CN101643576A - Zero halogen flame resistance alloy composite and preparation method thereof - Google Patents
Zero halogen flame resistance alloy composite and preparation method thereof Download PDFInfo
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- CN101643576A CN101643576A CN200910165324A CN200910165324A CN101643576A CN 101643576 A CN101643576 A CN 101643576A CN 200910165324 A CN200910165324 A CN 200910165324A CN 200910165324 A CN200910165324 A CN 200910165324A CN 101643576 A CN101643576 A CN 101643576A
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Abstract
The invention discloses a zero halogen flame resistance alloy composite which mainly comprises 80-95 parts of resin mixture, 20-5 parts of phosphates fire retardant and 0.1-2 parts of polytetrafluoroethylene by weight, wherein the resin mixture comprises 40-90wt% of polycarbonate and 10-60wt% of rubber modified graft copolymer. The invention also discloses a preparation method of the zero halogenflame resistance alloy composite. In the method of the invention, a mixture of various phosphates is used as fire retardant so as to largely reduce the dosage of fire retardant and ensure that the polycarbonate alloy has not only has good flame resistance and high heat resistance, but also does not generate a large amount of toxic gases and smoke and strong cancer-causing substances which is different than the PC alloy with halogen fire retardant. The method of the invention has simple operation and environmental friendly composite product and realizes the combination of high flame resistanceand high heat resistance.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of Zero halogen flame resistance alloy composite that mainly contains polycarbonate and rubber-modified graft copolymer with and preparation method thereof.
Background technology
Polycarbonate (PC) is high performance engineering plastics, and it has very good shock resistance and thermotolerance, is applied in the various fields more and more widely.Yet, the polycarbonate price is very high always, and its melt viscosity is bigger, pure polycarbonate is relatively more difficult as extruding with injection moulding processing with common plastic working means, very difficult when particularly producing the comparatively complicated product of thinner thickness or shape, be exactly that polycarbonate ftractures under stress easily in addition.In order to improve the performance of polycarbonate, industrial usually with polycarbonate and rubber-modified graft copolymer, as acrylonitrile-butadiene-styrene copolymer (ABS) blending and modifying together, this can reduce the viscosity of polycarbonate on the one hand, improve its processibility and improve its stress cracking resistance, also can increase substantially the thermotolerance of ABS on the other hand, the PC alloy that is obtained not only over-all properties is very outstanding, and cost performance is also very high, thereby its market scale growth is very fast, and the speed with every year nearly 30% is increasing on Chinese market in recent years.
In actual life, show that through years of researches using the flame retardant resistance macromolecular material is to prevent and reduce one of effective measures of fire.Fire retardant material is compared with fire retardant material not, the former fires than difficult point, and the rate of flame propagation during burning is little, and mass loss rate and heat release rate are all lower, sometimes propagation of flame can be extinguished to certain distance automatically, so fire retardant material can prevent little fire and develop into tragic fire, and fire was eliminated in its budding stage, reduces fire hazard, even flame is failed from putting out, fire retardant material also can delay the generation of big fire, provides the more time to evacuating personnel, reduces fire losses.The most important Application Areas of PC alloy is electric, in order to guarantee the safety in utilization of these electronic and electrical equipments, generally all requires used PC alloy to have high flame retardant resistance (self-extinguishing).Pure polycarbonate is owing to the aromatic ring rigid structure of its molecular chain itself, and oxygen index is the polymkeric substance that can put out certainly up to 26.But, rubber-modified graft copolymer, owing to its a large amount of rubber constituent and alkane composition, oxygen index is about 16 as ABS, is easy to burning.The PC alloy that the direct blend of PC and rubber-modified graft copolymer obtains is generally not fire retardant material, and its flame retardant resistance is lower, does not have from putting out characteristic.
Giving the general method of macromolecular material flame retardant resistance is to introduce fire retardant in its preparation or modifying process, up to the present consumption is very big, flame retardant resistance higher and to the influence of the mechanical property of macromolecular material less be halogenated flame retardant, the fire retardant that comprises chlorine system and bromine system, but the material that halogenated flame retardant is fire-retardant, in combustion processes, can discharge than not more toxic gas volume of fire retardant material and cigarette amount, this not only can cause more dead disaster, also can produce secondary pollution and environmental pollution, even more serious is, show after deliberation, halogenated flame retardant especially can produce dioxin after the halogenated diphenyl ether burning, be many halogenated diphenyls Bing diox and many halogenated diphenyls and furans, this material has strong carinogenicity, and this has limited its application, and people have carried out many researchs in the hope of substituting halogen fire retardant with halogen-free flame retardants.The halogen-free flame retardants of consumption maximum is a metal hydroxides on the market now, comprises aluminium hydroxide and magnesium hydroxide, but owing to can discharge water outlet under their born alkalescence and the high temperature, thereby therefore the degraded of catalyst, polyester can not be used for PC and alloy thereof.The patent CN1617905 of General Electric discloses perfluoro butyl potassium sulfonate (PPFBS) fire retardation PC, and the PPFBS that adds minute quantity in PC can reach the UL94V-0 flame retardant rating, but PPFBS only to pure PC fire-retardant effectively, the PC alloy is not had flame retardant effect substantially.The patent CN1412246A of Asahi Chemical Industry discloses with organopolysiloxane and inorganic alkaline metal salt or alkaline earth salt composite flame-proof PC alloy, but it can not realize high flame retardant rating.Nitrogen flame retardant such as melamine cyanurate (MC) etc. also are widely used as halogen-free flame retardants, but a large amount of nitrogen flame retardants that studies show that does not have fire retardation substantially to PC and PC alloy.The halogen-free flame retardants that now is used for the PC alloy in a large number substantially all is the fire retardant of phosphoric acid ester system, but these phosphoric acid ester are small molecules mostly, it under the normal temperature the lower solid of liquid or fusing point, the introducing of these phosphoric acid ester can reduce the mechanical property and the thermal characteristics of PC alloy to a great extent, especially for the low slightly PC alloy of PC content, need to add a large amount of phosphoric acid ester obtaining high flame retardant resistance, but greatly reduced the thermotolerance (heat-drawn wire) and the mechanical property of material.In order to obtain high thermotolerance, the method of adding filler (mica or talcum powder) in the PC alloy that Japan Supreme Being people's patent CN1514856A discloses at organic phosphate flame-retardant, though mica or talcous adding have improved the thermotolerance of PC flame-retardant alloy, largely reduced the shock strength of material; The patent CN1388816A of Korea S LG chemical company comes the fire retardation PC alloy with phosphoric acid ester and resol, and the synergy of using resol and phosphoric acid ester has reduced the amount of the phosphoric acid ester of required interpolation, but the introducing of resol has reduced the shock strength of PC alloy.
Summary of the invention
The objective of the invention is to be to address the above problem, the halogen-free, flame-retardant composition of high flame retardant resistance, mechanical property and resistance toheat of a kind of PC of giving alloy is provided.
Another object of the present invention is to provide the preparation method of above-mentioned composition.
In order to solve the problem of mentioning in the background technology, we have carried out a large amount of research, found that for having the good flame synergistic effect between the different phosphoric acid ester of PC alloy, the mixture that mixes with the different phosphate acid esters of certain proportioning carries out fire-retardant to the PC alloy, especially for the PC alloy that hangs down the PC component, can reduce the consumption of phosphoric acid ester significantly, the flame resistance alloy composite that obtains is the flame retardant resistance height not only, and mechanical property and thermotolerance are all very high.
Purpose of the present invention can reach by following measure:
A kind of Zero halogen flame resistance alloy composite, said composition mainly by
(A) resin compound of 80-95 weight part, resin compound is made up of the polycarbonate of 40-90wt% and the rubber-modified graft copolymer of 10-60wt%;
(B) the phosphoric acid ester fire retardant of 20-5 weight part and
(C) tetrafluoroethylene of 0.1-2 weight part is formed.
Also can add other auxiliary agents therein, also can form by above-mentioned three components separately.
Resin compound is made up of 40-90wt% polycarbonate and 10-60wt% rubber-modified graft copolymer.Consider that for thermotolerance that improves composition and flame retardant resistance aspect polycarbonate is selected aromatic copolycarbonate for use, is preferably bisphenol A polycarbonate.Rubber-modified graft copolymer comprises rigidity mutually and rubber phase, rubber phase be dispersed in rigidity mutually in, wherein at least a portion rigidity by chemical graft to rubber phase.Rubber phase is in order to improve the shock resistance of material, and suitable rubber polymer is a polydiolefin, comprises a kind of polybutadiene polymers or poly-(styrene butadiene) multipolymer.In order to improve the flowability of material, generally select for use polystyrene (containing the vinylbenzene or derivatives thereof) polymkeric substance to be used as the rigidity phase as monomer, and in order to improve the consistency of its solvent resistance and itself and PC, introducing vinyl cyanide or its derivative monomer in polymkeric substance.In preferred embodiments, rubber-modified graft copolymer uses acrylonitrile-butadiene-styrene copolymer (ABS), its rigidity is acrylonitritrile-styrene resin (AS) mutually, and rubber phase is polyhutadiene (PBD), wherein is grafted with AS on the surface of polyhutadiene.The preparation method of ABS generally can be divided into two kinds, a kind of is the polymerization of carrying out AS in the presence of disperse phase (PBD), another kind is exactly the AS grafting polyhutadiene (being commonly called as high glue powder) of synthetic respectively AS and high rubber phase (PBD) content, is exactly ABS with AS and high glue powder mixing again.
Consider the over-all properties of prepared Zero halogen flame resistance alloy composite, the balance of flame retardant resistance, thermotolerance and shock resistance particularly, the content of polyhutadiene is preferably between 5-25wt% among the ABS, as be lower than the then shock resistance deficiency of composition of 5wt%, as to be higher than 25wt% then be the flame retardant resistance and the thermotolerance that can reduce composition significantly.The content of vinyl cyanide preferably between 20-30wt%, between 24-28wt%, can greatly improve the consistency of PC and ABS like this among the rigidity phase AS, thereby obtains the alloy composite of high comprehensive performance.
The used phosphoric acid ester fire retardant of the present invention is for containing the phosplate of (B1) 0-70wt% and (B2) mixture of the polyphosphate of 30-100wt%, and wherein the structural formula of phosplate is as the formula (1):
Wherein R1, R2 or R3 respectively be the alkyl of the C1-C10 that do not replace or replace independently or do not replace or the aryl of the C6-C10 of replacement.
Consider the thermostability of phosplate, R1, R2 and R3 are general preferred from aromatic yl group, as trimethylphenyl phosphoric acid ester (TCP), cumyl phenyl phosphate ester (IPPP) and triphenyl (TPP), consider from the flame retardant resistance aspect, the preferred especially higher TPP of phosphorus content, its molecular formula as the formula (3):
The structural formula of described polyphosphate is as the formula (2):
Wherein R4, R5, R6 or R7 are respectively the aryl of the C6-C10 of not replacement or replacement independently, and n is the integer of 1-5, and X is the arylidene that does not replace or replace.Wherein " aryl " described in aryl and the arylidene for be generally replace or the benzene of non-replacement, biphenyl, terphenyl, many benzene for fat hydrocarbon, naphthalene, anthracene or phenanthrene etc.The described substituting group of each group can be the alkyl of C1-C4, amino, hydroxyl etc. in formula (1) and the formula (2).
From cost consideration, preferably select biphosphonate cheap and easy to get (n=1) for use, especially aryl condensation polyphosphate, Resorcinol two (diphenyl phosphoester) (RDP) and dihydroxyphenyl propane two (diphenyl phosphoester) (BDP), its chemical molecular formula of RDP and BDP is respectively suc as formula shown in (4) and the formula (5).And consider the then preferred especially mixture of forming by RDP and BDP from the flame retardant resistance aspect.
In order to obtain high flame retardant resistance, mechanical property and stable on heating combination, flame-retardant mixture is mixed by 0-70wt% phosplate and 30-100wt% polyphosphate and forms, and when (B1) phosplate was 0wt%, the phosphoric acid ester fire retardant was (B2) polyphosphate mixture that contains two or more.The phosphoric acid ester fire retardant is preferably the phosplate that contains (B1) 20-70wt% and (B2) mixture of the polyphosphate of 30-80wt%, the polyphosphate that wherein contains two or more in the phosphoric acid ester fire retardant, polyphosphate are preferably the mixture of 30-70wt%RDP and 70-30wt%BDP composition.Fire retardant of the present invention particularly preferably is, the mixture of being made up of 20-70wt% triphenyl, 15-40wt% Resorcinol two (diphenyl phosphoester) and 15-40wt% dihydroxyphenyl propane pair (diphenyl phosphoester).
Also contain the tetrafluoroethylene of 0.1-2wt% in the Zero halogen flame resistance alloy composite of the present invention as Antidrip agent.
Other auxiliary agent comprises oxidation inhibitor, UV light stabilizing agent, lubricant, releasing agent etc., it is functional that the use of these auxiliary agents can improve some of composition, but its basic flame retardant properties and mechanics mechanical property there is not any influence substantially, can select general these commercially available auxiliary agents for use, they are not necessary for the present invention.The consumption of other auxiliary agents can be according to the purpose of adding auxiliary agent consumption interpolation routinely.
The preparation method of Zero halogen flame resistance alloy composite of the present invention, can select in following two kinds of methods any one for use:
1. with polycarbonate, rubber-modified graft copolymer, tetrafluoroethylene and solid phosphate ester (perhaps also comprising other auxiliary agent) by being transported to the forcing machine from main opening for feed after the proportioning pre-mixing, again the liquid phosphoric acid ester is mixed into liquid mixture by desired proportioning, then this liquid mixture is joined in the forcing machine with special-purpose liquid feeding device or peristaltic pump, under 200-270 ℃, carry out melt blending, make Zero halogen flame resistance alloy composite;
2. with polycarbonate, rubber-modified graft copolymer and tetrafluoroethylene (perhaps also comprising other auxiliary agent) by being transported to the forcing machine from main opening for feed after the proportioning pre-mixing, phosphoric acid ester (liquid phosphoric acid ester and solid phosphate ester) is mixed into liquid mixture by desired proportioning, then this liquid mixture is joined in the forcing machine with special-purpose liquid feeding device or peristaltic pump, under 200-270 ℃, carry out melt blending, make Zero halogen flame resistance alloy composite.
The solid phosphate ester of this place speech is meant that fusing point more than normal temperature (25 ℃), generally be to be in the solid phosphoric acid ester, and the liquid phosphoric acid ester is meant fusing point below normal temperature (25 ℃), generally is the phosphoric acid ester that is in liquid.The general fusing point of solid phosphate ester flame retardant is lower, and is directly reinforced with main hopper or side feeding, builds bridge easily and causes production not carry out continuously at charging opening.Our solid phosphate ester of discovering can be dissolved in the liquid phosphoric acid ester well, thereby solid phosphate ester can be dissolved in the liquid phosphoric acid ester in advance and form mixture, liquid feeding device or peristaltic pump by special use joins in the forcing machine together, thereby improved expressing technique.
Beneficial effect of the present invention:
The mixture that has used multiple phosphoric acid ester in the present invention is as fire retardant, can reduce the consumption of fire retardant significantly, make polycarbonate alloy not only have excellent flame retardancy and high heat resistance simultaneously, and it is different with the PC material that contains halogenated flame retardant, can in combustion processes, can not discharge a large amount of toxic gas volumes and cigarette amount, can not produce strong carinogenicity material yet.The inventive method is simple to operate, the composition environmental friendliness of preparation, and realized the combination of high flame retardant and high heat resistance.
Embodiment
The present invention will be described in detail with reference to the following examples and Comparative Examples, but these examples do not limit the scope of the invention.
Embodiment and Comparative Examples have been used following component.
(A) resinous principle
(A1) polycarbonate
Polycarbonate: IR2500, Japanese Idemitsu Petrochemical Co., Ltd..
(A2) rubber-modified graft copolymer
Acrylonitritrile-styrene resin: 1200C, toray Co., Ltd..
Acrylonitrile-styrene-methylmethacrylate copolymer: 1920B, toray Co., Ltd..
Acrylonitrile-butadiene-styrene copolymer: HR2600P, toray Co., Ltd..
MBS: EXL-2691, ROHM AND HAAS.
By 1200C or 1920B, form rubber-modified graft copolymer with HR2600P or EXL-2691.
A1/A2 is the weight ratio of polycarbonate and rubber-modified graft copolymer.
(B) phosphate flame retardant
(B1) phosplate
TPP: triphenyl, Israel's chemical engineering industry, solid.
IPPP: cumyl phenyl phosphate ester, Tianjin Lianrui Chemical Co.,Ltd, liquid.
(B2) polyphosphate
RDP: Resorcinol two (diphenyl phosphoester), Israel's chemical engineering industry, liquid.
BDP: dihydroxyphenyl propane two (diphenyl phosphoester), Israel's chemical engineering industry, liquid.
PX200: aryl condensation polyphosphate, big eight KCCs of Japan, solid.
(C) tetrafluoroethylene
PTFE: anti-dripping agent polytetrafluoroethylene powder, 3M company.
In other the auxiliary agent oxidation inhibitor select four for use [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, IR1010, vapour crust fine chemistry industry is produced, lubricant is selected the hard esteramides of ethylene, EBS for use.
Performance test methods:
Thermotolerance
HDT: with the thermotolerance that heat-drawn wire is come indicator gained alloy, its test is carried out in the load of 1.80MPa by standard ISO 75.
Flame retardant resistance
Test by standard UL94 with the vertical combustion method.Concrete is, Bunsen burner is placed the batten lower end of vertical placement, and igniting 10S removes burning things which may cause a fire disaster then, the record sample flaming combustion time; Certainly put out in the 30S after removing flame as sample, then once more Bunsen burner is placed batten lower end igniting 10S, the record burning things which may cause a fire disaster is removed back sample flaming combustion time and flameless combustion time, observe simultaneously and whether produce molten drop and molten drop and whether ignite and be put in the absorbent cotton of batten below, each sample is got 5 battens and is one group and tests, do not pass through as first group of test, can get one group again and test.Its flame retardant resistance grade is divided into V-0, and V-1, and V-2 judge that by the listed index of table 1 wherein the flame retardant resistance of V-0 is best respectively, as all not in the listed indication range of table 1, then is judged to be NC (can not classify), and its flame retardant resistance is the poorest.
Table 1 UL94 burning grade is judged index
Embodiment and Comparative Examples
A1/A2＝50/50
Comparative Examples 1
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 2-1; use the pre-mixing of high-speed mixing whipping appts even at normal temperatures; compound joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) from main hopper and melt extrudes; 260 ℃ of extrusion temperatures; rotating speed 200rpm; tie rod after extruding is cut into the particle about length 3mm with dicing machine after tank cooling; this pellet is through 80 ℃ of vacuum-dryings after 8 hours; be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day smart company produces); carry out the mensuration of UL94 and HDT, it the results are shown in Table 2-1.
Comparative Examples 2
Take by weighing resin raw material, TPP and PTFE respectively in ratio shown in the table 2-1, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, compound joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) from main hopper and melt extrudes, 230 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-1.
Comparative Examples 3
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 2-1, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, compound is from main hopper, RDP with peristaltic pump quantitatively the venting port before the forcing machine vacuum port join TEX30 α parallel dual-screw extruding machine (Japan's system steel) and melt extrude, 240 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-1.
Comparative Examples 4
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 2-1, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, compound is from main hopper, BDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with special-purpose liquid feeding device and melt extrudes, 240 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-1.
Comparative Examples 5
Take by weighing resin raw material, PX200 and PTFE respectively in ratio shown in the table 2-1, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, joining TEX30 α parallel dual-screw extruding machine (Japan's system steel) from main hopper melt extrudes, 240 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-1.
Embodiment 1
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 2-2, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's system steel) with special-purpose liquid feeding device after liquid flame retardant RDP and BDP also take by weighing in proportion and stir melt extrudes, 230 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-2.
Embodiment 2
Take by weighing resin raw material, PX200 and PTFE respectively in ratio shown in the table 2-2, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's system steel) with special-purpose liquid feeding device after liquid flame retardant RDP and BDP also take by weighing in proportion and stir melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 2-2.
Embodiment 3
Take by weighing resin raw material, TPP and PTFE respectively in ratio shown in the table 2-2, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's system steel) with special-purpose liquid feeding device after liquid flame retardant RDP and BDP also take by weighing in proportion and stir melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 2-2.
Embodiment 4
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 2-2, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat TPP dissolving back with peristaltic pump quantitatively the venting port before the forcing machine vacuum port join TEX30 α parallel dual-screw extruding machine (Japan's system steel) and melt extrude, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 2-2.
Embodiment 5
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 2-2, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat TPP dissolving back with peristaltic pump quantitatively the venting port before the forcing machine vacuum port join TEX30 α parallel dual-screw extruding machine (Japan's system steel) and melt extrude, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 2-2.
Embodiment 6
Take by weighing resin raw material, TPP and PTFE respectively in ratio shown in the table 2-2, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant RDP and BDP also take by weighing in proportion and stir, with peristaltic pump quantitatively the venting port before the forcing machine vacuum port join TEX30 α parallel dual-screw extruding machine (Japan's system steel) and melt extrude, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 2-2.
The proportioning and the performance thereof of table 2-1 Zero halogen flame resistance alloy composite
The proportioning and the performance thereof of table 2-2 Zero halogen flame resistance alloy composite
From table 2-1 as can be seen, do not add the polycarbonate alloy of phosphoric acid ester, its heat-drawn wire (HDT) is very high, but the plastification owing to phosphoric acid ester makes its HDT value reduce significantly after adding phosphoric acid ester.Comparative Examples 2,3,4 and 5 only adds a kind of phosphoric acid ester merely, as can be seen for the polycarbonate alloy of high rubber graft copolymer content, need to add quite a large amount of phosphoric acid ester, but its incendivity also is difficult to reach V-0, and its HDT is very low, can not satisfy the requirement of use.Embodiment 1-6 uses the mixture of multiple different phosphate acid esters, and reaching the required phosphoric acid ester consumption of V-0 grade can reduce significantly, makes that its HDT value is higher.Realized the combination of high flame retardant and high heat resistance.For embodiment 5 and embodiment 6, their composition and performance are just the same, difference is in embodiment 6, solid phosphate ester TPP joins the forcing machine from main hopper with other solid material, because the most fusing point of solid phosphate ester lower (is 50 ℃ as the TPP fusing point), thereby can cause charging opening place material to build bridge, that extrudes is stable bad, and in embodiment 5, we find that TPP can be dissolved in the liquid phosphoric acid ester, so TPP is dissolved in the mixing solutions of RDP and BDP earlier and mixes, one joins in the forcing machine by liquid feeding device again, such technology can not built bridge, and the stability of extruding is greatly improved.
A1/A2＝55/45
Comparative Examples 6
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 3; use the pre-mixing of high-speed mixing whipping appts even at normal temperatures; compound joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) from main hopper and melt extrudes; 260 ℃ of extrusion temperatures; rotating speed 200rpm; tie rod after extruding is cut into the particle about length 3mm with dicing machine after tank cooling; this pellet is through 80 ℃ of vacuum-dryings after 8 hours; be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day smart company produces); carry out the mensuration of UL94 and HDT, it the results are shown in Table 3.
Comparative Examples 7
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 3, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant RDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
Embodiment 7
Take by weighing resin raw material, TPP and PTFE respectively in ratio shown in the table 3, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant BDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
Embodiment 8
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 3, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
Embodiment 9
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 3, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with peristaltic pump and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
Embodiment 10
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 3, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
Embodiment 11
Take by weighing resin raw material, PTFE and IR1010 respectively in ratio shown in the table 3, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 3.
The proportioning of table 3 Zero halogen flame resistance alloy composite and performance thereof
As can be seen from Table 3, only by the polycarbonate alloy of one organic phosphate flame-retardant, even add very a large amount of, the flame retardant resistance of alloy is also bad, and because the adding of a large amount of phosphoric acid ester makes the thermotolerance of alloy reduce significantly, if and use the composite mixture group of multiple phosphoric acid ester to be fire retardant, its addition can reduce greatly, has realized the combination of high flame retardant and high heat resistance.From embodiment 8 and embodiment 11 as can be seen, add flame retardant resistance and the HDT not influence of oxidation inhibitor to composition.
A1/A2＝60/40
Comparative Examples 8
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 4; use the pre-mixing of high-speed mixing whipping appts even at normal temperatures; compound joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) from main hopper and melt extrudes; 260 ℃ of extrusion temperatures; rotating speed 200rpm; tie rod after extruding is cut into the particle about length 3mm with dicing machine after tank cooling; this pellet is through 80 ℃ of vacuum-dryings after 8 hours; be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day smart company produces); carry out the mensuration of UL94 and HDT, it the results are shown in Table 4.
Comparative Examples 9
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 4, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant BDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 4.
Embodiment 12
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 4, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 4.
Embodiment 13
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 4, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with peristaltic pump and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 4.
The proportioning of table 4 Zero halogen flame resistance alloy composite and performance thereof
Compare with Comparative Examples 9, embodiment 12 and 13 has used the mixture of multiple different phosphate acid esters, and the consumption of phosphoric acid ester greatly reduces, and the flame retardant resistance and the thermotolerance of polycarbonate alloy all are greatly enhanced.
A1/A2＝70/30
Comparative Examples 10
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 5; use the pre-mixing of high-speed mixing whipping appts even at normal temperatures; compound joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) from main hopper and melt extrudes; 260 ℃ of extrusion temperatures; rotating speed 200rpm; tie rod after extruding is cut into the particle about length 3mm with dicing machine after tank cooling; this pellet is through 80 ℃ of vacuum-dryings after 8 hours; be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day smart company produces); carry out the mensuration of UL94 and HDT, it the results are shown in Table 5.
Comparative Examples 11
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 5, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant BDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 5.
Embodiment 14
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 5, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 5.
Embodiment 15
Take by weighing resin raw material, PTFE, IR1010 and EBS respectively in ratio shown in the table 5, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with peristaltic pump and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 5.
Embodiment 16
Take by weighing resin raw material, PTFE, IR1010 and EBS respectively in ratio shown in the table 5, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with peristaltic pump and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 5.
Compare with Comparative Examples 11, embodiment 14 and 15 has used the mixture of multiple different phosphate acid esters, and the consumption of phosphoric acid ester greatly reduces, and the flame retardant resistance and the thermotolerance of polycarbonate alloy all are greatly enhanced.Other rubber-modified graft copolymer is used in embodiment 16 explanations instead, and the mixture that uses the different phosphate acid esters also can obtain the polycarbonate alloy of excellent flame retardancy and thermotolerance combination as fire retardant.
The proportioning of table 5 Zero halogen flame resistance alloy composite and performance thereof
A1/A2＝80/20
Comparative Examples 12
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 6; use the pre-mixing of high-speed mixing whipping appts even at normal temperatures; compound joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) from main hopper and melt extrudes; 260 ℃ of extrusion temperatures; rotating speed 200rpm; tie rod after extruding is cut into the particle about length 3mm with dicing machine after tank cooling; this pellet is through 80 ℃ of vacuum-dryings after 8 hours; be injection molded into the standard batten with NEX1000 injection moulding machine (a Japan day smart company produces); carry out the mensuration of UL94 and HDT, it the results are shown in Table 6.
Comparative Examples 13
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 6, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant RDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 6.
Comparative Examples 14
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 6, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant RDP quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 6.
Embodiment 17
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 6, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 6.
Embodiment 18
Take by weighing resin raw material, TPP and PTFE respectively in ratio shown in the table 6, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mixing the back joins the forcing machine from main hopper, fire retardant IPPP, RDP and BDP also take by weighing in proportion and stir, quantitatively joining TEX30 α parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device melt extrudes, 230 ℃ of extrusion temperatures, other identical with embodiment 1.It the results are shown in Table 6.
Compare with Comparative Examples 13, embodiment 17 has used the mixture of multiple different phosphate acid esters, and the consumption of phosphoric acid ester greatly reduces, and the flame retardant resistance and the thermotolerance of polycarbonate alloy all are greatly enhanced.And compare with Comparative Examples 14, embodiment 18 has used the mixture of two kinds of phosplates and two kinds of polyphosphate compositions as fire retardant, also can obtain all good polycarbonate alloy of flame retardant resistance and thermotolerance.
The proportioning of table 6 Zero halogen flame resistance alloy composite and performance thereof
Claims (8)
1, a kind of Zero halogen flame resistance alloy composite, it is characterized in that said composition mainly by
(A) resin compound of 80-95 weight part,
(B) the phosphoric acid ester fire retardant of 20-5 weight part and
(C) tetrafluoroethylene of 0.1-2 weight part is formed,
Wherein said resin compound is made up of the polycarbonate of 40-90wt% and the rubber-modified graft copolymer of 10-60wt%.
2, Zero halogen flame resistance alloy composite according to claim 1 is characterized in that described phosphoric acid ester fire retardant is for containing the phosplate of (B1) 0-70wt% and (B2) mixture of the polyphosphate of 30-100wt%; And when (B1) phosplate was 0wt%, the phosphoric acid ester fire retardant was (B2) polyphosphate mixture that contains two or more.
3, Zero halogen flame resistance alloy composite according to claim 2, it is characterized in that described phosphoric acid ester fire retardant for containing the phosplate of (B1) 20-70wt% and (B2) mixture of the polyphosphate of 30-80wt%, wherein contains two or more polyphosphate in the phosphoric acid ester fire retardant.
4, according to claim 2 or 3 described Zero halogen flame resistance alloy composites, the structural formula that it is characterized in that described phosplate as the formula (1):
Wherein R1, R2 or R3 do not replace or the alkyl of the C1-C10 of replacement or the aryl of C6-C10;
The structural formula of described polyphosphate is as the formula (2):
Wherein R4, R5, R6 or R7 are respectively the aryl of the C6-C10 of not replacement or replacement independently, and n is the integer of 1-5, and X is the arylidene that does not replace or replace.
5, Zero halogen flame resistance alloy composite according to claim 4, it is characterized in that described phosplate is trimethylphenyl phosphoric acid ester, cumyl phenyl phosphate ester or triphenyl, described polyphosphate is Resorcinol two (diphenyl phosphoester), dihydroxyphenyl propane two (diphenyl phosphoester) or aryl condensation polyphosphates.
6, Zero halogen flame resistance alloy composite according to claim 5 is characterized in that described phosphoric acid ester fire retardant is for containing the mixture of 20-70wt% triphenyl, 15-40wt% Resorcinol two (diphenyl phosphoester) and 15-40wt% dihydroxyphenyl propane two (diphenyl phosphoester).
7, the preparation method of the described Zero halogen flame resistance alloy composite of a kind of claim 1, it is characterized in that polycarbonate, rubber-modified graft copolymer, tetrafluoroethylene and solid phosphate ester, perhaps also comprise other auxiliary agents, be transported to the forcing machine from main opening for feed after the pre-mixing, again the liquid phosphoric acid ester is mixed into liquid mixture, then this liquid mixture is joined in the forcing machine with liquid feeding device or peristaltic pump, under 200-270 ℃, carry out melt blending, make Zero halogen flame resistance alloy composite.
8, the preparation method of the described Zero halogen flame resistance alloy composite of a kind of claim 1, it is characterized in that polycarbonate, rubber-modified graft copolymer and tetrafluoroethylene, perhaps also comprise other auxiliary agent, be transported to the forcing machine from main opening for feed after the pre-mixing, phosphoric acid ester is mixed the back to join in the forcing machine by liquid feeding device or peristaltic pump, under 200-270 ℃, carry out melt blending, make Zero halogen flame resistance alloy composite.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101982498A (en) * | 2010-09-30 | 2011-03-02 | 深圳市金缙业科技有限公司 | Halogen free antiflaming polycarbonate and rubber modified graft copolymer alloy and preparation method thereof |
| CN102464876A (en) * | 2010-11-15 | 2012-05-23 | 苏州汉扬精密电子有限公司 | Polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) waste material modification and recovery formula |
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| CN113603998A (en) * | 2021-08-30 | 2021-11-05 | 安庆会通新材料有限公司 | Low-odor flame-retardant antibacterial HIPS material for electric appliances and preparation method thereof |
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| EP0483628B1 (en) * | 1990-10-29 | 1996-05-29 | BASF Aktiengesellschaft | Flame-proof thermoplastic moulding compositions based on polycarbonates fee of chlorine or bromine, and copolymers of styrene and acrylonitrile |
| DE4309142A1 (en) * | 1993-03-22 | 1994-09-29 | Bayer Ag | Flameproofed moulding compositions based on polycarbonates/graft polymer |
| US5723526A (en) * | 1993-09-08 | 1998-03-03 | Teijin Chemicals Ltd | Resin composition and molded article |
| JPH1135816A (en) * | 1997-07-23 | 1999-02-09 | Techno Polymer Kk | Flame-retardant thermoplastic resin composition |
| TW444041B (en) * | 1998-02-13 | 2001-07-01 | Gen Electric | Flame retardant carbonate polymer composition with improved hydrolytic stability |
| KR100540583B1 (en) * | 1999-07-12 | 2006-01-10 | 제일모직주식회사 | Flame retardant hermoplastic resin composition |
| JP2003041112A (en) * | 2001-07-31 | 2003-02-13 | Asahi Kasei Corp | Polycarbonate-based flame retardant resin composition and thin-walled molded product |
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| WO2003080728A1 (en) * | 2002-03-27 | 2003-10-02 | Teijin Chemicals, Ltd. | Flame-retardant aromatic polycarbonate resin composition |
| DE10328665A1 (en) * | 2003-06-26 | 2005-01-13 | Bayer Materialscience Ag | Polycarbonate molding compounds with improved melt flowability and chemical resistance |
| CN101230188A (en) * | 2007-01-26 | 2008-07-30 | 佛山市顺德区汉达精密电子科技有限公司 | Polycarbonate/acrylonitrile-butadiene-phenylethene copolymer alloy |
| CN101139459B (en) * | 2007-08-30 | 2011-12-21 | 上海金发科技发展有限公司 | Non-bittern flame-proof thermostable polycarbonate and acrylonitrile-butadiene-phenylethene grafted copolymer alloy resin and method for preparing same |
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| CN101982498A (en) * | 2010-09-30 | 2011-03-02 | 深圳市金缙业科技有限公司 | Halogen free antiflaming polycarbonate and rubber modified graft copolymer alloy and preparation method thereof |
| CN102464876A (en) * | 2010-11-15 | 2012-05-23 | 苏州汉扬精密电子有限公司 | Polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) waste material modification and recovery formula |
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