CN101982498A - Halogen free antiflaming polycarbonate and rubber modified graft copolymer alloy and preparation method thereof - Google Patents
Halogen free antiflaming polycarbonate and rubber modified graft copolymer alloy and preparation method thereof Download PDFInfo
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- CN101982498A CN101982498A CN2010105012257A CN201010501225A CN101982498A CN 101982498 A CN101982498 A CN 101982498A CN 2010105012257 A CN2010105012257 A CN 2010105012257A CN 201010501225 A CN201010501225 A CN 201010501225A CN 101982498 A CN101982498 A CN 101982498A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention provides a halogen free antiflaming polycarbonate and rubber modified graft copolymer alloy. The raw materials include 80-95 parts by weight of resin mixture, 5-20 parts by weight of phosphate antiflaming agent, 0.1-2 parts of polytetrafluoroethylene; wherein the resin mixture is composed of 40-90wt% of polycarbonate and 10-60wt% of rubber modified graft copolymer. The copolymer of the invention adopts mixture of multiple phosphates as antiflaming agent, usage amount of antiflaming agent can be greatly reduced, so that polycarbonate alloy not only has good flame resistance and high heat resistance but also is different from PC material containing halogen series antiflaming agent, no toxic gas or smoke can be released in reburning process, and no carcinogenicity substance can be produced. The preparation method of the invention has simple operation, the prepared alloy is environmentally friendly, and combination of high flame resistance and high heat resistance is realized.
Description
[technical field]
The present invention relates to polymeric material field, be specifically related to a kind of halogen-free and flame-retardant polycarbonate and rubber-modified graft copolymer Alloy And Preparation Method.
[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 big, 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, order also can increase substantially the thermotolerance of ABS on the one 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 spontaneous combustion, fire retardant material also can delay the generation of big fire, gives evacuating personnel the more time is provided, and 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 hydroxyl 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 that halogen is flame retardant resistance, 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, 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.
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 basically 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, 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 difficult hot (heat-drawn wire) and the mechanical property of material.In order to obtain high thermotolerance, there is bibliographical information in the PC of organic phosphate flame-retardant alloy, to add the method for filler (mica or talcum powder), though mica or talcous adding have improved the thermotolerance of PC flame-retardant alloy, largely reduced the shock strength of material.
[summary of the invention]
The objective of the invention is to be to address the above problem, the PC/ABS alloy of the high flame retardant resistance of a kind of PC of giving, mechanical property and resistance toheat is provided.
To achieve the above object of the invention, the present invention proposes following technical scheme:
A kind of halogen-free and flame-retardant polycarbonate and rubber-modified graft copolymer alloy comprise following compositions in portion by weight in its raw material:
Resin compound 80-95 part
Phosphoric acid ester fire retardant 5-20 part
Tetrafluoroethylene 0.1-2 part;
Wherein, described resin compound is made up of the polycarbonate of 40-90wt% and the rubber-modified graft copolymer of 10-60wt%.
In above-mentioned halogen-free and flame-retardant polycarbonate and the rubber-modified graft copolymer alloy, described phosphoric acid ester fire retardant is made up of 0-70wt% phosplate and 30-100wt% polyphosphate, and when phosplate was 0wt%, described phosphoric acid ester fire retardant contained two or more polyphosphate mixture.
In above-mentioned halogen-free and flame-retardant polycarbonate and the rubber-modified graft copolymer alloy, described phosphoric acid ester fire retardant is made up of 20-70wt% phosplate and 30-80wt% polyphosphate.
In above-mentioned halogen-free and flame-retardant polycarbonate and the rubber-modified graft copolymer alloy, described phosplate is triphenyl and/or cumyl phenyl phosphate ester.
In above-mentioned halogen-free and flame-retardant polycarbonate and the rubber-modified graft copolymer alloy, described polyphosphate is to be selected from Resorcinol two (diphenyl phosphoester), dihydroxyphenyl propane two (diphenyl phosphoester), tetraphenyl (bisphenol-A) bisphosphate or aryl condensation polyphosphate.
In above-mentioned halogen-free and flame-retardant polycarbonate and the rubber-modified graft copolymer alloy, described polycarbonate is an aromatic copolycarbonate.
In above-mentioned halogen-free and flame-retardant polycarbonate and the rubber-modified graft copolymer alloy, described rubber-modified graft copolymer is by acrylonitritrile-styrene resin or acrylonitrile-styrene-methylmethacrylate copolymer, forms with acrylonitrile-butadiene-styrene copolymer or the copolymerization of MBS modify and graft.
In above-mentioned halogen-free and flame-retardant polycarbonate and the rubber-modified graft copolymer alloy, also comprise oxidation inhibitor, lubricant, UV light stabilizing agent, releasing agent in the described raw material.
Among the present invention, resin combination 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 distributed 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.For 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 anti-dissolubility and itself and PC, introducing third rare nitrile 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, rubber phase is polyhutadiene (PBD), the preparation method who wherein is grafted with AS.ABS on the surface of polyhutadiene generally can be divided into two kinds, a kind of is the polymerization of carrying out AS under disperse phase (PBD) exists, 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 halogen-free and flame-retardant polycarbonate and rubber-modified graft copolymer alloy, the balance of flame retardant resistance, thermotolerance and shock resistance particularly, the content that removes divinyl among the ABS is preferably between 5-25wt%, as be lower than the then shock resistance deficiency of composition of 5wt%, as be higher than 25wt% then be can beat the flame retardant resistance and the thermotolerance of amplitude reduction composition.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 of high comprehensive performance.
In order to obtain high flame retardant resistance, mechanical property and stable on heating combination, 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 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% as Antidrip agent in halogen-free and flame-retardant polycarbonate of the present invention and the rubber-modified graft copolymer alloy.
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 most important for the present invention.The consumption of other auxiliary agents can be according to the purpose of adding auxiliary agent consumption interpolation routinely.
Another object of the present invention provides the preparation method of aforementioned halogen-free and flame-retardant polycarbonate and rubber-modified graft copolymer alloy, its step is, getting polycarbonate, acrylonitrile-butadiene-styrene copolymer, tetrafluoroethylene is transported to the forcing machine from main opening for feed after by predetermined proportioning pre-mixing, again phosphate flame retardant is mixed with liquid mixture by predetermined amount, adopt feeding device or peristaltic pump to join in the forcing machine this liquid mixture then, under 200-270 ℃, carry out melt blending, promptly.
Above-mentioned preparation method, also can be to get solid phosphoric acid ester moiety in the described phosphate flame retardant to be transported to the forcing machine from main opening for feed after by predetermined proportioning and polycarbonate, acrylonitrile-butadiene-styrene copolymer, tetrafluoroethylene pre-mixing, again the liquid phosphoric acid ester in the phosphate flame retardant is mixed with liquid mixture by predetermined amount, adopts feeding device or peristaltic pump to join in the forcing machine this liquid mixture then.
Above-mentioned solid phosphate ester 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.Solid phosphate ester can be dissolved in the liquid phosphoric acid ester well simultaneously, 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.
As can be seen from the above technical solutions, owing to used the mixture of multiple phosphoric acid ester as fire retardant in the starting material of halogen-free and flame-retardant polycarbonate of the present invention and rubber-modified graft copolymer alloy, 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 can not discharge a large amount of toxic gases and cigarette amount in the reignition process, can not produce strong carinogenicity material yet.Preparation method of the present invention is simple to operate, the alloy 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.
Wherein, embodiment and Comparative Examples have been used following component.
(A) resin Composition
(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, solid.
BDP: dihydroxyphenyl propane two (diphenyl phosphoester, Israel's chemical engineering industry, solids.
PX200: aryl condensation polyphosphate, big eight KCCs of Japan, solid.
(C) polytetrafluoroethylene PTFE: anti-dripping agent polytetrafluoroethylene powder, 3M company.
(D) other auxiliary agent
Wherein 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.
The performance test methods that relates in the embodiment of the invention and the comparative example:
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
UL94 tests with vertical combustion bill standard.Specifically be, Bunsen burner is placed the batten lower end of vertical placement, igniting 10S, remove burning things which may cause a fire disaster then, the record sample flaming combustion time: after removing flame, put out certainly in the 30S 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, V-1, and V-2 judges 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), its flame retardant resistance is the poorest.
Table 1UL94 burning grade is judged index
Embodiment and Comparative Examples
First group: A1/A2=50/50
Embodiment 1
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 2-2, use the high-speed mixing device pre-mixing even at normal temperatures, mixing the back joins the forcing machine from main hopper, quantitatively joining TEX30a 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 2-1.
Embodiment 2
Take by weighing resin raw material, PX200 and TFE respectively in ratio shown in the table 2-1, 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 TEX30a 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 2-1.
Embodiment 3
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, mixing the back adds individual to forcing machine from main hopper, quantitatively joining TEX30a 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 temperature have been squeezed, other identical with example 1.It the results are shown in Table 2-1.
Embodiment 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, 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 TEX30a parallel dual-screw extruding machine (Japan's system steel) and melt extrude, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 2-1.
Embodiment 5
Take by weighing resin raw material and PTEE respectively in ratio shown in the table 2-1, stirring with high-speed mixing at normal temperatures accompanies the device pre-mixing even, 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 TEX30a parallel dual-screw extruding machine (Japan's system steel) and melt extrude, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 2-1.
Embodiment 6
Take by weighing resin raw material respectively in ratio shown in the table 2-1, TPP and PTEE, stirring with high-speed mixing at normal temperatures accompanies the device pre-mixing even, mixing the back joins the forcing machine from main hopper, fire retardant RDP and BDP also take by weighing evenly in proportion, with peristaltic pump quantitatively the venting port before the forcing machine vacuum port join TEX30a parallel dual-screw extruding machine (Japan's system steel) and melt extrude, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 2-1.
The proportioning and the performance thereof of table 2-1 Zero halogen flame resistance alloy composite
Comparative Examples 1
Weigh 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; compound joins TEX30a 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 bar 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 2-2.
Comparative Examples 2
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, compound joins TEX30a homophase twin screw extruder (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 2-2.
Comparative Examples 3
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, compound is from main hopper, RDP with peristaltic pump quantitatively the venting port before the forcing machine vacuum port join TEX30a 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 2-2.
Comparative Examples 4
Take by weighing resin raw material and PTFE respectively in ratio shown in the table 2-2, mix with the high-speed mixing whipping appts at normal temperatures, compound is from main hopper, BDP quantitatively joins TEX30a 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 2-2.
Comparative Examples 5
Take by weighing resin raw material, PX200 and PTFE respectively in ratio shown in the table 2-2, use the high-speed stirring apparatus pre-mixing even at normal temperatures, join TEX30a parallel dual-screw extruding machine (Japan system steel) from main hopper and melt extrude, 240 ℃ of extrusion temperatures, other identical with Comparative Examples 1.It the results are shown in Table 2-2.
The proportioning and the performance thereof of table 2-2 Zero halogen flame resistance alloy composite
From table 2-2 as can be seen, do not add the polycarbonate alloy of phosphoric acid fat, its heat-drawn wire (HDT) is very high, but the plastification owing to phosphoric acid fat makes its HDT reduce significantly after adding phosphoric acid fat.Comparative Examples 2,3,4 and 5 as can be seen, pure of unit adds a kind of phosphoric acid fat, for the polycarbonate alloy of high rubber graft copolymer content, needs to add quite a large amount of phosphoric acid fat, but its incendivity is difficult to reach V-0, and its HDTD is very low, can not satisfy the requirement of use.Embodiment 1-6 uses the mixture of multiple different phosphoric acid fat, and reaching the required phosphoric acid fat 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.In embodiment 6, solid phosphoric acid fat TPP joins the forcing machine from main hopper with other solid material, because the most fusing point of solid phosphoric acid fat 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 RDPT 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.
Second group: 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 TEX30a parallel dual-screw extruding machine (Japan's system steel) from major ingredient 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 bar 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 PTEE respectively in ratio shown in the table 3, even with the pre-mixing of high-speed mixing whipping appts under temperature commonly used, mixing the back joins the forcing machine from main hopper, fire retardant RDP joins TEX30a parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 3.
Embodiment 7
Take by weighing resin raw material respectively in ratio shown in the table 3, TPP and PTEE, 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 TEX30a 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 PTEE respectively in ratio shown in the table 3, even with the pre-mixing of high-speed mixing whipping appts under temperature commonly used, 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 joins TEX30a parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 3.
Embodiment 9
Take by weighing resin raw material and PTEE respectively in ratio shown in the table 3, even with the pre-mixing of high-speed mixing whipping appts under temperature commonly used, 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 joins TEX30a parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 3.
Embodiment 10
Take by weighing resin raw material and PTEE respectively in ratio shown in the table 3, even with the pre-mixing of high-speed mixing whipping appts under temperature commonly used, 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 joins TEX30a parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 3.
Embodiment 11
Take by weighing resin raw material respectively in ratio shown in the table 3, PTEE and IR1010, even with the pre-mixing of high-speed mixing whipping appts under temperature commonly used, mixing the back joins the forcing machine from main hopper, fire retardant TPP, RDP and BDP also take by weighing in proportion and stir, and treat that TPP dissolving back quantitatively joins TEX30a parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 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, alloy resistive also not so good, and because the adding of a large amount of phosphoric acid ester makes the thermotolerance of alloy reduce significantly, and if 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 example 8 and example 11 as can be seen, add flame retardant resistance and the HDT not influence of oxidation inhibitor to composition.
The 3rd group: A1/A2=60/40
Comparative Examples 8
Show that in table 4 ratio takes by weighing resin raw material and PTEE respectively; use the pre-mixing of high-speed mixing whipping appts even at normal temperatures; compound joins TEX30a 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 bar 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 PTEE 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 TEX30a parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 4.
Embodiment 12
Take by weighing resin raw material and PTEE respectively in ratio shown in the table 4, even with the pre-mixing of high-speed mixing whipping appts under temperature commonly used, 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 joins TEX30a parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 4.
Embodiment 13
Take by weighing resin raw material and PTEE respectively in ratio shown in the table 4, even with the pre-mixing of high-speed mixing whipping appts under temperature commonly used, 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 TEX30a parallel dual-screw extruding machine (Japan's system steel) with peristaltic pump and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 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 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.
The 4th group: A1/A2=70/30
Comparative Examples 10
Take by weighing resin raw material and PTEE respectively in ratio shown in the table 5; use the pre-mixing of high-speed mixing whipping appts even at normal temperatures; compound joins TEX30a 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 bar 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
Show that in table 5 ratio takes by weighing resin raw material and PTEE respectively, 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 TEX30a parallel dual-screw extruding machine (Japan's system steel) with liquid feeding device and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 5.
Embodiment 14
Show that in table 5 ratio takes by weighing resin raw material and PTEE respectively, even with the pre-mixing of high-speed mixing whipping appts under temperature commonly used, 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 TEX30a parallel dual-screw extruding machine (Japan's system steel) with peristaltic pump and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 5.
Embodiment 15
Take by weighing resin raw material respectively in ratio shown in the table 5, PTFE, IR1010 and EBS, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mix the back and join the forcing machine fire retardant TPP from main hopper, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30a parallel dual-screw extruding machine (Japan's system steel) with peristaltic pump and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 5.
Embodiment 16
Take by weighing resin raw material respectively in ratio shown in the table 5, PTFE, IR1010 and EBS, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mix the back and join the forcing machine fire retardant TPP from main hopper, RDP and BDP also take by weighing in proportion and stir, treat that TPP dissolving back quantitatively joins TEX30a parallel dual-screw extruding machine (Japan's system steel) with peristaltic pump and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 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
The 5th group: A1/A2=80/20
Comparative Examples 12
Show that in table 6 ratio takes by weighing resin raw material and PTEE respectively; use the pre-mixing of high-speed mixing whipping appts even at normal temperatures; compound joins TEX30a 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 bar 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 PTEE respectively in table 6 ratio, 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 feeding unit quantitatively joins TEX30a parallel dual-screw extruding machine (Japan's system steel) and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 6.
Comparative Examples 14
Take by weighing resin raw material and PTEE respectively in table 6 ratio, 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 feeding unit quantitatively joins TEX30a parallel dual-screw extruding machine (Japan's system steel) and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 6.
Embodiment 17
Take by weighing resin raw material and PTEE respectively in table 6 ratio, even with the pre-mixing of high-speed mixing whipping appts under temperature commonly used, 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 TEX30a parallel dual-screw extruding machine (Japan's system steel) with peristaltic pump and melt extrudes, 230 ℃ of extrusion temperatures, other identical with example 1.It the results are shown in Table 6.
Embodiment 18
Take by weighing resin raw material respectively in ratio shown in the table 6, TPP and PTEE, use the pre-mixing of high-speed mixing whipping appts even at normal temperatures, mix the back and join the forcing machine fire retardant IPPP, RDP from main hopper, BDP also takes by weighing in proportion and stirs, quantitatively join TRX30a parallel dual-screw extruding machine (Japan system steel) with liquid feeding device and melt extrude, 230 ℃ of extrusion temperatures, other with to implement 1 identical.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.Now 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
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. halogen-free and flame-retardant polycarbonate and rubber-modified graft copolymer alloy comprise following compositions in portion by weight in its raw material:
Resin compound 80-95 part
Phosphoric acid ester fire retardant 5-20 part
Tetrafluoroethylene 0.1-2 part;
Wherein, described resin compound is made up of the polycarbonate of 40-90wt% and the rubber-modified graft copolymer of 10-60wt%.
2. halogen-free and flame-retardant polycarbonate according to claim 1 and rubber-modified graft copolymer alloy, it is characterized in that, described phosphoric acid ester fire retardant is made up of 0-70wt% phosplate and 30-100wt% polyphosphate, and when phosplate was 0wt%, described phosphoric acid ester fire retardant contained two or more polyphosphate mixture.
3. halogen-free and flame-retardant polycarbonate according to claim 1 and rubber-modified graft copolymer alloy is characterized in that, described phosphoric acid ester fire retardant is made up of 20-70wt% phosplate and 30-80wt% polyphosphate.
4. according to claim 2 or 3 described halogen-free and flame-retardant polycarbonates and rubber-modified graft copolymer alloy, it is characterized in that described phosplate is triphenyl and/or cumyl phenyl phosphate ester.
5. according to claim 2 or 3 described halogen-free and flame-retardant polycarbonates and rubber-modified graft copolymer alloy, it is characterized in that described polyphosphate is to be selected from Resorcinol two (diphenyl phosphoester), dihydroxyphenyl propane two (diphenyl phosphoester), tetraphenyl (bisphenol-A) bisphosphate or aryl condensation polyphosphate.
6. halogen-free and flame-retardant polycarbonate according to claim 1 and rubber-modified graft copolymer alloy is characterized in that described polycarbonate is an aromatic copolycarbonate.
7. halogen-free and flame-retardant polycarbonate according to claim 1 and rubber-modified graft copolymer alloy, it is characterized in that, described rubber-modified graft copolymer is by acrylonitritrile-styrene resin or acrylonitrile-styrene-methylmethacrylate copolymer, forms with acrylonitrile-butadiene-styrene copolymer or the copolymerization of MBS modify and graft.
8. halogen-free and flame-retardant polycarbonate according to claim 1 and rubber-modified graft copolymer alloy is characterized in that, also comprise oxidation inhibitor, lubricant, UV light stabilizing agent, releasing agent in the described raw material.
9. the preparation method of described halogen-free and flame-retardant polycarbonate of claim 1 and rubber-modified graft copolymer alloy, its step is, getting polycarbonate, acrylonitrile-butadiene-styrene copolymer, tetrafluoroethylene is transported to the forcing machine from main opening for feed after by predetermined proportioning pre-mixing, again phosphate flame retardant is mixed with liquid mixture by predetermined amount, adopt feeding device or peristaltic pump to join in the forcing machine this liquid mixture then, under 200-270 ℃, carry out melt blending, promptly.
10. the preparation method of halogen-free and flame-retardant polycarbonate according to claim 9 and rubber-modified graft copolymer alloy, it is characterized in that, getting solid phosphoric acid ester moiety in the described phosphate flame retardant is transported to the forcing machine from main opening for feed after by predetermined proportioning and polycarbonate, acrylonitrile-butadiene-styrene copolymer, tetrafluoroethylene pre-mixing, again the liquid phosphoric acid ester in the phosphate flame retardant is mixed with liquid mixture by predetermined amount, adopts feeding device or peristaltic pump to join in the forcing machine this liquid mixture then.
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| CN101445653A (en) * | 2008-12-11 | 2009-06-03 | 上海交通大学 | Preparation method of non-halogen flame-retarded makrolan/acrylonitrile-butadiene-styrene copolymer alloy |
| CN101643576A (en) * | 2008-08-05 | 2010-02-10 | 东丽纤维研究所（中国）有限公司 | Zero halogen flame resistance alloy composite and preparation method thereof |
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| CN101643576A (en) * | 2008-08-05 | 2010-02-10 | 东丽纤维研究所（中国）有限公司 | Zero halogen flame resistance alloy composite and preparation method thereof |
| CN101445653A (en) * | 2008-12-11 | 2009-06-03 | 上海交通大学 | Preparation method of non-halogen flame-retarded makrolan/acrylonitrile-butadiene-styrene copolymer alloy |
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| CN109161178A (en) * | 2018-07-19 | 2019-01-08 | 厦门聚信义塑胶有限公司 | A kind of flame retardant plastics and preparation method thereof |
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