CN104693692A - Flame-resistance polytrimethylene terephthalate composition and product thereof - Google Patents
Flame-resistance polytrimethylene terephthalate composition and product thereof Download PDFInfo
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- CN104693692A CN104693692A CN201310652732.4A CN201310652732A CN104693692A CN 104693692 A CN104693692 A CN 104693692A CN 201310652732 A CN201310652732 A CN 201310652732A CN 104693692 A CN104693692 A CN 104693692A
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Abstract
The invention relates to a flame-resistance composition, which basically comprises the following components: a)about 20-60wt% of polytrimethylene terephthalate resin; b)about 20-55wt% of fiber reinforcing agent; c)about 10-30wt% of fire retardant, which is a mixture of phosphinate and aromatic polyphosphoester; d)about 1-10wt% of aromatic polycarbonate; and e)about 0.1-10wt% of additive, wherein the weight percentage is based on total weight of the flame resistance composition. The flame-resistance composition and a mould prepared by the flame-resistance composition have excellent machinery performance and can display increased flame retardation performance, so that a V-0 grade of a UL94 flame retardation standard can be reached. (thickness of testing sample stripes is 0.8mm ).
Description
Technical field
The present invention relates to flame retardance poly propylene glycol ester terephthalate composition, particularly relate to the Poly(Trimethylene Terephthalate) composition comprising halogen-free flame retardants and glass fiber reinforcement.
Background technology
Comprise the polyester product of the glass fiber reinforcement of fire retardant, as polybutylene terephthalate (being usually called for short " PBT ") and polyethylene terephthalate (being usually called for short " PET "), be widely used in electronic apparatus (E/E) equipment.Poly(Trimethylene Terephthalate) (usually referred to as " PTT ", " PPT " or " 3GT ") is a kind of new aromatic polyester after PBT and PET.PTT resin is more excellent than PBT and PET in mechanical characteristics, weathering resistance, heat-resistant aging and resistance to hydrolysis.Due to the excellent properties of PTT, it can be widely used in the every field such as dress material, decoration and engineering plastics.But usually add in these products and have halogen-containing fire retardant, and these halogen-containing flame retardant polyester products are by some environmental legislations and regulations, such as RoHS and WEEE, strict restriction uses, and therefore the use of these polyester products is faced with increasing environmental problem.
Although be developed some not halogen-containing fire retardants to meet the requirement of environmental legislation and regulations, but adding of these halogen-free flame retardantss causes the mechanical property of this polyester product to reduce usually, therefore be difficult to fully substitute halogen-containing flame retardant polyester product, thus limit the widespread use of the polyester product containing halogen-free flame retardants.
US2009/0088512A1 discloses a kind of flame retardant polyester composition and comprises: the thermoplastic polyester of (a) 40-64.9 % by weight, the polycarbonate of (b) 5-10 % by weight, formula (I) phosphinates of (c) 10-15 % by weight, the bisphosphinic acid salt of formula (II) and/or their polymkeric substance, the melamine pyrophosphate of (d) 5-10 % by weight, the strongthener (glass fibre) of (e) 15-30 % by weight and other additives of (f) 0.1-2 % by weight.Described composition is because of the fire retardant containing melamine class, and it easily produces mold deposit in injection moulding production process, needs often to shut down to clear up, thus has a strong impact on production efficiency.
DE19904814 discloses a kind of thermoplastic shaping material, it comprises: the polyester of (a) 20-98 % by weight, the polycarbonate of (b) 1-50 % by weight, formula (I) phosphinates of (c) 1-40 % by weight, the bisphosphinic acid salt of formula (II), and/or their polymkeric substance, the nitrogenous flame ratardant of (d) 0-40 % by weight, such as trimeric cyanamide-tricyanic acid affixture, the at least one ester obtained by the unsaturated aliphatic carboxylic acid with 10-40 carbon atom and the representative examples of saturated aliphatic alcohol or amine with 2-40 carbon atom of (e) 0-50 % by weight or acid amides, and the optional additive of (f) 0-60 % by weight.Embodiments all in this specification sheets be about 30 % by weight PBT, the polycarbonate of 20 % by weight, the glass fibre of 30 % by weight and the phospho acid calcium of 20 % by weight or the equal amount of mixture of phospho acid calcium and trimeric cyanamide based flame retardant.Although described thermoplastic shaping material can solve the migration problem of component (c) in polyester (a) by the polycarbonate (b) adding high-content; if the fire retardant (d) of its fire retardant systems mixing melamine class; it easily produces mold deposit in injection moulding is produced; need often to shut down to clear up, thus have a strong impact on production efficiency.
Still exploitation one is needed to have good flame-retardance energy concurrently at present, the PTT matrix material containing halogen-free flame retardants and fiberglass reinforced of mechanical property and processing characteristics, in order to substitute the PTT matrix material of traditional halogen-containing flame retardant, thus widen the application of halogen-free flame-retardance PTT matrix material in electronic and electrical equipment.
Summary of the invention
The invention provides a kind of flame retardance poly propylene glycol ester terephthalate composition comprising halogen-free flame retardants and glass fiber reinforcement, the moulded product obtained by said composition not only has excellent mechanical property, and show the flame retardant properties of raising unexpectedly, thus reach the V-0 rank (thickness of its test bars is 0.8mm) of UL94 flame-retardant standard.
The invention provides a kind of flame-retardant composition, it is substantially composed of the following components:
The polytrimethylene terephthalate of (a) about 20-60 % by weight;
The fiber enhancer of (b) about 20-55 % by weight;
The fire retardant of (c) about 10-30 % by weight, it is the mixture of phosphinates and aromatic polyphosphate ester;
The aromatic copolycarbonate of (d) about 1-10 % by weight; With
The additive of (e) about 0.1-10 % by weight, it is selected from: antioxidant, anti-dripping agent, chainextender, the tinting material comprising dyestuff and pigment, releasing agent, flow ability modifying agent, hydrolysis-resisting agent, lubricant, nucleator, thermo-stabilizer, UV light stabilizing agent and its combination;
Wherein said weight percentage is the gross weight based on described flame-retardant composition.
The present invention goes back the moulded product of providing package containing flame-retardant composition of the present invention, or the moulded product obtained by flame-retardant composition of the present invention.Described moulded product has excellent mechanical property and flame retardant properties.
The present invention provides again a kind of method preparing flame-retardant composition of the present invention, comprising:
I. the component (a) of flame-retardant composition of the present invention, (b), (c), (d) and (e) is provided for;
Ii. in the forcing machine of 240 DEG C-270 DEG C mixing said ingredients to form mixed uniformly flame-retardant composition; With
Iii. by described flame-retardant composition extruding pelletization;
Wherein, the flame retardant properties of described flame-retardant composition meets the V-0 rank of UL94, and the thickness of its test bars is 0.8mm.
Embodiment
Unless otherwise indicated, all publication that the present invention mentions, patent application, patent and other reference are incorporated into herein all by reference in full, are equivalent to be presented in herein in full.
Unless otherwise defined, all technology used herein and scientific terminology have usual the understood same implication of one skilled in the art of the present invention.In case of conflict, be as the criterion with the definition of this specification sheets.
Term used herein " comprises ", " comprising ", " having ", " having ", " containing " or its any other variant are intended to contain comprising of non-exclusionism.Such as, comprise the composition of a series of key element, technique, method, goods or equipment and might not be only limited to those key elements, but can also comprise these compositions, technique, method, goods or equipment the key element clearly do not enumerated or other intrinsic key elements.
Term " by ... composition/form " do not comprise any key element, step or the composition clearly do not enumerated.If there is in the claims, this conjunction does not comprise making this claim be limited to described material the material do not described, but still comprises the impurity usually relevant to the material described by those.When conjunction " by ... composition/form " appears at the characteristic of claim, but not immediately preamble time, it is only limitted to the key element set forth in characteristic; Other key elements are not required to get rid of in entirety by Accessory Right.
Term " substantially by ... composition " is for also comprising the combination of other material, step, feature, component or key element, method or equipment outside definite division literal described those materials, step, feature, component or key element, prerequisite is essential characteristic and the novel feature that these other material, step, feature, component or key elements substantially do not affect invention required for protection.Conjunction " substantially by ... composition " be in " comprising " and " by ... form " between rank, position.
Term " comprise " intention comprise conjunction " substantially by ... composition " and " by ... form " embodiment that contains.Similarly, conjunction " substantially by ... composition " intention comprises conjunction " by ... the composition " embodiment that contains.
In this article, term " by ... obtained " be equal to " comprising ".
When term " about " and " approximately " are for describing the end value of numerical value or scope, disclosed content is understood to include occurrence or involved end value.
In addition, contrary unless expressly stated, "or" refers to the "or" of pardon but not exclusive "or".Such as, below arbitrary condition all applicable elements A "or" B:A be true (or existence) and B is false (or not existing), A is false (or not existing) and B is true (or existence), and A and B is true (or existence).
Unless otherwise indicated, all percentage ratio, number, ratio etc. are all by weight.
" % by mole " refers to molar percentage.
In time stating certain amount, concentration or other value or parameter with the form of scope, preferable range or preferred numerical upper limits and preferred numerical lower limits, be to be understood that and be equivalent to specifically disclose any scope by any pair range limit or preferred value being combined with any range lower limit or preferred value, and do not consider whether this scope specifically discloses.Unless otherwise noted, numerical range listed herein is intended to the end points comprising scope, and all integers within this scope and mark.
In this article, " halogen-free flame retardants " refers to that in fire retardant, content of halogen is less than 100ppm.
Describe the present invention below.First component (a)-(e) of composition flame-retardant composition of the present invention described.
(a) Poly(Trimethylene Terephthalate)
In flame-retardant composition of the present invention, the Poly(Trimethylene Terephthalate) (PTT) of described component (a) can be PTT homopolymer, PTT multipolymer or its blend.Preferably PTT homopolymer.
Term " homopolymer " refers to the polymkeric substance only containing a kind of repeating unit.In the present invention, " PTT homopolymer " refers to the polymkeric substance obtained by the polycondensation of 1,3-PD and terephthalic acid or terephthalic acid equivalent.Wherein, " terephthalic acid equivalent " refer to glycol reaction in show substantially with the compound of terephthalic acid same nature.For the object of the invention, terephthalic acid equivalent comprises the low carbon number alcohol ester (such as terephthalic acid diformazan alcohol ester) of such as terephthalic acid and forms the derivative (such as carboxylic acid halides and acid anhydrides) of ester.Generally speaking, preferred terephthalic acid and terephthalate.Be used for preparing the 1,3-PD of PTT preferably by biochemical method, obtained (" biological process obtains " 1,3-PD) by renewable resources.
Term " multipolymer " refers to by the polymkeric substance of two or more monomer polymerizations, the polymkeric substance namely containing two or more repeating units.In the present invention, " PTT multipolymer " preferably comprises 70 % by mole or higher or 80 % by mole or higher or 90 % by mole or higher or 95 % by mole or higher propylene glycol ester terephthalate, other parts are derived from removing terephthalic acid and 1, monomer outside ammediol (such as: phthalic acid, NDA, hexanodioic acid, nonane diacid; Ethylene glycol, 1,2-PD, BDO etc.) polymkeric substance.
Term " blend " refers to and carries out by described PTT homopolymer and described PTT multipolymer the mixture that mixes with Different Weight %.In the present invention, " PTT blend " preferably comprises the PTT homopolymer of 70 % by weight or higher or 80 % by weight or higher or 90 % by weight or higher or 95 % by weight or higher.
The preparation method being applicable to PTT homopolymer of the present invention or PTT multipolymer 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).
The molecular weight of polymkeric substance can be measured with its limiting viscosity (Intrinsic Viscosity, IV), can measure according to the method for ASTM D4603-96.Limiting viscosity usually can increase along with the molecular weight of polymkeric substance and increase, but its numerical value also depends on macromolecular kind, its shape or configuration, and tests solvent used.In a preferred embodiment of the invention, described in flame-retardant composition of the present invention, the limiting viscosity of polytrimethylene terephthalate is about 0.8-2.0, is preferably about 0.9-1.5.
Being applicable to PTT resin of the present invention also can be commercially available, and the commodity of such as E.I.Du Pont De Nemours and Co. of the U.S. (DuPont E.I.du Pont de Nemours and Company, is hereafter called " E.I.Du Pont Company ") are called
product, such as, being divided into according to its dulling agent content has greatly light, partly has the different sortses such as light, half delustring, full-dull; Each kind comprises again the PTT resin that several have different qualities viscosity (IV).
In one embodiment, with the total weight of flame-retardant composition of the present invention, in described flame-retardant composition, the amount of the polytrimethylene terephthalate of component (a) is about 20-60 % by weight, or about 25-50 % by weight, or about 30-45 % by weight.
(b) fiber enhancer
In flame-retardant composition of the present invention, the fiber enhancer of described component (b) is had no particular limits.Its effect is mechanical strength such as tensile strength, the flexural strength of improving described flame-retardant composition, and in order to suppress the contraction of layered product.
Known fiber toughener comprises: inorganic fibre, and such as glass fibre, carbon fiber, graphite fibre, silicon-aluminum fiber, Zirconium oxide fibre, ceramic fiber, steel fiber are as the fiber of stainless steel, aluminium, titanium, copper or brass; And organic fibre, such as Para-aromatic Aramide Fibre, nylon fiber or vegetable fibre.The one or two or more in them can be used, or its combination.With regard to reinforced effects, described fiber enhancer is preferably glass fibre, carbon fiber or Para-aromatic Aramide Fibre.In view of commercially available property and cost, glass fibre is preferred.
In one embodiment, in flame-retardant composition of the present invention, the fiber enhancer of described component (b) is glass fibre, carbon fiber or Para-aromatic Aramide Fibre.In another embodiment, in flame-retardant composition of the present invention, the fiber enhancer of described component (b) is glass fibre.
Various glass fibre can be adopted according to glass fibre of the present invention.In these glass fibre, preferably by the chopped strand (chopped strand) that E-glass (non-alkali glass) is obtained.
The fiber diameter of described fiber enhancer is not particularly limited, such as 1-100 micron, is preferably about 3-30 micron, and is more preferably about 5-15 micron.The average fiber length of described fiber enhancer is also not particularly limited, and is generally no more than 10 millimeters, is preferably about 2-5 millimeter.
In addition, the fiber enhancer of described component (b) can as required by using surface treatment agent (such as, classify with the functional group of compound, comprise containing the compound of epoxy group(ing), containing acrylic acid compound, compound containing isocyanic ester, silane compound or the compound containing titanate (ester)) carry out surface treatment.Described fiber enhancer (b) can carry out preliminary surface process by above-mentioned surface treatment agent, or can carry out surface treatment when preparing material by adding surface treatment agent.Described glass fibre preferably uses silane compound (also referred to as silane coupling agent) to carry out surface treatment, to strengthen the cementability to described polytrimethylene terephthalate.
In one embodiment, in flame-retardant composition of the present invention, the mean diameter of the fiber enhancer of described component (b) is 1-100 micron, or 3-30 micron, or 5-15 micron; And its mean length is no more than 10 millimeters, or it is about 2-5 millimeter.
The example of the glass fibre be applicable to comprises T-120 and T-275 and is produced by Nippon Electric Glass Co.Ltd.; ChopVantage
tMhP 3660 and HP3786 provided by PPG Industries Fiber Glass.
The example of suitable carbon fiber comprises that toray company sells
carbon fiber and Japanese Di Ren company sell
carbon fiber.
The example of suitable Para-aromatic Aramide Fibre comprises that Du Pont sells
fiber, and Japanese Di Ren company sells
In one embodiment, with the total weight of flame-retardant composition of the present invention, in described flame-retardant composition, the amount of the glass fibre of described component (b) is about 20-55 % by weight, or about 25-50 % by weight.
(c) fire retardant
In flame-retardant composition of the present invention, the fire retardant of described component (c) its be the mixture of phosphinates and aromatic polyphosphate ester.
Described phosphinates is selected from dimethylphosphinic acid salt, ethylimethyphosphinic acid salt, diethyl phosphinates, methyl-n-propylphosphinic acid salt, methyl two (methyl-phosphinic acid salt), benzene-Isosorbide-5-Nitrae-(dimethylphosphinic acid salt), methylphenylphosphinic acid salt, diphenyl phosphonic acid salt and its mixture.
The positively charged ion of described phosphinate flame retardant is selected from calcium, aluminium, zinc, iron and boron, is preferably selected from calcium, aluminum and zinc.
In the preferred embodiment of the present invention, the phosphinates in the fire retardant of described component (c) is selected from dimethylphosphinic acid aluminium, ethylimethyphosphinic acid aluminium, aluminum diethylphosphinate, methylpropylphosphinic acid aluminium, phospho acid calcium, diethyl phospho acid zinc and its mixture.
In flame-retardant composition of the present invention, described phosphinates can be used with different physical aspects.In order to obtain better dispersion effect in PTT base material, preferred described phosphinates is used, as the median size (d of commercially available aluminum diethylphosphinate with fine-powder (the dispersed fine particles) form of dispersion
50) be 25-150 micron, can directly use, need not again through attrition process.The mixture of different phosphinates can also be used.
The example of suitable phosphinates comprises that Clariant Corporation (Clariant) sells
oP1240, OP1230, OP935 and OP950.
In flame-retardant composition of the present invention, aromatic polyphosphate ester in the fire retardant of described component (c) is selected from: two (diphenyl phosphoester) (RDP) of Resorcinol, two (2, the 6-3,5-dimethylphenyl) phosphoric acid ester (RDX) of Resorcinol, two (diphenyl phosphate) (BDP) of bisphenol-A, two (diphenyl phosphoester) (Doher-7000) of Resorcinol and its mixture.
Commercially available aromatic polyphosphate ester includes but not limited to RDP, BDP, RDX and/or Doher-7000, it can contain chemical industry (Zhejiang Wansheng Chemical Co., Ltd.) purchased from large eight chemistry of Japan (Daihachi Chemical Industry) and Zhejiang ten thousand.
In flame-retardant composition of the present invention, the weight ratio of the phosphinates in the fire retardant of described component (c) and aromatic polyphosphate ester is 2:1 to 4:1, is preferably 2.5:1 to 3.5:1.
In addition, in flame-retardant composition of the present invention, with the total weight of flame-retardant composition of the present invention, the amount (i.e. total consumption of phosphinates and aromatic polyphosphate ester) of the fire retardant of described component (c) is about 10-30 % by weight, is preferably about 15-25 % by weight.
In one embodiment, in flame-retardant composition of the present invention, the weight ratio of the phosphinates in the fire retardant of described component (c) and aromatic polyphosphate ester is 2:1 to 4:1, or 2.5:1 to 3.5:1.
In one embodiment, with the total weight of flame-retardant composition of the present invention, in described flame-retardant composition, the amount of the fire retardant of described component (c) is about 10-30 % by weight, or about 15-25 % by weight.
(d) aromatic copolycarbonate
In flame-retardant composition of the present invention, the aromatic copolycarbonate of described component (d) is by diphenol and carbonate precursor, is obtained by solution method or scorification; Such as obtained by diphenol and phosgene reaction, or it is obtained to carry out transesterification reaction by diphenol and dipheryl carbonate base ester.
The example of described diphenol includes but not limited to 2, two (4-hydroxy phenyl) propane (i.e. dihydroxyphenyl propane) of 2-, two (4-hydroxy phenyl) methane, 1, two (4-hydroxy phenyl) ethane of 1-, two (the 4-hydroxyl-3 of 2,2-, 5-3,5-dimethylphenyl) propane, 4,4' dihydroxy diphenyl, two (4-hydroxy phenyl) naphthenic hydrocarbon, bis oxide (4-hydroxy phenyl), sulfuration two (4-hydroxy phenyl), two (4-hydroxy phenyl) sulfone, two (4-hydroxy phenyl) sulfoxide, two (4-hydroxy phenyl) ether, two (4-hydroxy phenyl) ketone etc.
Described carbonate precursor comprises carbonyl carboxylic acid halides, carbonyl ester, haloformate; Comprise phosgene specifically, dihalo formic acid hexichol phenolic ester, dipheryl carbonate base ester, methylcarbonate, diethyl carbonate etc.
Consider cost and commercially available property, the aromatic copolycarbonate of described component (d) is preferably the aromatic copolycarbonate using dihydroxyphenyl propane as diphenol raw material, the i.e. aromatic copolycarbonate of bisphenol A-type.In another embodiment, described aromatic copolycarbonate is according to ISO1133, and the melt flow index (MFI) recorded under the load of 300 DEG C and 1.2 kilograms is about 5-20 gram/10 minutes, is preferably about 6-12 gram/10 minutes.
Suitable polycarbonate comprises, the MAKROLON that such as Bayer AG (Bayer) sells
tM, SABIC innovation Plastics Company (SABIC Innovative Plastics) sells
di Ren chemical company (Teijin Chemical) sells
mitsubishi (Mitsubishi) is sold
and the Dow Chemical Company (Dow) sells
In one embodiment, with the total weight of flame-retardant composition of the present invention, in described flame-retardant composition, the amount of the aromatic copolycarbonate of described component (d) is about 1-10 % by weight, or about 2-8 % by weight.
(e) additive
In flame-retardant composition of the present invention, the additive of described component (e) is selected from antioxidant, anti-dripping agent, chainextender, the tinting material comprising dyestuff and pigment, releasing agent, flow ability modifying agent, hydrolysis-resisting agent, lubricant, nucleator, thermo-stabilizer, UV light stabilizing agent and its combination.
The suitable amounts of these additives and the method for these additives being mixed polymer composition are well known by persons skilled in the art.See such as Modern Plastics Encyclopedia.
Suitable antioxidant includes but not limited to hindered phenol compound, comprises such as commodity and is called
the tetramethylolmethane four (3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester) of 1010 and
octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester of 1076), all can purchased from BASF.Other suitable antioxidants comprise phosphorite, and such as Addivant (Middlebury, CT, USA) sells
626 (two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites) and
619 (distearyl pentaerythrityl diphosphites), and BASF sells
168 (three (2,4-di-tert-butyl-phenyl) phosphorous acid esters).The consumption of antioxidant is about the about 0.1-2 % by weight of flame-retardant composition gross weight.
The fluoropolymer of known anti-dripping agent such as chemical modification can be dispersed in thermoplastic compounds, improves its flame retardant properties by its obtained moulding part because of given anti-dripping melt.The fluoropolymer such as particle of tetrafluoroethylene, tetrafluoroethylene hexafluoropropylene copolymer etc. can be coated with acrylic copolymer, styrol copolymer or styrene-acrylonitrile copolymer guarantees good dispersion in the polymer matrix.Commercially available anti-dripping agent comprises
sN3300 or
sN3306, it is manufactured by Shangneng Polymer Tech Co., Ltd., Guangzhou (ShinePolymer).The consumption of anti-dripping agent is about the about 0.1-1 % by weight of flame-retardant composition gross weight.
Suitable flow ability modifying agent includes but not limited to polyoxypropylene glyceryl, PULLRONIC F68 glycerine or its any mixture, and the molecular-weight average of described flow ability modifying agent is determined as about 2000-10000 by gel permeation chromatography (GPC), or about 2200-7500, or about 2500-5000.The commercially available acquisition of described flow ability modifying agent, such as, the polyoxypropylene glyceryl of different molecular weight can purchased from Hai'an, Jiangsu petroleum chemical plant (Jiangsu Haian Petrochemical Plant), and the PULLRONIC F68 glycerine of different molecular weight and PO/EO mol ratio also can be buied from Sigma-Aldrich.The consumption of flow ability modifying agent is about the about 0.1-2 % by weight of flame-retardant composition gross weight.
Proper lubrication agent includes but not limited to: Emery Olechmicals (Germany) sells
pTS HOB7119, and Clariant Corp., (Charlotte, N.C., USA) sells
eT132,
eT141 and Licomont wax OP.The consumption of lubricant is about the about 0.1-1 % by weight of flame-retardant composition gross weight.
As the amount of the additive of the component (e) of composition of the present invention, with the total weight of flame-retardant composition of the present invention, for about 0.1-10 % by weight, or about 0.5-7.5 % by weight, as long as they do not damage the fundamental sum novel features of described composition, and do not have obvious disadvantageous effect to the performance of described composition.
In one embodiment, with the total weight of flame-retardant composition of the present invention, in described flame-retardant composition, the amount of the additive of described component (e) is about 0.1-10 % by weight, or about 0.5-7.5 % by weight.
Flame-retardant composition of the present invention is the blend in melting-mixing, wherein all polymeric constituents are dispersed in each other well, and all non-polymeric ingredients are also scattered in wherein equably, and are combined with polymeric matrix, described blend is made to form unified entirety.Any melting-blending means can be used by component (a), (b), (c), (d) and (e) are obtained by mixing described blend.Use melt mixer, such as singe screw or twin screw extruder, blender, kneader, Banbury mixer etc., can mix described constituent materials and obtain resin combination.Or, a part in described component and matrix resin can be mixed to form masterbatch in melting-mixing machine, and then the remainder in described component be added, and further melting-mixing until even.
The mixing order prepared in flame-retardant composition of the present invention can be by the charging of each component and melting, or can by reinforcing filler and/or the charger charging from the side of other components etc., and this is understood by one of ordinary skill in the art.
Melting-mixing temperature used should higher than the fusing point of each component, but lower than its minimum decomposition temperature, and must for principal polymeric component, namely resin base material and other concrete each components correspondingly adjust.Be applicable to the mixing temperature of flame-retardant composition of the present invention usually at about 230-290 DEG C, be preferably the scope of about 240-270 DEG C.
Moulded product can be obtained by flame-retardant composition of the present invention as above actually by any extruding process thereof well known by persons skilled in the art or hot-forming method.Such as, injection moulding, injection moulding altogether, compression moulding, quadric injection mould and profile are extruded.Therefore, described moulded product can be injection moulding, compression molding or profile extrusion moulding and the moulded product prepared or film.
One of the present invention is preferred embodiment comprise above-mentioned flame-retardant composition or the moulded product obtained by above-mentioned flame-retardant composition.
Flame-retardant composition of the present invention may be used for the various product of molding, is particularly suitable for manufacturing trolley part; And such as, for the manufacture of Electrical and Electronic related products, housing of TV set, counter body, mobile communication equipment shell and business automation equipment shell.Described flame-retardant composition can also make the form of film and sheet material.
Embodiment
Following embodiment is exemplary, can not form limit improperly scope of the present invention.Abbreviation " E " expression " embodiment ", " CE " expression " comparative example ", numeral has prepared described composition in which embodiment thereafter.All embodiments and comparative example are prepared all in a similar manner and test.Except as otherwise noted, per-cent is weight percent.
Each embodiment and comparative example starting material used are in table 1:
table 1
detailed step
A) mix: each component of each embodiment or comparative example (is referred to table 2 and table 3) in proportion and sends into twin screw extruder (ZE25A47D UTXi, KraussMaffei Berstorff), blended granulation is with obtained corresponding flame-retardant composition.For the forcing machine comprising 10 heating zone designs, the temperature of forcing machine is set in 120/180/250/250/250/250/250/250/250/250oC.Die head temperature is 250oC, and screw speed is 200-450rpm, extrudes output and is set as 20 kgs/hr.
B) molding: after molding, is dried to moisture content by the pill extruded and is less than 200ppm.For mechanical properties test, on Sumitomo100 ton mould machine, prepare test bars according to ISO3167 molding, the screw diameter of mould machine is 32 millimeters, and nozzle diameter is 5 millimeters.Barrel temperature is set in 260 DEG C, and die temperature is 80 DEG C.The basic configuration of described test bars is dumb-bell shape batten, long 150 millimeters, and centre portions is of a size of wide 10 millimeters × thick 4 millimeters × long 80 millimeters.
test mode
Modulus in flexure (0.05%-0.25%) and the flexural strength under 3.5% strain measure according to ISO178:2001 (E).
The mechanical properties of tensile modulus (0.05%-0.25%), tensile strength and tension fracture elongation rate measures according to ISO527:1993 (E).
Fire retardancy test: be according to title for " Tests for Flammability of Plastic Materials; UL94 ", the method for Underwriter's Laboratory Bulletin94, long 127 millimeters of batten, wide 12.7 millimeters, thickness is 0.8 millimeter, tests.According to the method, based on 5 battens, the test-results of lighting gained for 10 times, material is divided into 5VA, 5VB, V-0, V-1, V-2, and six of HB grades.Obtain the material of V-0 grade, become by the major axis of a batten 180 degree to put (namely vertical combustion is tested) with flame, after removing burning burning things which may cause a fire disaster, the flaming combustion of single batten and/or the time of glowing are no more than 10 seconds, add up to be no more than 50 seconds combustion time, and the vertical sample placed does not produce the drippage material can lighting absorbent cotton.
The each component consumption of embodiment and comparative example, and its flame retardant properties and mechanical property evaluation the results are shown in table 2 and table 3.
table 2
* ND: without test data, the crystallinity because of the composition of comparative example 4 is too poor and cannot prepare the flame retardant test batten of 0.8 millimeter.
As can be seen from the data of table 2, the flame-retardant composition prepared in the embodiment of the present invention is by the aromatic copolycarbonate of addO-on therapy (d), compared with the composition of comparative example, not only increase their mechanical property, when not increasing the flame retardant content of component (c), improve its flame retardant properties unexpectedly, bring up to V-0 rank from the V-1 of UL94.
By in table 2, the relatively mechanical properties results of comparative example 1-3 and corresponding embodiment 1-3, can see: for the PTT resin of different qualities viscosity, be considerably improved flexural strength (increasing about 5-15%) and the tensile strength (increasing about 8-18%) of the present composition by the aromatic copolycarbonate of the component (d) of adding 4-6%.
In addition, can also be seen by the data of table 2: close at flame retardant (c) total content, also containing the aromatic copolycarbonate (d) of equivalent, embodiment 3 uses the flame retardant of mixture as component (c) of phosphinates and aromatic polyphosphate ester, relative to the comparative example 4 only using phosphinates, there is higher flexural strength (increasing about 17%) and tensile strength (increasing about 15%).
Be 2:1 to 4:1 according to the weight ratio of phosphinates and aromatic polyphosphate ester in the flame retardant of the component (c) of embodiment 1-3, be preferably 2.5:1 to 3.5:1; And the total amount of the fire retardant of described component (c) is preferably about 15-25 % by weight.
table 3
By in table 3, the relatively measuring mechanical property result of comparative example 3 and embodiment 4-6, can see: by adding component (d) aromatic copolycarbonate of about 3-9%, the flexural strength of fire-retardant combination of the present invention and tensile strength, relative to flexural strength and the tensile strength of comparative example 3, improve about 8-16%.Meanwhile, when not increasing the flame retardant content of component (c), improve its flame retardant properties unexpectedly, bringing up to V-0 rank from the V-1 of UL94.
In addition, the mechanical property of comparing embodiment 4 and embodiment 7,8 and flame retardant properties test result, can see: the flow ability modifying agent adding the polyoxypropylene glyceryl class of 0.8% not only increases tension fracture elongation rate, also shorten it unexpectedly and add up to combustion time, namely improve its flame retardant properties further.
The mechanical property of comparing embodiment 7 and embodiment 8 and flame retardant properties data, both there is no marked difference.As can be seen here, described flow ability modifying agent directly can carry out melt blending with other components, to obtain fire-retardant combination of the present invention (as embodiment 7); Or first add the obtained PTT resin granular material containing 2% flow ability modifying agent in PTT resin, then carry out secondary melt blending with other components, also can obtain fire-retardant combination of the present invention (as embodiment 8).
In a preferred embodiment, flame-retardant composition of the present invention is made up of following component substantially:
The Poly(Trimethylene Terephthalate) of (a) about 25-50 % by weight;
The glass fibre of (b) about 25-50 % by weight;
The fire retardant of (c) about 15-25 % by weight, it is the mixture of phosphinates and aromatic polyphosphate ester;
The aromatic copolycarbonate of (d) about 1-10 % by weight; With
The additive of (e) about 1-5 % by weight, it is selected from: antioxidant, anti-dripping agent, chainextender, the tinting material comprising dyestuff and pigment, releasing agent, flow ability modifying agent, hydrolysis-resisting agent, lubricant, nucleator, thermo-stabilizer, UV light stabilizing agent and its combination;
Wherein said weight percentage is the gross weight based on described flame-retardant composition.
Although with typical embodiment example and describe the present invention, its intention is not limit the invention in shown details, multiple amendment and alternative may to be there is under spirit of the present invention not deviating from.Thus, when those skilled in the art can just obtain with the improvement of open invention herein by means of only normal experiment and be equal to, then be sure of in all these improvement and the equivalent the spirit and scope of the present invention be included in defined in claim.
Claims (10)
1. a flame-retardant composition, it is substantially composed of the following components:
The polytrimethylene terephthalate of (a) 20-60 % by weight;
The fiber enhancer of (b) 20-55 % by weight;
The fire retardant of (c) 10-30 % by weight, it is the mixture of phosphinates and aromatic polyphosphate ester;
The aromatic copolycarbonate of (d) 1-10 % by weight; With
The additive of (e) 0.1-10 % by weight, it is selected from: antioxidant, anti-dripping agent, chainextender, the tinting material comprising dyestuff and pigment, releasing agent, flow ability modifying agent, hydrolysis-resisting agent, lubricant, nucleator, thermo-stabilizer, UV light stabilizing agent and its combination;
Wherein said weight percentage is the gross weight based on described flame-retardant composition.
2. flame-retardant composition as claimed in claim 1, the polytrimethylene terephthalate of wherein said component (a) is Poly(Trimethylene Terephthalate) homopolymer, comprises the Poly(Trimethylene Terephthalate) multipolymer of the propylene glycol ester terephthalate of at least 70 % by mole or its blend, and the limiting viscosity of described polytrimethylene terephthalate is 0.8-2.0g/dL.
3. flame-retardant composition as claimed in claim 1, the fiber enhancer of wherein said component (b) is glass fibre, carbon fiber or Para-aromatic Aramide Fibre, and the mean diameter of described fiber enhancer is 1-100 micron and mean length is no more than 10 millimeters.
4. flame-retardant composition as claimed in claim 1, the phosphinates wherein in described component (c) fire retardant is selected from: dimethylphosphinic acid aluminium, ethylimethyphosphinic acid aluminium, aluminum diethylphosphinate, methylpropylphosphinic acid aluminium, phospho acid calcium, diethyl phospho acid zinc and its mixture.
5. flame-retardant composition as claimed in claim 1, aromatic polyphosphate ester wherein in described component (c) fire retardant is selected from: Resorcinol two (diphenyl phosphoester), Resorcinol two [two (2,6-3,5-dimethylphenyl) phosphoric acid ester], bisphenol-A two (diphenyl phosphate), Resorcinol two (diphenyl phosphoester) and its mixture.
6. flame-retardant composition as claimed in claim 1, the phosphinates wherein in described component (c) fire retardant and the weight ratio of aromatic polyphosphate ester are 2:1 to 4:1.
7. flame-retardant composition as claimed in claim 1, the aromatic copolycarbonate of wherein said component (d) is the polycarbonate of bisphenol A-type, and the melt flow index of described aromatic copolycarbonate is determined as 5-20 gram/10 minutes by ISO1133 method.
8. flame-retardant composition as claimed in claim 1, the additive of wherein said component (e) is flow ability modifying agent, it is polyoxypropylene glyceryl, PULLRONIC F68 glycerine or its any mixture, and the molecular-weight average of described flow ability modifying agent is determined as 2000-10000 by gel permeation chromatography (GPC).
9. moulded product, it comprises the flame-retardant composition according to any one of claim 1-8, or the flame-retardant composition according to any one of claim 1-8 obtains.
10. prepare claim 1 or the method for composition, comprising:
I. each component (a) of the flame-retardant composition of claim 1, (b), (c), (d) and (e) is provided for;
Ii. in the forcing machine of 240 DEG C-270 DEG C mixing said ingredients to form mixed uniformly flame-retardant composition; With
Iii. by described flame-retardant composition extruding pelletization;
The flame retardant properties of wherein said flame-retardant composition meets the V-0 rank of UL94, and the thickness of its test bars is 0.8mm.
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