2006/025824A1.
  • the average number molecular weight of the flame retardant (b), i.e. the phosphorus containing polyester of Formula 1, is from about 9,000 to about 50,000; or from about 9,500 to about 40,000; or from about 10,000 to about 30,000.
  • Suitable flame retardant (b), i.e. the phosphorus containing polyester of Formula 1 can be synthesized by methods known to one skilled in the art, for example, the condensation polymerization method disclosed in Patent Application JP2007-112875 A, which is obtained by reacting directly 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- oxide (DOPO, CAS No. 35848-25-5), itaconic acid (CAS No. 2170-03-8), ethylene glycol and suitable catalyst.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- oxide
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- oxide
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- oxide
  • itaconic acid CAS No. 2170-03-8
  • the phosphorus containing polyester of Formula 1 is also commercially available, for example, the phosphorus containing homopolymer under trade name of ME-P8 from Sanko Co. Ltd., Japan.
  • the amount of the phosphorus containing polyester of Formula 1 (b) is from about 0.5 weight % to about 10 weight %, or from about 1 weight % to about 6 weight %, based on the total weight of the flame retardant composition.
  • nanoparticles is broadly defined as the particles with at least one dimension smaller than 1 ⁇ .
  • the shape of the nanoparticles can be sphere, needle, rod, plate, or other irregular shape.
  • the ratio between the length of the largest dimension and the length of the smallest dimension is defined as aspect ratio.
  • alumina oxide nanoparticles (c) employed in the present invention are within the aforementioned definitions, there is no special limitation for the shape, size, and particle distribution curve shown as unimodal or bimodal.
  • Alumina oxide nanoparticles (c) of the present invention are typically spherical or nearly spherical shape.
  • the primary particle size (i.e., non- agglomeration state) of the alumina oxide nanoparticles (c) employed in the present invention is about 100 nm or less, or from about 1 nm to about 80 nm, or from about 10 nm to about 70 nm, or from about 20 nm to about 50 nm.
  • Alumina oxide nanoparticles (c) of the present invention can form agglomerates, which have a size of from about 50 nm to about 300 nm, depending on the dispersion degree of the alumina oxide nanoparticles (c) in the polymer matrix.
  • the size of the nanoparticles and the dispersion of them in the polymer matrix can be determined by for example, confocal laser scanning electron microscope (SEM). Description of the method can refer to "Confocal and Two-Photon Microscopy", Alberto Diaspro editing; ISBN 0-471-40920-0, Wiley-Liss, John Wiley & Sons, Inc. Publishing, Chapter 2, Page 19-38, and the literature cited therein. In addition, the size of the nanoparticles and the dispersion of them in the polymer matrix can be determined by TEM, too.
  • Suitable alumina oxide nanoparticles (c) are commercially available; for examples, Hangzhou Wan Jing New Material Co., Ltd. provides alumina oxide nanoparticles under trade name of nano alumina oxide that have various size and surface treatment.
  • the amount of alumina oxide nanoparticles (c) is from about 0.1 weight % to about 6 weight %, or from about 0.2 weight % to about 4 weight %, or from about 0.3 weight % to about 2 weight %, based on the total weight of the flame retardant composition.
  • the flame retardant compositions of the present invention may optionally include additives selected from the group consisting of antioxidants, colorants (including dyes and pigments), hydrolysis resistants, lubricants, nucleating agents, coupling agents, thermal stabilizers, anti-static agents and ultraviolet light stabilizers.
  • additives selected from the group consisting of antioxidants, colorants (including dyes and pigments), hydrolysis resistants, lubricants, nucleating agents, coupling agents, thermal stabilizers, anti-static agents and ultraviolet light stabilizers.
  • the antioxidants for example, are hindered phenol antioxidants.
  • the colorants are usually dry powders to impart color to the compositions or articles (e.g., fibers), which may be inorganic or organic, natural or synthetic; generally, the colorants are inert (for example, charge neutral and do not react with the polymer).
  • the hydrolysis resistants are carbodiimide hydrolysis resistants.
  • the lubricants for example, are TAF lubricants.
  • the nucleating agent may be inorganic or organic, such as nano silicon oxide, organic carboxylate salt, organic phosphonate salts, etc.
  • the coupling agents for example, are silane or titanate coupling agents.
  • the heat stabilizers for example, are large molecules hindered amines, phosphate and copper halides.
  • the ultraviolet light stabilizers for example, are benzotriazole ultraviolet absorbers or benzophenone ultraviolet absorbers.
  • the anti-static agents include five common types of anti-static agents, i.e., amine derivative, quaternary ammonium salts, sulfuric acid esters, phosphate esters and polyethylene glycol derivatives.
  • the amount of the optional additive (d) is generally form 0 to about 10 weight %, or from about 0.01 weight % to about 6 weight %, or from about 0.1 weight % to about 2 weight %, based on the total weight of the flame retardant composition, so long as they do not detract from the basic and novel characteristics of the flame retardant compositions and do not significantly adversely affect the performance of the flame retardant compositions.
  • the flame retardant compositions of the present invention may be prepared by general blend techniques known in the art, the components (a)-(c) and the optional additives (d) are typically in powder or granule form at room temperature, the blended compositions can be obtained by combining the components (a)-(c) and the optional additive (d) using various methods, e.g., heating and mixing at molten state simultaneously , pre-mixing (such as dry mixing) before heating, or mixing after heating separately. Mixing and heating described above can be processed in the equipments known in the art such as extruder or other mixer, etc.
  • the components (a)-(c) and optional additives (d) in powder or granular form are blended at the melt temperature, extruded and comminuted into pellets or other suitable shapes.
  • pellets is used generically in this regard, although sometimes called “chips”, “flakes”, etc.
  • the flame retardant composition is prepared by melt blending the components (a)-(c) and optional additive (d).
  • the flame retardant compositions of the present invention can be produced into molded articles by conventional molding apparatus; or can be spun into as-spun yarn, and then drawn into filaments by re-melting the pellets prepared therefrom, or spun directly using the conventional spinning apparatus know to one skilled in the art.
  • the blending temperatures should be higher than the melting point of each component, but lower than the lowest decomposition temperature of each component, and must be adjusted according to the PTT resin (a), component (b), component (c) and/or component (d) of the flame retardant composition.
  • the blending temperature is generally from about 180°C to about 290°C, preferably at least about 220°C, and more preferably up to about 280°C, depending on each component of the present invention.
  • the component (b), component (c) and/or component (d) can be uniformly dispersed in the PTT resin matrix of component (a) through melt blending, and the structure of the resulting flame retardant composition of the present invention can be determined by electron microscope such as transmission electron microscopy (TEM) and scanning electron microscope (SEM).
  • the PTT -based flame retardant composition of the present invention can be produced into fibrous articles, films, molded articles and other shaped articles of various shape and forms.
  • the term "fibrous articles” includes, but are not limited to, filaments, fibers, staple fibers, yarns, fabrics, carpets or other textile products, and are for applications such as garments, home furnishings, carpets, and other consumer products.
  • the flame retardant compositions of the present invention can be produced into filaments with various shape and fineness, the filaments can be produced into fibers or yarns through steps comprising doubling, twisting and stranding, or be cut into staple fibers.
  • the filaments, fibers, staple fibers and yarns can be produced into fabrics, carpets, and other textile products.
  • the fibrous articles of the present invention may be knitted, woven or nonwoven.
  • Nonwoven fabric of the present invention is a web or matt of fibers or staple fibers which are bound by the application of heat, entanglement, and/or pressure.
  • a filament may be round or in other shape such as octalobal, delta, sunburst (also known as sol), scalloped oval, trilobal, tetra-channel (also known as quatra-channel), scalloped ribbon, ribbon, starburst, etc.
  • the filament may be solid, hollow, or multi- hollow, and are preferably solid.
  • the general size of a suitable filament for most applications such as fabrics and carpets is at least about 0.5 dpf (denier per filament), and up to about 35 dpf.
  • the monofilament may be thicker and is from about 10 dpf to about 2000 dpf.
  • PTT-based flame retardant compositions of the present invention is preferably for fibrous articles, include filaments, fibers, staple fibers, yarns, fabrics, and carpets.
  • use of the flame retardant composition of the present invention is for fibrous articles, films or molded articles.
  • use of the flame retardant composition of the present invention is for fibrous articles, wherein the fibrous articles include filaments, fibers, staple fibers, yarns, fabrics, or carpets.
  • PTT-based flame retardant compositions are obtained by blending PTT with the phosphorous containing polyester of Formula 1 (b) and alumina oxide nanoparticles (c). Additionally, the flame retardant compositions of the present invention can be successfully spun into filaments without blocking the spinning die, i.e., good spinability because the phosphorous containing polyester of Formula 1 (b) and alumina oxide nanoparticles (c) were uniformly dispersed in the PTT matrix. Furthermore, the mechanical properties of the fibrous articles produced from the flame retardant compositions are not significantly adversely affected. When compared to PTT fibrous articles without flame retardant, the mechanical properties of the fibrous articles produced from the inventive flame retardant compositions are not significantly worsen, sometimes are even improved. EXAMPLES
  • PTT polytrimethylene terephthalate under trade name of Sorona ® semidull grade with intrinsic viscosity (IV) of 1.02 dL/g was obtained from E. I. DuPont de Nemours and Company (DuPont).
  • ME-P8 phosphorus containing polyester of Formula 1, CAS No. 403614-60-8, was purchased from Sanko Co. Ltd., Japan, the number average molecular weight was about 10,000, and the phosphorus content is 7.8-8.2 %.
  • Alumina oxide nanoparticles purchased from Hangzhou Wan Jing New Material Co. Ltd., trade name: nano alumina oxide, surface treated with 2% silane coupling agent, particle size was 30-50 nm as measured by TEM.
  • IRGANOX ® 1010 antioxidant, tetrakis(methylene-3-(3,5-di-t-butyl-4- hydroxyl- phenyl)propionate)methane (CAS No. 6683-19-8), a phenolic antioxidant, purchased from BASF.
  • each example and comparative example were fed batchwise to a twin screw extruder (Coperion Co. Ltd., ZSK-26 MC) to obtain the corresponding flame retardant composition as pellets.
  • the temperature of the extruder was set to be 180/240/240/240/240/240/240/240/230°C with a die temperature of 230 °C, the screw speed was at 300 rpm with a throughput of 20 Kg/hour.
  • the batch size of each example is about 4.0 Kg (molded articles) or 10 Kg (fibrous articles); moreover, 0.2 % of antioxidant was additionally added based on the total weight of each batch.
  • test specimen according to GB/T 2406.2-2009 was molded on a Sumitomo 100 Ton molding machine with a screw diameter of 32 mm and a nozzle diameter of 5 mm.
  • the barrel temperature was set to be 240 °C, and the molding temperature was 80 °C.
  • the test specimen for mechanical property tests had the basic dumbbell shape, 150 mm long, with the center section 10 mm wide by 4 mm thick by 80 mm long.
  • the test specimen for flame retardant property tests had the rectangle shape with 10 mm wide by 4 mm thick by 80 mm long.
  • the extruded pellets were dried in an oven at 120 °C for 8 hours prior to melt spinning, then the dried pellets were metered to a single screw extruder (Fuji E0200), then at suitable temperature (250 °C-270 °C), to a Fuji melt-spinning tester (Model ABE) at the speed of 27 mL/min to obtain the fibers; the Fuji melt-spinning tester was equipped with a 36 hole spinneret pack, with a diameter of 100 mm, each hole has a diameter of 0.3 mm and a L/D ratio of 2.
  • the spun fibers were drawn in a drawing twisting machine (Suzhou Tefa Electromechanical Technology Development Co.
  • pellets of other Examples and Comparative Examples were all melt spun with same parameters to evaluate the spinability of the respective flame retardant compositions.
  • mechanical properties of the as-prepared fibers were tested to evaluate their tenacity and elongation at break.
  • LOI Limiting Oxygen Index
  • the basic testing and mechanism of LOI test include: placing the test specimen in a transparent cylinder with an upward flowing mixture of nitrogen and oxygen inside, igniting the top of the test specimen to observe the burning, and comparing the continuous burning duration and the burned length with the criteria in relevant standard. A series of tests were done under various oxygen concentrations, and the minimum oxygen concentration needed for burning was recorded. 1.
  • LOI test of molded article in the present invention, LOI of molded article was tested according to the standard of GB/T 2406.2-2009, and the test equipment was from Textile Research Institute, Shandong province (Model JF-3LSY-605 automatic oxygen index tester), the testing steps are as follows:
  • LOI test of textile LOI of the rectangular fabric is test according to the standard of GB/T 5454-1997, and the test equipment is purchased from Textile Research Institute, Shandong City (Model JF-3LSY-605 automatic oxygen index tester), the testing steps are as follows:
  • the test specimen Igniting the top of the test specimen of fabric sample in 10-15 seconds, if the test specimen cannot be ignited, it indicates that the oxygen concentration is too low. If the test specimen can be ignited, recoding its after-glow duration, sustained burning duration and burned length. If the after-glow duration, or the sustained burning duration, or the total of the after-glow duration and the sustained burning is more than 2 minutes, or the burned length is greater than 40 mm, it indicates the oxygen concentration used in the test is the minimum oxygen concentration needed for igniting the test specimen.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • 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)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions retardatrices de flamme à base de poly(téréphtalate de triméthylène) et des articles fibreux produits à partir de celles-ci. Les compositions retardatrices de flamme comprennent (a) 74 % en poids à 99,4 % en poids de poly(téréphtalate de triméthylène) ; (b) 0,5 % en poids à 10 % en poids d'un retardateur de flamme, qui est un polyester contenant du phosphore de formule 1, dans laquelle n est un entier se situant dans la plage de 22 à 150 ; (c) 0,1 % en poids à 6 % en poids de nanoparticules d'oxyde d'aluminium ; et (d) 0 à 10 % en poids d'un additif facultatif ; le pourcentage en poids étant sur la base du poids total de la composition retardatrice de flamme.
PCT/US2013/076794 2012-12-24 2013-12-20 Compositions retardatrices de flamme à base de poly(téréphtalate de triméthylène) WO2014105669A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201210567564.4 2012-12-24
CN201210567564.4A CN103897353A (zh) 2012-12-24 2012-12-24 基于聚对苯二甲酸丙二醇酯的阻燃组合物

Publications (1)

Publication Number Publication Date
WO2014105669A1 true WO2014105669A1 (fr) 2014-07-03

Family

ID=49943571

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/076794 WO2014105669A1 (fr) 2012-12-24 2013-12-20 Compositions retardatrices de flamme à base de poly(téréphtalate de triméthylène)

Country Status (2)

Country Link
CN (1) CN103897353A (fr)
WO (1) WO2014105669A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019141624A1 (fr) * 2018-01-16 2019-07-25 Evonik Degussa Gmbh Compositions contenant des nanoparticules
US10633591B2 (en) 2017-10-05 2020-04-28 International Business Machines Corporation Flame retardant itaconic acid-based compounds

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105755616B (zh) * 2016-04-15 2018-02-02 安踏（中国）有限公司 一种生物质双组份纱线、面料及服装
CN107739433B (zh) * 2017-09-21 2020-02-07 四川大学 一种端羟基含磷聚酯、制备方法及应用以及一种无卤阻燃增强增韧环氧复合材料
JP7327537B2 (ja) * 2017-12-26 2023-08-16 三菱ケミカル株式会社 ポリエステルフィルムの製造方法
CN112410921A (zh) * 2020-11-19 2021-02-26 湖州欣缘纺织有限公司 一种具有阻燃功能的防静电涤纶长丝的制备方法

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6281325B1 (en) 1999-08-25 2001-08-28 E. I. Du Pont De Nemours And Company Preparation of poly(trimethylene terephthalate)
US20060025824A1 (en) 2004-05-12 2006-02-02 Freeman Gary A Automatic therapy advisor
JP2006144184A (ja) 2004-11-22 2006-06-08 Kaneka Corp 難燃性ポリエステル系人工毛髪
JP2007112875A (ja) 2005-10-19 2007-05-10 Kaneka Corp 難燃性ポリエステル樹脂組成物
US20090198011A1 (en) * 2007-12-18 2009-08-06 Kailash Dangayach Polymer composition containing flame retardant and process for producing the same
CN101532189A (zh) 2009-04-07 2009-09-16 江苏中鲈科技发展股份有限公司 一种阻燃ptt聚酯纤维及其生产方法
US20090253837A1 (en) * 2005-03-31 2009-10-08 Kaneka Corporation Flame Retardant Polyester Resin Composition
CN101709137A (zh) 2009-11-25 2010-05-19 四川大学 含磷聚对苯二甲酸丙二醇酯阻燃共聚酯/纳米复合材料及其制备方法
US20100181696A1 (en) * 2008-03-06 2010-07-22 Udo Glauner Halogen-free flame retardants
US20120322923A1 (en) * 2009-12-31 2012-12-20 Chemische Fabrik Budenheim Kg Flame retardant composition for thermoplastic molding compounds

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6281325B1 (en) 1999-08-25 2001-08-28 E. I. Du Pont De Nemours And Company Preparation of poly(trimethylene terephthalate)
US20060025824A1 (en) 2004-05-12 2006-02-02 Freeman Gary A Automatic therapy advisor
JP2006144184A (ja) 2004-11-22 2006-06-08 Kaneka Corp 難燃性ポリエステル系人工毛髪
US20090253837A1 (en) * 2005-03-31 2009-10-08 Kaneka Corporation Flame Retardant Polyester Resin Composition
JP2007112875A (ja) 2005-10-19 2007-05-10 Kaneka Corp 難燃性ポリエステル樹脂組成物
US20090198011A1 (en) * 2007-12-18 2009-08-06 Kailash Dangayach Polymer composition containing flame retardant and process for producing the same
US20100181696A1 (en) * 2008-03-06 2010-07-22 Udo Glauner Halogen-free flame retardants
CN101532189A (zh) 2009-04-07 2009-09-16 江苏中鲈科技发展股份有限公司 一种阻燃ptt聚酯纤维及其生产方法
CN101709137A (zh) 2009-11-25 2010-05-19 四川大学 含磷聚对苯二甲酸丙二醇酯阻燃共聚酯/纳米复合材料及其制备方法
US20120322923A1 (en) * 2009-12-31 2012-12-20 Chemische Fabrik Budenheim Kg Flame retardant composition for thermoplastic molding compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ALBERTO DIASPRO: "Confocal and Two-Photon Microscopy", WILEY-LISS, JOHN WILEY & SONS, INC. PUBLISHING, ISBN: 0471409200, article "2", pages: 19 - 38

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10633591B2 (en) 2017-10-05 2020-04-28 International Business Machines Corporation Flame retardant itaconic acid-based compounds
WO2019141624A1 (fr) * 2018-01-16 2019-07-25 Evonik Degussa Gmbh Compositions contenant des nanoparticules
JP2021511396A (ja) * 2018-01-16 2021-05-06 エボニック オペレーションズ ゲーエムベーハー ナノ粒子含有組成物
US11718747B2 (en) 2018-01-16 2023-08-08 Evonik Operations Gmbh Nanoparticle containing compositions

Also Published As

Publication number Publication date
CN103897353A (zh) 2014-07-02

Similar Documents

Publication Publication Date Title
KR101913669B1 (ko) 폴리에스테르 섬유를 위한 난연제로서의 포스포네이트 중합체, 공중합체, 및 이들의 각각의 올리고머
WO2014105669A1 (fr) Compositions retardatrices de flamme à base de poly(téréphtalate de triméthylène)
KR101314878B1 (ko) 고권축성 2성분 섬유
US5348699A (en) Fibers from copolyester blends
KR101162372B1 (ko) 폴리(트리메틸렌 테레프탈레이트) 이성분 섬유
KR101059594B1 (ko) 폴리(트리메틸렌 디카르복실레이트) 섬유, 그의 제조 및용도
JP2010510397A (ja) 難燃剤を含有するポリマー繊維、この製造方法およびこのような繊維を含有する材料
JP2003514092A (ja) 酸性染色性ポリエステル組成物
AU2014341887A1 (en) Multipolymer fibers and method of making same
EP1534492B1 (fr) Fibres de poly(trimethylene terephthalate) et leur fabrication
WO2006094315A2 (fr) Composition pour produire des fils de polyester ignifuges
US6630240B2 (en) Bulky polyester multifilament composite yarn and process for producing the same
JP5312142B2 (ja) ポリカーボネート繊維およびその製造方法、ならびに繊維集合物
CN103665780B (zh) 基于聚对苯二甲酸丙二醇酯的阻燃组合物
KR101737010B1 (ko) 폴리에스테르 수지 조성물, 이로부터 제조된 가발모용 원사 및 그 제조방법
EP2764144A1 (fr) Tissu comprenant des filaments de poly(arylate de triméthylène)
EP2758571A1 (fr) Fibres de poly(triméthylène arylate), leur procédé de fabrication et tissu préparé avec celles-ci
KR101231602B1 (ko) 인공 모발용 인계 폴리에스테르계 섬유 및 이로부터 인공 모발 섬유를 제조하는 방법
JP2011106060A (ja) ポリアリーレンスルフィド繊維
JP2023121109A (ja) 共重合ポリエステル樹脂及びその製造方法
US20110263171A1 (en) Poly(trimethylene arylate) fibers, process for preparing, and fabric prepared therefrom
KR101043149B1 (ko) 폴리(트리메틸렌 테레프탈레이트) 섬유, 그의 제조 및 용도
JP2010059580A (ja) 芯鞘型複合繊維

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13818936

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13818936

Country of ref document: EP

Kind code of ref document: A1