CN103146155A - Flame-retardant polytrimethylene terephthalate composition and preparation method thereof - Google Patents
Flame-retardant polytrimethylene terephthalate composition and preparation method thereof Download PDFInfo
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- CN103146155A CN103146155A CN2011104046621A CN201110404662A CN103146155A CN 103146155 A CN103146155 A CN 103146155A CN 2011104046621 A CN2011104046621 A CN 2011104046621A CN 201110404662 A CN201110404662 A CN 201110404662A CN 103146155 A CN103146155 A CN 103146155A
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Abstract
The invention relates to a flame-retardant polytrimethylene terephthalate composition and a preparation method thereof. The flame-retardant polytrimethylene terephthalate composition comprises 1, about 30 to 70wt% of polytrimethylene terephthalate, 2, about 1 to 50wt% of glass fibers, 3, about 5 to 20wt% of a phosphinate flame retardant, 4, about 1 to 20wt% of a nitrogen-containing flame retardant, 5, about 0.1 to 2wt% of aromatic phosphite, and 6, about 0 to 6wt% of an additive. A composite material prepared from the flame-retardant polytrimethylene terephthalate composition satisfies high flame retardant standards such as the UL94 V-0 grade, and has excellent mechanical properties.
Description
Technical field
The present invention relates to flame retardant resistance polytrimethylene terephthalate composition, particularly relate to the polytrimethylene terephthalate composition that comprises halogen-free flame retardants and glass fibre enhancing.
Background technology
Comprise the polyester product of the glass fibre enhancing of fire retardant, as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), be widely used in electronic apparatus (E/E) equipment.But usually add in these products, halogen-containing fire retardant is arranged, and these halogen-containing flame retardant polyester products are by some environmental legislations and regulations, for example RoHS and WEEE, strict restriction is used, so the use of these polyester products is faced with increasing environmental problem.
Although people have developed some not halogen-containing fire retardants to satisfy the requirement of environmental legislation and regulations, but the mechanical property that usually causes this polyester product that adds of these halogen-free flame retardantss reduces, therefore be difficult to fully substitute halogen-containing flame retardant polyester product, thereby limited the widespread use of the polyester product that contains halogen-free flame retardants.
WO2009/009249 discloses a kind of halide content less than 5 % by weight, preferably less than the composition of 100ppm, it comprises a) polyester, the b of 20-80 % by weight) fire retardant, the c that are selected from phosphinates, diphosphinic acid salt and/or their derivative of 5-35 % by weight) material that is selected from trimeric cyanamide polyphosphate, melamine cyanurate, melamine pyrophosphate and/or melamine phosphate, the d of 1-25% weight) polyetherimide, the e of 0-25 % by weight) reinforcing filler of optional existence of 0-50 % by weight, and conventional additives.Wherein said polyester can be PET, PBT or polytrimethylene terephthalate (PTT) etc., and described reinforcing filler can be selected from granular filler, glass fibre or their combination.Yet the mechanical property that comprises the moulded product of said composition such as tensile strength, still significantly lower than the polymer blend of traditional halogen-containing flame retardant, thereby limits it and uses widely.
US2004192812 discloses a kind of halogen-free flame-retarded polyester composition, it comprises a) thermoplastic polyester of 20-97 % by weight, b) phosphinates of 1-40 % by weight and/or diphosphinic acid salt and/or their polymkeric substance, metal ion wherein can be calcium or aluminium, c) the 1-30 % by weight contains nitrogen combustion inhibitor, melamine compound for example, d) the 0-5 % by weight by having the saturated of 10-40 carbon atom or unsaturated aliphatic carboxylic acid and at least a ester or acid amides with the acquisition of the representative examples of saturated aliphatic alcohol of 2-40 carbon atom or amine, e) the optional additive of 0-60 % by weight, carbon fiber for example, glass fibre, granulated glass sphere etc.Components b wherein) median particle diameter d
50Less than 10 microns, preferably less than 7 microns.By using the fine grain phosphinates through grinding, to have greatly reduced the migration of additive in the flame-proof composite material and corrosion phenomenon during with metallic contact according to stating the technical problem that this invention solves.Yet the mechanical property that comprises the moulded product of said composition as tensile strength, is starkly lower than traditional halogen-containing polymer blend equally, has limited it and has used widely.
Still need at present to develop a kind of PTT matrix material that contains halogen-free flame retardants and glass enhancing that has good flame-retardance energy and mechanical property concurrently, with the PTT matrix material of alternative traditional halogen-containing flame retardant, thereby 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 retardant resistance polytrimethylene terephthalate composition that comprises halogen-free flame retardants and glass fibre enhancing, can be satisfied the V-0 rank (thickness of its test bars is 0.8mm) of UL94 by the flame retardant properties of the matrix material of said composition preparation, have simultaneously excellent mechanical property.
According to an aspect of the present invention, provide a kind of flame-retardant composition, it comprises:
(a) polytrimethylene terephthalate of about 30-70 % by weight;
(b) glass fibre of about 1-50 % by weight;
(c) the phosphinates fire retardant of about 5-20 % by weight;
(d) approximately the 1-20 % by weight contain nitrogen combustion inhibitor;
(e) the aromatic series phosphorous acid ester of about 0.1-2 % by weight; With
(f) additive of about 0-6 % by weight,
Wherein said weight percentage is based on the gross weight of described flame-retardant composition, the flame retardant properties of described flame-retardant composition meets the V-0 rank of UL94, the thickness of its test bars is 0.8mm, and its flexural strength that records according to ISO178 and ISO527 method respectively and tensile strength are than only comprising (a), (b), (c), (d) and (f) analog value of the comparative composition of component is high by 10% at least.
According to another aspect of the present invention, provide a kind of method for preparing fire-retardant combination of the present invention, comprising:
I. be provided for each component (a), (b), (c), (d), (e) of flame-retardant composition of the present invention and (f);
Ii. in the forcing machine of 240 ℃-270 ℃ mixing said ingredients to form mixed uniformly flame-retardant composition;
Iii. with described flame-retardant composition extruding pelletization;
Wherein, the flame retardant properties of described flame-retardant composition meets the V-0 rank of UL94, the thickness of its test bars is 0.8mm, and its flexural strength that records according to ISO178 and ISO527 method respectively and tensile strength are than only comprising (a), (b), (c), (d) and (f) analog value of the comparative composition of component is high by 10% at least.
According to a further aspect of the invention, provide the moulded product that comprises flame-retardant composition of the present invention, described moulded product has excellent flame retardant properties and mechanical property.
Embodiment
Unless otherwise indicated, all publications that the present invention mentions, patent application, patent and other reference all are incorporated into herein by reference in full, are equivalent to be presented in full this paper.
Unless otherwise defined, all technology used herein and scientific terminology have the common same implication of understanding of one skilled in the art of the present invention.In the situation that conflict, be as the criterion with the definition of this specification sheets.
Unless otherwise indicated, all percentage ratio, umber, ratio etc. are all by weight.
When 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 to be equivalent to specifically to have disclosed any scope that combines by with any a pair of range limit or preferred value and any range lower limit or preferred value, and do not consider whether this scope specifically discloses.Unless otherwise noted, the listed numerical range of this paper 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 ... consist of " be equal to " comprise/comprise ".Term used herein " comprises ", " comprising ", " having ", " having ", " containing " 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.
Conjunction " by ... form " do not comprise any key element of clearly not enumerating, step or composition.If there is in the claims, this conjunction will make claim be limited to described material and not comprise the material of not describing, but still comprise and those described materials relevant impurity usually.When conjunction " by ... form " appear at the characteristic of claim, but not when being right after preamble, the key element that it only limits to set forth in characteristic; Other key elements are not required to get rid of in integral body by Accessory Right.
Conjunction " substantially by ... form " be used for also comprising outside literal the above those materials, step, feature, component or the key element of definite division combination, method or the equipment of other material, step, feature, component or key element, prerequisite is essential characteristic and the novel feature that these other materials, step, feature, component or key element substantially do not affect invention required for protection.Conjunction " substantially by ... form " be in " comprising " and " by ... form " between a rank.
Conjunction " substantially do not comprise " or " substantially not containing " certain/a little components represent the gross weight based on composition, composition of the present invention should contain lower than 1 % by weight, preferably lower than this component of 0.1 % by weight.
Conjunction " comprise " intention comprise conjunction " substantially by ... form " and " by ... composition " embodiment of containing.Similarly, conjunction " substantially by ... form " intention comprise conjunction " by ... form " embodiment that contains.
When term " about " was used for describing the end value of numerical value or scope with " approximately ", disclosed content was understood to include occurrence or related end value.
In addition, unless clearly represent contrary, "or" refers to the "or" of pardon but not exclusive "or".For example, below arbitrary condition all applicable elements A "or" B:A be that true (or existence) and B are false (or not existing), A is that false (or not existing) and B are true (or existence), and A and B are true (or existence).
In this application, " halogen-free flame retardants " refers to that in fire retardant, content of halogen is less than 100ppm.
The below describes the present invention.At first the component (a)-(f) that forms thermoplastic compounds of the present invention is described.
In flame-retardant composition of the present invention, the polytrimethylene terephthalate (PTT) of described component (a) is a kind of polyester.Polyester polymers is that those skilled in the art are well-known, can comprise any polycondensation product that is derived from two pure and mild dicarboxylic acid (comprising dicarboxylic ester) by esterification or transesterification reaction.
The polytrimethylene terephthalate (PTT) of component (a) can be by the polycondensation preparation of 1,3-PD and terephthalic acid.Perhaps, polytrimethylene terephthalate can also be by 1,3-PD and dimethyl terephthalate (DMT) preparation.The 1,3-PD that is used for preparing PTT obtains (" biological process obtains " 1,3-PD) preferably by biochemical method by renewable resources.Because it is well-known that polyester and preparation method thereof is those skilled in the art, in order to compose a piece of writing for purpose of brevity, no longer it is conducted further description herein.
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.For example, use Y-900 type Viscotek to force the stream viscometer, with the concentration of 0.5% (weight/volume), polymer dissolution in phenol/tetrachloroethane (60/40 % by weight) solution, is tested at 25 ℃.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 test solvent used.
In the preferred embodiment of the present invention, described in flame-retardant composition of the present invention, the limiting viscosity of polytrimethylene terephthalate is about 0.8-1.2, or is about 0.9-1.1.
The polytrimethylene terephthalate that can buy on market includes but not limited to available from E.I.Du Pont Company (DuPont)
And available from shell chemical company (Shell Chemicals)
In the preferred embodiment of the present invention, gross weight in flame-retardant composition of the present invention, flame-retardant composition of the present invention comprises the 30-70 % by weight, or the 40-60 % by weight, or the polytrimethylene terephthalate of the described component (a) of 45-55 % by weight.
In flame-retardant composition of the present invention, the glass fibre of described component (b) is had no particular limits.In the preferred embodiment of the present invention, use the relative lime-aluminium borosilicate glass without sodium that is commonly referred to " E " glass, also can use the low soda glass that is commonly referred to " C " glass.Described glass fibre can prepare by traditional method, for example steam or air blown, flame blowing and mechanical pull.Glass fibre typically have a diameter from the 1-50 micron, preferred 1-20 micron.Described glass fibre can be combined into fibrous bundle, yarn, rope, rove or be woven into felt.The glass fibre of component used in the present invention (b) is preferably chopped strand (chopped strand), and its length is less than 10 centimetres, or less than 5 centimetres.
In the preferred embodiment of the present invention, the glass fibre of component described in flame-retardant composition of the present invention (b) is chopped strand, and the diameter of described chopped strand is the 1-50 micron, or the 1-20 micron; And its length is less than 10 millimeters, or less than 5 millimeters.
In the preferred embodiment of the present invention, in the gross weight of flame-retardant composition of the present invention, flame-retardant composition of the present invention comprises the 1-50 % by weight, or the 5-45 % by weight, or the glass fibre of the described component (b) of 10-35 % by weight.
In thermoplastic polyester composition of the present invention, the phosphinates fire retardant of described component (c) is selected from the phosphinates with following formula I or has the diphosphinic acid salt of Formula Il and their polymkeric substance.
R in formula I
1And R
2Hydrogen, C independently of one another
1-C
6Alkyl, described alkyl is optional with hydroxyl; The C of preferred linearity or cladodification
1-C
4Alkyl, for example methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, the tertiary butyl, n-pentyl; C
6-C
20Aryl, for example phenyl, naphthyl; C
7-C
20Alkylaryl, for example aminomethyl phenyl, ethylphenyl, tert-butyl-phenyl, methyl naphthyl, ethyl naphthyl, tertiary butyl naphthyl; C
6-C
20Arylalkyl, for example phenyl methyl, phenylethyl, phenyl propyl, phenyl butyl.
R
3The C of linearity or cladodification
1-C
10Alkylidene group, for example methylene radical, ethylidene, positive propylidene, isopropylidene, positive butylidene, uncle's butylidene, positive pentylidene, just octylene, positive inferior decyl; Arylidene, for example phenylene, naphthylidene; Alkyl arylene, for example methylphenylene, ethyl phenylene, tertiary butyl phenylene, methyl naphthylidene, ethyl naphthylidene, tertiary butyl naphthylidene; Aryl alkylene, for example phenylmethylene, phenyl ethylidene, phenyl propylidene, phenyl butylidene;
M is alkaline-earth metal, basic metal, aluminium, zinc, iron or boron;
M is the integer of 1-3;
N is the integer of 1-3; With
X is 1 or 2.
In the preferred embodiment of the present invention, the phosphinates fire retardant of described component (c) is to be selected from dimethyl phosphinates, ethyl-methyl phosphinates, diethyl phosphinates, methyl-n-propylphosphinic acid salt, methyl two (methyl-phosphinic acid salt), benzene-Isosorbide-5-Nitrae-(dimethyl phosphinates), aminomethyl phenyl phosphinates and diphenyl phosphonic acid salt.
In the preferred embodiment of the present invention, the positively charged ion of the phosphinates fire retardant of described component (c) is to be selected from calcium, aluminium, zinc, iron and boron.
In the embodiment of present invention further optimization, the phosphinates fire retardant of described component (c) is to be selected from dimethyl phospho acid aluminium, ethyl-methyl phospho acid aluminium, diethyl phospho acid aluminium, methyl-propyl phospho acid aluminium, phospho acid calcium and diethyl phospho acid zinc.
In flame-retardant composition of the present invention, the phosphinates of described component (c) can be used with different physical aspects.In order to obtain better dispersion effect in the PTT base material, preferred described phosphinates is used with fine-powder (the dispersed fine particles) form of disperseing, as the median size (d of commercially available diethyl phospho acid aluminium
50) be the 25-150 micron, can directly use, need not be again through attrition process.Can also use the mixture of different phosphinates.
In the preferred embodiment of the present invention, in the gross weight of flame-retardant composition of the present invention, flame-retardant composition of the present invention comprises the 5-20 % by weight, or the phosphinates fire retardant of the described component (c) of 8-15 % by weight.
In the preferred implementation of flame-retardant composition of the present invention, the nitrogen combustion inhibitor that contains of described component (d) is to be selected from melamine derivative, and it comprises melamine cyanurate, trimeric cyanamide biborate, trimeric cyanamide oxalate, melamine phosphate, melamine pyrophosphate and trimeric cyanamide polyphosphate.
In the further preferred embodiment of flame-retardant composition of the present invention, the nitrogen combustion inhibitor that contains of described component (d) is to be selected from melamine cyanurate, melamine phosphate, melamine pyrophosphate, trimeric cyanamide polyphosphate and trimeric cyanamide biborate.
In the preferred embodiment of the present invention, in the gross weight of flame-retardant composition of the present invention, flame-retardant composition of the present invention comprises the 1-20 % by weight, or the described component (d) of 5-15 % by weight contain nitrogen combustion inhibitor.
in the preferred implementation of flame-retardant composition of the present invention, the aromatic series phosphorous acid ester of described component (e) is to be selected from: triphenyl phosphite, tricresyl phosphite (2-aminomethyl phenyl) ester, tricresyl phosphite (4-aminomethyl phenyl) ester, tricresyl phosphite (4-tert-butyl-phenyl) ester, tricresyl phosphite (2,4-3,5-dimethylphenyl) ester, tricresyl phosphite (2,6-3,5-dimethylphenyl) ester, tricresyl phosphite (2,6-Dimethoxyphenyl) ester, tricresyl phosphite (2-isopropyl phenyl) ester, phosphorous acid (2,6-di-isopropyl) phenyl diphenyl, tricresyl phosphite (2,6-diisopropyl phenyl) ester, tricresyl phosphite (4-tert-butyl-phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, phosphorous acid two (4-tert-butyl-phenyl)-2,4-di-tert-butyl-phenyl ester, phosphorous acid two (2,4-di-tert-butyl-phenyl)-4-tert-butyl-phenyl ester, tricresyl phosphite (4-tert-pentyl phenyl) ester, tricresyl phosphite (2,4-di-tert-pentyl-phenyl) ester, phosphorous acid two (4-tert-pentyl phenyl)-2,4-di-tert-pentyl-phenyl ester, with phosphorous acid two (2,4-di-tert-pentyl-phenyl)-4-tert-pentyl phenyl ester.
in the further preferred embodiment of flame-retardant composition of the present invention, the aromatic series phosphorous acid ester of described component (e) is to be selected from: triphenyl phosphite, tricresyl phosphite (2-aminomethyl phenyl) ester, tricresyl phosphite (4-aminomethyl phenyl) ester, tricresyl phosphite (4-tert-butyl-phenyl) ester, tricresyl phosphite (2, the 4-3,5-dimethylphenyl) ester, tricresyl phosphite (2, the 6-3,5-dimethylphenyl) ester, tricresyl phosphite (2, the 6-Dimethoxyphenyl) ester, tricresyl phosphite (2-isopropyl phenyl) ester, tricresyl phosphite (2, the 6-diisopropyl phenyl) ester, tricresyl phosphite (4-tert-butyl-phenyl) ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, tricresyl phosphite (4-tert-pentyl phenyl) ester, and tricresyl phosphite (2, the 4-di-tert-pentyl-phenyl) ester.
In the preferred embodiment of the present invention, in the gross weight of flame-retardant composition of the present invention, flame-retardant composition of the present invention comprises the 0.1-2 % by weight, or the aromatic series phosphorous acid ester of the described component (e) of 0.5-1.5 % by weight.
In the preferred implementation of flame-retardant composition of the present invention, the additive of described component (f) is to be selected from antioxidant, anti-dripping agent (such as tetrafluoroethylene, tetrafluoroethylene hexafluoropropylene copolymer etc.), tinting material to comprise dyestuff and pigment, releasing agent, hydrolysis-resisting agent, lubricant, nucleator, thermo-stabilizer, UV light stabilizing agent and their combination.
In the preferred embodiment of the present invention, in the gross weight of flame-retardant composition of the present invention, flame-retardant composition of the present invention comprises the 0-6 % by weight, or the 0.1-6 % by weight, or the additive of the described component (f) of 0.1-2 % by weight.
Flame-retardant composition of the present invention can form by technology known in the art.Described each component and optional additive are generally the form of powder or particle, can be used as mixture and extrude, and/or cut into pill or other suitable shape.Described each component can be mixed in any manner, for example, an embodiment comprises by forcing machine under molten state, each component of mixed powder or particle form, again the composition that mixes is extruded, then be ground into pill or other suitable shape; Another embodiment also comprises described each component is added in other mixing tank and carries out pre-mixing, and then mixes under molten state by forcing machine.
In fact can make moulded parts by flame-retardant composition of the present invention as above by any extruding process thereof well known by persons skilled in the art or hot-forming method.For example, injection moulding, injection moulding altogether, compression moulding, quadric injection mould and profile are extruded.Therefore, described goods can be injection moulding, compression molding or profile extrusion moulding and the moulded product or the film that prepare.
One of the present invention is preferred embodiment to comprise above-mentioned flame-retardant composition or by the prepared moulded parts of above-mentioned flame-retardant composition.
Flame-retardant composition of the present invention can be used for the various products of molding, is particularly suitable for making trolley part; And for the manufacture of the Electrical and Electronic related products, for example housing of TV set, counter body, mobile communication equipment shell and business automation equipment shell.Described flame-retardant composition can also be made the form of film and sheet material.
Embodiment
Following embodiment is exemplary, can not consist of restriction improperly to scope of the present invention.All embodiment and Comparative Examples all are prepared and test with same method.Except as otherwise noted, percentage ratio is by weight.
Each embodiment and Comparative Examples starting material used see Table 1:
Table 1
Detailed step
A) mix: (see each component of each embodiment or Comparative Examples for details table 2 and table 3) in proportion and send into twin screw extruder (ZSK-26MC of kebeilong Co., Ltd), the blend granulation is to make the flame-retardant composition of corresponding approximately 5-6 kilogram.For the forcing machine that comprises 10 heating zone designs, the Temperature Setting of forcing machine is at 120/180/250/250/250/250/250/250/250/250 ℃.Die head temperature is 250 ℃, and screw speed is 350rpm, and work output is 20 kg/hrs.
B) molding: before molding, the pill of extruding is dried to moisture content less than 40ppm.For the mechanical properties test, on 100 tons of mould machines of Sumitomo, prepare test bars according to the ISO3167 molding, the screw diameter of mould machine is 32 millimeters, nozzle diameter is 5 millimeters.Barrel temperature is set in 260 ℃, and die temperature is 80 ℃.The basic configuration of described test bars is the dumb-bell shape batten, long 150 millimeters, and wide 10 millimeters * 80 millimeters of thick 4 millimeters * length that centre portions is of a size of.
Testing method
Modulus in flexure (0.05%-0.25%) and the flexural strength under 3.5% strain are measured according to ISO178:2001 (E).
The mechanical properties of tensile modulus (0.05%-0.25%), tensile strength and tension fracture elongation rate is measured according to ISO 527:1993 (E).
Fire retardancy test: be to be " Tests for Flammability of Plastic Materials, UL94 " according to title, the method for Underwriter ' s Laboratory Bulletin 94, thickness of sample is 0.8mm, tests.According to the method, the test-results based on 5 sample gained is divided into 5VA with material, 5VB, V-0, V-1, V-2, and six grades of HB.Obtain the material of V-0 grade, that major axis with a sample becomes 180 degree to put (being the vertical combustion test) with flame, after removing the burning burning things which may cause a fire disaster, the burning of this sample and/or be no more than 10 seconds the mean time of glowing, and the vertical sample of placing does not produce the drippage material that can light absorbent cotton.
The each component consumption of embodiment and Comparative Examples, with and fire-retardant and mechanical property assessment result list in table 2 and table 3.
Table 2
Performance test data by table 2 can be found out, the flame retardant properties of the flame-retardant composition for preparing in the embodiment of the present invention not only meets the V-0 rank of UL94, compare with the composition of Comparative Examples simultaneously, have unexpectedly better mechanical property, particularly be embodied in the test result of their flexural strength of comparison and tensile strength.
By in table 2, Comparative Examples 1,2,3 and embodiment 1,3,4 measuring mechanical property result relatively, can see: for the PTT resin of different qualities viscosity, flexural strength and the tensile strength of the present composition have been improved significantly by adding 0.5% component (e) aromatic series phosphorous acid ester (being triphenyl phosphite), flexural strength and the tensile strength of corresponding Comparative Examples with respect to them improved 10% respectively at least.
From table 2, relatively Comparative Examples 1 and embodiment 1,2 measuring mechanical property result, can see: component (e) the aromatic series phosphorous acid ester (being triphenyl phosphite) of interpolation 0.5% and 1% has all improved flexural strength and the tensile strength of the present composition significantly, flexural strength and tensile strength with respect to Comparative Examples 1 have improved 10% at least.
Table 3
| The component name | Unit | Comparative Examples 4 | Comparative Examples 5 | Embodiment 5 | Embodiment 6 | Comparative Examples 6 | Comparative Examples 7 |
| (a2)PTT-2 | ％ | 39.8 | - | 39.6 | - | - | - |
| (a3)PTT-3 | ％ | - | 47.6 | - | 47.3 | - | - |
| (a’)PBT | ％ | - | - | - | - | 47.6 | 47.3 |
| (b) glass fibre | ％ | 44.8 | 29.7 | 44.5 | 29.6 | 29.7 | 29.6 |
| (c) diethyl phospho acid aluminium | ％ | 10.9 | 11.9 | 10.9 | 11.8 | 11.9 | 11.8 |
| (d) melamine cyanurate | ％ | 3.6 | 9.9 | 3.6 | 9.9 | 9.9 | 9.9 |
| (e) triphenyl phosphite | ％ | - | - | 0.5 | 0.5 | - | 0.5 |
| (f1) anti-dripping agent | ％ | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| (f2) antioxidant | ％ | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Total weight parts | ％ | 100 | 100 | 100 | 100 | 100 | 100 |
| The UL94 rank | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | |
| Modulus in flexure | MPa | 16083 | 11570 | 16596 | 11447 | 10884 | 10843 |
| Flexural strength | MPa | 187 | 175 | 227 | 200 | 172 | 178 |
| Tensile modulus | MPa | 8783 | 12848 | 18151 | 12677 | 12144 | 11777 |
| Tensile strength | MPa | 120 | 112 | 142 | 128 | 112 | 108 |
| Tension fracture elongation rate | (％) | 1.0 | 1.5 | 1.1 | 1.7 | 2.0 | 1.7 |
Performance test data by table 3 can be found out, the flame retardant properties of the flame-retardant composition for preparing in the embodiment of the present invention not only meets the rank of the V-0 of UL94, compare with the composition of Comparative Examples simultaneously, have unexpectedly better mechanical property, particularly be embodied in the test result of their flexural strength of comparison and tensile strength.
By in table 3, Comparative Examples 4,5 and embodiment 5,6 measuring mechanical property result relatively, can see: for the PTT resin of different qualities viscosity, flexural strength and the tensile strength of the present composition have been improved significantly by adding 0.5% component (e) aromatic series phosphorous acid ester (being triphenyl phosphite), flexural strength and the tensile strength of corresponding Comparative Examples with respect to them improved 10% respectively at least.
From table 3, the measuring mechanical property result that compares Comparative Examples 6 and Comparative Examples 7, can see: when component (a) is the PBT resin, when adding component (e) aromatic series phosphorous acid ester (being triphenyl phosphite) and not occuring to be the PTT resin as the present composition-be component (a), the effect that improves significantly its flexural strength and tensile strength that produces.
In a preferred embodiment of the present invention, described flame-retardant composition is comprised of following component substantially:
(a) polytrimethylene terephthalate of about 30-70 % by weight;
(b) glass fibre of about 1-50 % by weight;
(c) the phosphinates fire retardant of about 5-20 % by weight;
(d) approximately the 1-20 % by weight contain nitrogen combustion inhibitor;
(e) the aromatic series phosphorous acid ester of about 0.1-2 % by weight; With
(f) additive of about 0.1-6 % by weight,
Wherein said weight percentage is based on the gross weight of described flame-retardant composition, the flame retardant properties of described flame-retardant composition meets the V-0 rank of UL94, the thickness of its test bars is 0.8mm, and its flexural strength that records according to ISO178 and ISO527 method respectively and tensile strength are than only comprising (a), (b), (c), (d) and (f) analog value of the comparative composition of component is high by 10% at least.
Although come example and set forth the present invention with typical embodiment, its intention is not to limit the invention to shown details, because may have multiple change and alternative under purport of the present invention not deviating from.Thus, those skilled in the art only just may obtain improvement of the present invention disclosed herein and equivalent by normal experiment, and it is within the spirit and scope of the invention that appended claim limits that all these improvement and equivalent all should be considered as.
Claims (10)
1. flame-retardant composition comprises:
(a) polytrimethylene terephthalate of 30-70 % by weight;
(b) glass fibre of 1-50 % by weight;
(c) the phosphinates fire retardant of 5-20 % by weight;
(d) the 1-20 % by weight contains nitrogen combustion inhibitor;
(e) the aromatic series phosphorous acid ester of 0.1-2 % by weight; With
(f) additive of 0-6 % by weight,
Wherein said weight percentage is based on the gross weight of described flame-retardant composition, the flame retardant properties of described flame-retardant composition meets the V-0 rank of UL94, the thickness of its test bars is 0.8mm, and its flexural strength that records according to ISO178 and ISO527 method respectively and tensile strength are than only comprising (a), (b), (c), (d) and (f) analog value of the comparative composition of component is high by 10% at least.
2. flame-retardant composition as claimed in claim 1, wherein said phosphinates fire retardant (c) is phosphinates, diphosphinic acid salt or their polymkeric substance.
3. flame-retardant composition as claimed in claim 2, wherein said phosphinates fire retardant (c) is selected from: dimethyl phosphinates, ethyl-methyl phosphinates, diethyl phosphinates, methyl-n-propylphosphinic acid salt, methane two (methyl-phosphinic acid) salt, benzene-Isosorbide-5-Nitrae-(dimethyl phospho acid) salt, aminomethyl phenyl phosphinates and diphenyl phosphonic acid salt.
4. flame-retardant composition as claimed in claim 2 or claim 3, the positively charged ion of wherein said phosphinates fire retardant (c) is to be selected from: calcium, aluminium, zinc, iron and boron.
5. flame-retardant composition as claimed in claim 4, wherein said phosphinates fire retardant (c) is selected from: dimethyl phospho acid aluminium, ethyl-methyl phospho acid aluminium, diethyl phospho acid aluminium, methyl-propyl phospho acid aluminium, phospho acid calcium and diethyl phospho acid zinc.
6. flame-retardant composition as claimed in claim 1, the wherein said nitrogen combustion inhibitor (d) that contains is to be selected from melamine cyanurate, trimeric cyanamide biborate, trimeric cyanamide oxalate, melamine phosphate, melamine pyrophosphate and trimeric cyanamide polyphosphate.
7. flame-retardant composition as claimed in claim 1, wherein said aromatic series phosphorous acid ester (e) is selected from: triphenyl phosphite, tricresyl phosphite (2-aminomethyl phenyl) ester, tricresyl phosphite (4-aminomethyl phenyl) ester, tricresyl phosphite (4-tert-butyl-phenyl) ester, tricresyl phosphite (2,4-3,5-dimethylphenyl) ester, tricresyl phosphite (2,6-3,5-dimethylphenyl) ester, tricresyl phosphite (2,6-Dimethoxyphenyl) ester, tricresyl phosphite (2-isopropyl phenyl) ester, phosphorous acid (2,6-di-isopropyl) phenyl diphenyl, tricresyl phosphite (2,6-diisopropyl phenyl) ester, tricresyl phosphite (4-tert-butyl-phenyl) ester, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, phosphorous acid two (4-tert-butyl-phenyl)-2,4-di-tert-butyl-phenyl ester, phosphorous acid two (2,4-di-tert-butyl-phenyl)-4-tert-butyl-phenyl ester, tricresyl phosphite (4-tert-pentyl phenyl) ester, tricresyl phosphite (2,4-di-tert-pentyl-phenyl) ester, phosphorous acid two (4-tert-pentyl phenyl)-2,4-di-tert-pentyl-phenyl ester, with phosphorous acid two (2,4-di-tert-pentyl-phenyl)-4-tert-pentyl phenyl ester.
8. flame-retardant composition as claimed in claim 1, wherein said additive (f) is selected from: antioxidant, anti-dripping agent, tinting material comprise dyestuff and pigment, releasing agent, hydrolysis-resisting agent, lubricant, nucleator, thermo-stabilizer, UV light stabilizing agent and their combination.
9. moulded product, it comprises the flame-retardant composition of claim 1.
10. prepare the method for the flame-retardant composition of claim 1, comprising:
I. be provided for each component (a), (b), (c), (d), (e) of the flame-retardant composition of claim 1 and (f);
Ii. in the forcing machine of 240 ℃-270 ℃ mixing said ingredients to form mixed uniformly flame-retardant composition;
Iii. with described flame-retardant composition extruding pelletization;
Wherein, the flame retardant properties of described flame-retardant composition meets the V-0 rank of UL94, the thickness of its test bars is 0.8mm, and its flexural strength that records according to ISO178 and ISO527 method respectively and tensile strength are than only comprising (a), (b), (c), (d) and (f) analog value of the comparative composition of component is high by 10% at least.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105504792A (en) * | 2015-12-29 | 2016-04-20 | 湖州利鹏新材料科技有限公司 | Transparent flame-retardant nylon resin and preparation method thereof |
| CN106633682A (en) * | 2015-10-30 | 2017-05-10 | 杜邦公司 | A flame retardant composition including fiber-reinforced poly(ethylene terephthalate) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260226A (en) * | 2008-04-11 | 2008-09-10 | 卢文生 | Method for preparing high machinery performance halogen-free anti-flaming PBT composite and composite material |
| CN101768337A (en) * | 2009-01-06 | 2010-07-07 | 东丽纤维研究所（中国）有限公司 | Halogen-free antiflaming polyester, method for producing same and application thereof |
-
2011
- 2011-12-07 CN CN2011104046621A patent/CN103146155A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101260226A (en) * | 2008-04-11 | 2008-09-10 | 卢文生 | Method for preparing high machinery performance halogen-free anti-flaming PBT composite and composite material |
| CN101768337A (en) * | 2009-01-06 | 2010-07-07 | 东丽纤维研究所（中国）有限公司 | Halogen-free antiflaming polyester, method for producing same and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633682A (en) * | 2015-10-30 | 2017-05-10 | 杜邦公司 | A flame retardant composition including fiber-reinforced poly(ethylene terephthalate) |
| CN105504792A (en) * | 2015-12-29 | 2016-04-20 | 湖州利鹏新材料科技有限公司 | Transparent flame-retardant nylon resin and preparation method thereof |
| CN105504792B (en) * | 2015-12-29 | 2019-11-22 | 湖州利鹏新材料科技有限公司 | A kind of transparent flame-retarding nylon resin and preparation method thereof |
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