Background technology
In the prior art, the preparation method of fire retardant mylar mainly contains two kinds: the one, and the fire retardant of employing copoly type and terephthalic acid and terepthaloyl moietie carry out copolymerization, and the section of preparation flame retardant polyester is processed film through stretch processes again; The 2nd, the fire retardant of commixed type and PET Resin/Poyester Chips Bottle Grade carry out blend, extrude and process fire-retardant master granule, and then process film through stretch processes.
Main research at present concentrates on the method for fire retardants such as sneaking into bromine system, phosphorus system, inorganic system in the polyester film, perhaps will contain the composition of halogen or contain the method that the composition of phosphorus carries out copolymerization.
Liu Ji equality is in " China is fire-retardant " the 2nd phase in 2010; The 15-18 page or leaf in " the halogen-free flameproof The Characteristics of low-melting point PET ", is employed in the technology that the low-melting point polyester film surface applies; The PET film surface is arrived in ammonium polyphosphate/compositional flame-retardant material roller coating after handling; Be used for Electronic Packaging, but the reduction of its wet-hot aging performance, flame retardant resistance is also lower.Toray company is 200410002478.4 (publication No. CN1517402A at application number; Date of publication: announced in the one Chinese patent application on August 4th, 2004), be superimposed upon special organic and inorganic hybrid materials a kind of laminated film of the both sides formation of PET film.This structure makes film can control the inflammable gas diffusion, in the extremely short time, puts out a fire, and can also control the drippage of melt-combustion polymkeric substance fully, reaches UL 94 standard VTM-0 levels.
Development about the copolymerization fire retardant mylar mainly contains: Zang Guoqiang (fire-retardant film is used PET PREPARATION, " modern plastics processed and applied ",, 15 (3) phases, 12-14 page or leaf in 2002) adopts the DMT method, has synthesized flame retardant type PET, and has carried out the biaxially oriented film test; Application number is that (publication No.: CN1554703, date of publication: one Chinese patent application on December 15th, 2004) has been announced PET Resin/Poyester Chips Bottle Grade and fire retardant melt-mixing method production fire retardant mylar to 200310104141.X.Adopt the polyester film of this method preparation can not all reach VTM-0 flame retardant rating, the also transparency of not mentioned film.Application number is 200510094123.7, and (publication No.: CN1923889, date of publication: one Chinese patent application on March 7th, 2007) has been announced, is employed in the method synthesizing polyester that adds organosilicate in the production of polyester, processes fire retardant mylar.Wang Shuxia etc. (development of polyester for flame-retadant film and performance study [J]. " synthetic technology and application "; 2009,24 (3) phases, 1-4 page or leaf) employing PTA method; Through in the polyester process, adding the synthetic flame retardant polyester section of phosphonium flame retardant, and be that raw material is processed fire retardant mylar with this polyester.The polyester film of above-mentioned preparation exists to melt in the test of UL94 flame retardant rating and drips a phenomenon, does not in fact reach the requirement of VTM-0 flame retardant rating.Also not mentioned in addition such modification by copolymerization fire retardant mylar thermostability and index of transparency.
Because the complex process of copolymerization is produced the route adjustment greatly, cost is high; And the equipment that applies has high input, and the wet-hot aging performance of product all significantly reduces, and using in field of electronics all has bigger obstacle.Therefore, producing flame-resistant sheet material and film with novel blending fire retardant polyester, is the most effective and feasible method.
Publication No. is US6794432; Date of publication is that the U.S. Patent application on September 21st, 2004 has been described the Amgard P1045's (production of Albright wilison company) that adds 5-10%; The method of phosphonium flame retardant modified poly ester film; The fire-retardant film transmittance is up to more than 90%, but flame retardant resistance is relatively poor.Clariant is US2009/0088512 at application number; The applying date is the U.S. Patent application on April 2nd, 2009; DSM N. V. is US2006/0111519 at application number, and the applying date is in the U.S. Patent application on May 25th, 2006, adopts fire retardant and cyclic ester compound lubricants and toughner such as organophosphate, organic hypophosphite respectively; Realized thin-walled, high-performance and the easy processed polyesters product of plastic part, but unstable for film flame retardant resistance below the 350 μ m and mechanical property.
Number of patent application is 20110039987 (date of publication: on February 17th, 2011; Denomination of invention: U.S. Patent application Method for the production of block copolycarbonate/phosphonates and compositions therefrom), announced aromatic series polyphosphonates carbonate copolymer and preparation method thereof.
Publication No. is that (date of publication: one Chinese patent application on February 10th, 2010) discloses the flame retardant resistance of improving polyester film through copolymerization and blend two-step approach to CN101643574; But, be difficult in halogen-free flame-retardant system, obtain promote owing to added brominated flame-retardant in the flame-retardant system.People (Formation ofa flame retardant cyclodextrin inclusion compound and its app lication as a flame retardant for poly (ethylene terephthalate) .Polymer Degradation and Stability such as Huang L; Calendar year 2001; 71:279-284.) once acted synergistically with beta-cyclodextrin with fire retardant nitrogen with phosphorous; The flame retardant properties of fiber level PET plastics film is significantly improved, but the vertical combustion grade still is the VTM-2 level.
From international and domestic present Research, all fail ideal to fire retardant mylar and solve the contradiction of macromolecule material film halogen-free flameproof and mechanics, do not change the transparent relatively poor present situation of fire-retardant film yet.Adopting the blending fire retardant modification to solve the fire-retardant solution thinking of film, all is compatiblely fire-retardantly to carry out simultaneously with strengthening from promoting, mainly is to drip and/or promote into two aspects of charcoal from promoting to melt, and all is difficult to make the high performance thin film product of transparent halogen-free flameproof.
Existing technical disadvantages is: the cost that the fire retardant of employing copoly type and terephthalic acid and terepthaloyl moietie carry out copolymerization mode is high, complex process, and facility investment is big; The fire retardant of commixed type and PET Resin/Poyester Chips Bottle Grade carry out the mode of blend, because the addition of fire retardant is big, mechanical property is unstable, and material is opaque, can not be used for the display transparent field.
Summary of the invention
In order to overcome the defective of flame-retardant polyester material is processed in the prior art film transparency difference, the present invention provides a kind of macromolecular carbon forming flame-retardant polyester material and preparation method thereof and the film that made by this flame-retardant polyester material and preparation method thereof.Macromolecular carbon forming flame-retardant polyester material flame retardant resistance provided by the invention is better, and its preparation method production cost is low, technology simple, easy handling.The film flame retardant resistance and the transparency that macromolecular carbon forming flame-retardant polyester material provided by the invention makes are all better, and physical strength is good.Its preparation method technology is simple, easy handling.
In order to solve the problems of the technologies described above, the present invention provides following technical proposals:
The present invention provides a kind of macromolecular carbon forming flame-retardant polyester material, and its feature is, said polyester material comprises following component, and following umber is parts by weight:
Aromatic polyester 30-50 part, macromolecular carbon forming polymkeric substance 30-50 part, short char-forming agent 0.01-1 part, phosphorus flame retardant 10-18 part, transesterification catalyst 0.1-1 part; The total amount of said components is 100 parts.Said phosphorus flame retardant comprises common aromatic series bis-phenol phenyl polyphosphonates homopolymer; Like polyphenylene phosphonic acids sulfobenzide ester, dihydroxyphenyl propane phenyl poly phosphonic acid ester, polyphenylene phosphonic acids hexichol azo ester, polyphenylene phosphonic acids tetrabromo-bisphenol ester, polyphenylene phosphonic acids bisphenol S ester, phenolphthalein phenyl poly phosphonic acid ester; Gather thio-phenyl phosphonic acids sulfobenzide ester etc., and aromatic series polyphosphonates carbonate copolymer etc.
Phosphorus flame retardant of the present invention preferably contains the phosphinylidyne dichloro (phosphorothioic dichlorides) and diphenols compound of phenyl, the phosphorous high molecular weight flame retardant of carbonic ether copolymerization.
Said phosphorus flame retardant is the phosphorous unit of polyphosphazene polymer (phosphinate or SULPHOSUCCINIC ACID ESTER) the carbonate copolymer fire retardant that is suitable for 260-280 ℃ of processing temperature.
Further, said macromolecular carbon forming flame-retardant polyester material also comprises oxidation inhibitor.
Further, said macromolecular carbon forming flame-retardant polyester material comprises following component, and following umber is parts by weight:
Aromatic polyester 35-45 part, macromolecular carbon forming polymkeric substance 35-45 part, short char-forming agent 0.01-1 part, phosphorus flame retardant 10-18 part, transesterification catalyst 0.1-1 part; The total amount of said components is 100 parts.
Further; Said aromatic polyester comprises PET, PBT, PTT; Said macromolecular carbon forming polymkeric substance is polycarbonate or modified polycarbonate; Said short char-forming agent is a sulphonate, and said phosphorus flame retardant is the polyphosphonates carbonate copolymer, and said transesterification catalyst is metal complex or MOX.
Further, said polyphosphonates carbonate copolymer, general structure is following:
X=O or S; Z is a following substituting group functional group:
R wherein
1, R
2It is the aliphatics substituting group.Preferred R
1, R
2Be methyl or ethyl.
The limiting viscosity of said phosphorus flame retardant is 1.0-1.4dl/g, and the preferred limiting viscosity of fire retardant is 1.3dl/g, and Tg is 110-140 ℃, and preferred Tg is 129 ℃, and fusing point is 256-260 ℃, and phosphorus content is 2.0-4.0%, and preferred phosphorus content is 3.1%.
Further, said sulphonate comprises alkali metal sulfonate, alkaline earth metal sulfonate, fluoro sulfonate.Said fluoro sulfonate comprises fluorinated alkyl sulfonate, and wherein, alkyl comprises propyl group, butyl, amyl group, heptyl or octyl group.
Further, said phosphorus flame retardant is polyphenylene phosphonic acids sulfobenzide ester carbonate copolymer (PSPPP-co-PC) or polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymer (PBPPP-co-PC).
Further, said transesterification catalyst is a metal complex, and metals ion comprises Ti, Sb, and Rh, Co, part comprises methyl ethyl diketone, the west is alkali not.Transesterification catalyst can be an acetylacetone cobalt.
Further, said transesterification catalyst is a metal alkoxide, comprises Ti (OR)
4, R is the aliphatics substituting group.
The present invention also provides the preparation method of above-mentioned macromolecular carbon forming flame-retardant polyester material, and its feature is that said method comprises the steps:
(1) with polyester, macromolecular carbon forming agent is dry; Preferably make its moisture content below 200ppm;
(2) polyester and phosphorus flame retardant high-speed stirring are mixed; Wherein, the stirrer rotating speed is 750r/min;
(3) with step 2 products therefrom and macromolecular carbon forming agent, short char-forming agent, transesterification catalyst, high-speed stirring is mixed;
(4) the fusion agent under the condition of vacuumizing of step 3 products therefrom is gone out, promptly get said macromolecular carbon forming flame-retardant polyester material.
Further, also comprise oxidation inhibitor in the above-mentioned steps (3).
The present invention also provides a kind of macromolecular carbon forming fire retardant mylar, and its feature is that the material of said polyester film is above-mentioned macromolecular carbon forming flame-retardant polyester material.The thickness of said film is 50-200 μ m.
Further, the thickness of said film is 60-100 μ m.Perhaps, the thickness of said film is 150-180 μ m.
The present invention also provides the preparation method of above-mentioned macromolecular carbon forming fire retardant mylar, and its feature is that said macromolecular carbon forming flame-retardant polyester material makes said macromolecular carbon forming fire retardant mylar through stretch processes.
Preferably; 45 parts PC and sulphonate put into for 0.1 part is prepared into matrix material in the twin screw extruder, and then with 45 parts aromatic polyester, 9.8 parts of phosphorus flame retardants; 0.1 part transesterification catalyst; At temperature 250-300 ℃, pressure is under the vacuum condition of 10-150Pa and melt extrudes, and makes flame-retardant polyester material.
The manufacturing step of said fire retardant mylar is preferably the flame retardant polyester melt that makes dry 2-8 hour of 120-150 ℃ of scope, after material moisture is lower than 200ppm, gets into extruder system, then through biaxial oriented stretch, promptly gets fire retardant mylar.
Fire retardant mylar provided by the invention, its fire retardant mechanism is: PC more is prone to take place crosslinked in the presence of the sulphonate fire retardant as the macromolecular carbon forming polymkeric substance, generate more aromatics, constitutes charcoal layer presoma.Simultaneously because the transesterification between PC and the polyester (PET, PBT, PTT); Make physics and chemical action between phosphonium flame retardant and the PET mate more; Make the charcoal layer interaction that early stage charcoal layer presoma and the PET later stage of PC form; Formed more perfect protectiveness charcoal layer, improved the coagulation phase fire retardation of fire retardant, the carbon residue XPS through different steps obtains corresponding confirmation.
Because PC and PET are under the catalysis of transesterification catalyst (as: acetylacetone cobalt); The amorphous compatible system that transesterification reaction generates single Tg-100 ℃ takes place in the molten state (to be seen from differential scanning calorimetric DSC collection of illustrative plates; DSC has only the amorphous compatible system of a glass transition, and wherein Tg is 100 ℃).The mechanical property and the flame retardant properties of blend have not only been improved; Also make the transmittance of polymkeric substance be improved, among the present invention, regulate fire retardant as required; The content of transesterification catalyst just can generate the fire retardant mylar of different fire-retardant, light transmissions.
The present invention adopts high-molecular weight phosphorus flame retardant effect PC and polyester melt transesterification matrix material, induces polyester (PET, PBT, PTT) to become charcoal with macromolecular carbon forming agent, has improved the flame retardant properties and the mechanical property of traditional fire retardant mylar goods; Make that also the transparency of polyester film goods is kept; Its oxygen index is high, flame retardant rating high (flame retardant properties is better): after traditional fire-retardant film goods were lighted in 3 seconds, all with the behavior of fusion drippage; The absorbent cotton under the experimental installation has ignited; And by fire retardant mylar provided by the invention in when test, can not be lighted in 3 seconds, absorbent cotton does not ignite yet.
Compared with prior art; Macromolecular carbon forming flame-retardant polyester material provided by the invention is in melt extruding the process of processing; Original position generation transesterification reaction generates inlay and break copolymer; Thereby PC and PET form homogeneous system, reduce the addition of fire retardant and to the HDT of film, the influence of mechanical property, and then obtain flame retardant resistance and light transmission preferably.Macromolecular carbon forming flame-retardant polyester material provided by the invention and by its polyester film that makes extensively model be used for LCD, LED and show, high transparent demonstration and high transparent aerospace display window and goods printing opacity and the safe field that particular requirement is arranged.Preparing method's technology of macromolecular carbon forming flame-retardant polyester material provided by the invention, polyester film is simple, easy handling.
Embodiment
As shown in Figure 1, the thickness of macromolecular carbon forming fire retardant mylar 1 provided by the invention is 50-200 μ m.
Phenyl-phosphonic acid sulfobenzide ester carbonate copolymer (PSPPP-co-PC) described in the present invention and polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymer (PBPPP-co-PC) can be bought from market; Also can adopt prior art oneself preparation, number be preparing method's preparation that 20110039987 U.S. Patent application is announced like, application reference; Perhaps adopt following preparation method.
The preparation method of phenyl-phosphonic acid sulfobenzide ester carbonate copolymer (PSPPP-co-PC):
The midbody of polyphenylene phosphonic acids sulfobenzide ester carbonate copolymer (PSPPP-co-PC) is a polyphenylene phosphonic acids sulfobenzide ester, and the compound method of its preparation is following, and wherein polyphenylene phosphonic acids sulfobenzide ester synthesis reaction formula is:
Whipping appts is being housed and the calcium chloride that adds 1mol phosphenyl oxychloride, 1mol bisphenol S and 0.08mol in 500 milliliters of three-necked flasks of import and export of nitrogen is being arranged, feeding nitrogen then and under agitation heat to 250 ℃ gradually, making it frit reaction 3 hours; After question response finishes cooling, add chloroform to reactant and dissolve fully, pouring volume then into is 5 times of reactant solution volumes and above methyl alcohol; Deposition is separated out the white powder product; White powder product suction filtration from co-precipitation methyl alcohol is gone out, and dry then, drying can be taked natural air drying; Also can take oven dry, preferably vacuum drying.Product productive rate 89%, 170 ℃ of product melt temperatures.
The building-up reactions formula of polyphenylene phosphonic acids sulfobenzide ester carbonate copolymer (PSPPP-co-PC) is:
In the four-hole boiling flask that whisking appliance, TM, prolong, weighing apparatus pressure funnel are housed, add 2mol dihydroxyphenyl propane, 1mol midbody polyphenylene phosphonic acids sulfobenzide ester, 12mol NaOH, 6L water, 0.25mol triethylamine and 5mol phase-transfer catalyst cetyl trimethylammonium bromide (TMBA); The 1mol trichloromethyl carbonate is dissolved in 4L CH
2Cl
2In, in violent stirring, be added drop-wise in the 60min in the reaction flask, continue reaction 10min.Separate organic phase, be washed with distilled water to neutrality, the absolute ethyl alcohol deposition is filtered, with distilled water wash 2 times, and at 70 ℃ of following vacuum-drying 24h, must the white fiber shaped polymer.
The preparation method of polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymer (PBPPP-co-PC):
The midbody of polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymer (PBPPP-co-PC) is a polyphenylene phosphonic acids dihydroxyphenyl propane ester, and the compound method of its preparation is following, and polyphenylene phosphonic acids dihydroxyphenyl propane ester synthesis reaction formula is:
Whipping appts is being housed and the calcium chloride that adds 1mol phosphenyl oxychloride, 1mol dihydroxyphenyl propane and 0.08mol in 500 milliliters of three-necked flasks of import and export of nitrogen is being arranged, feeding nitrogen then and under agitation heat to 200 ℃ gradually, making it frit reaction 5 hours; Improve temperature to 250 ℃ reaction 3 hours again, after question response finishes cooling, add phenylcarbinol to reactant and dissolve fully; Pouring volume then into is 5 times of reactant solution volumes and above ethanol, and deposition is separated out the white powder product, and white powder product suction filtration from co-precipitation ethanol is gone out; Dry then; Drying can be taked natural air drying, also can take oven dry, preferably vacuum drying.Product productive rate 90%, 140 ℃ of product melt temperatures.
The building-up reactions formula of polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymer (PBPPP-co-PC) is:
In the four-hole boiling flask that whisking appliance, TM, prolong, weighing apparatus pressure funnel are housed, add 2mol dihydroxyphenyl propane, 1mol midbody polyphenylene phosphonic acids dihydroxyphenyl propane ester, 12mol NaOH, 6L water, 0.25mol triethylamine and 5mol phase-transfer catalyst cetyl trimethylammonium bromide (TMBA); The 1mol trichloromethyl carbonate is dissolved in 4L CH
2Cl
2In, in violent stirring, be added drop-wise in the 60min in the reaction flask, continue reaction 10min.Separate organic phase, be washed with distilled water to neutrality, the absolute ethyl alcohol deposition is filtered, with distilled water wash 2 times, and at 70 ℃ of following vacuum-drying 24h, must the white fiber shaped polymer.
Other raw material that the following embodiment of the present invention is used and reagent are product common on the market, can adopt:
PET, Yizheng Fiber Optical plant Fabritex S.r.l. in Jiangsu produces, and limiting viscosity is 0.64dl/g;
PC, German bayer company produces, product type 2805, limiting viscosity 0.44dl/g;
Trichloromethyl carbonate, technical grade, purity 99%, inscription chemical industry ltd of Qingdao city enterprise;
Dihydroxyphenyl propane, bisphenol S, phosphenyl oxychloride, cetyl trimethylammonium bromide, methylene dichloride; Phenylcarbinol, methyl alcohol, ethanol, calcium chloride, NaOH; Triethylamine, acetylacetone cobalt (II) or acetylacetone cobalt (III), above-mentioned these reagent are analytical pure, available from Chemical Reagent Co., Ltd., Sinopharm Group.
Metal sulfonate; Like perfluorinated sulfonic acid sodium (NaFBS), perfluorinated sulfonic acid potassium (KFBS), N-methyl N-phenyl benzenesulfonamides sodium salt (NaBSMP), perfluoro butyl potassium sulfonate (PPFBS), 2; 4,5-trichlorobenzene sodium sulfonate (STB), benzenesulfonyl Phenylsulfonic acid potassium (KSS), technical pure; Purity 97% is available from Dongguan Heng Qiao chemical industry ltd.
The preparation method of macromolecular carbon forming flame-retardant polyester material provided by the invention comprises the steps:
According to 100 parts of macromolecular carbon forming flame-retardant polyester materials, wherein, aromatic polyester 30-50 part, macromolecular carbon forming polymkeric substance 30-50 part, short char-forming agent 0.01-1 part, phosphorus flame retardant 10-18 part, transesterification catalyst 0.1-1 part.
The proportionally weighing of above-mentioned starting material, aromatic polyester and macromolecular carbon forming polymkeric substance are dry, afterwards 250-350 ℃ with vacuumize under the 10-150Pa condition, twin screw melt extrudes, and prepares said macromolecular carbon forming flame-retardant polyester material.
Above-mentioned macromolecular carbon forming flame-retardant polyester material can also add oxidation inhibitor, and the addition of oxidation inhibitor is an addition commonly used in the prior art, and preferably its content is 0.4% of macromolecular carbon forming flame-retardant polyester material gross weight.Said oxidation inhibitor comprises oxidation inhibitor commonly used, like antioxidant 1010, and oxidation inhibitor 168.
It is subsequent use that the present invention can prepare the macromolecular carbon forming flame-retardant polyester material earlier, and the preparation method of macromolecular carbon forming fire retardant mylar comprises the steps:
(1) the macromolecular carbon forming flame-retardant polyester material that makes is carried out drying under 120-180 ℃, make the material contained humidity be lower than 200ppm;
(2) step (1) products therefrom through melt extrude, biaxial oriented stretch, promptly get fire retardant mylar.
The preparation method of macromolecular carbon forming fire retardant mylar provided by the invention can also comprise specifically comprising the steps: the preparation process of macromolecular carbon forming flame retardant polyester
(1) mechanical pre-mixing
With aromatic polyester, polycarbonate drying; Aromatic polyester and phosphorus flame retardant high-speed stirring are mixed, and the stirrer rotating speed is 750r/min, is prepared into to handle material; To handle material, short char-forming agent, transesterification catalyst, oxidation inhibitor, the polycarbonate high-speed stirring is mixed, and the stirrer rotating speed is 750r/min.
(2) melting mixing
Step (1) products therefrom at 260-280 ℃, is vacuumized under the condition and melt extrudes into sheet;
(3) preparation of fire-retardant film
Step (2) gained sheet is cast sheet (40 ℃), longitudinal stretching (110 ℃, 3.2 times), cross directional stretch (100 ℃, 3 times), heat setting type (200 ℃ and 170 ℃), winding process through overcooling make the fire retardant mylar that thickness is 50-200 μ m.
Among the following embodiment, the preparation method of macromolecular carbon forming fire retardant mylar is identical with above-mentioned preparation method.Described umber is a weight part.
Embodiment 1:
Component content
42.5 parts of polybutylene terephthalates (PBT)
13.7 parts of polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymers (PBPPP-co-PC)
0.1 part of the short char-forming agent of KFBS
0.1 part of acetylacetone cobalt (II)
0.6 part in oxidation inhibitor
43 parts of polycarbonate (PC)
Embodiment 2:
Component content
41.5 parts of polybutylene terephthalates (PBT)
12.5 parts of polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymers (PBPPP-co-PC)
0.1 part of the short char-forming agent of KSS
0.1 part of acetylacetone cobalt (III)
0.6 part in oxidation inhibitor
44.2 parts of polycarbonate (PC)
Embodiment 3:
Component content
43.5 parts of polybutylene terephthalates (PET)
14.5 parts of polyphenylene phosphonic acids sulfobenzide ester carbonate copolymers (PSPPP-co-PC)
0.1 part of the short char-forming agent of PPFBS
0.1 part of acetylacetone cobalt (III)
0.6 part in oxidation inhibitor
41.2 parts of polycarbonate (PC)
Embodiment 4:
Component content
42.5 parts of polybutylene terephthalates (PET)
14.5 parts of polyphenylene phosphonic acids sulfobenzide ester carbonate copolymers (PSPPP-co-PC)
0.1 part of the short char-forming agent of PPFBS
0.1 part of acetylacetone cobalt (III)
0.6 part in oxidation inhibitor
42.2 parts of polycarbonate (PC)
Embodiment 5:
Component content
48 parts of PTTs (PET)
10 parts of polyphenylene phosphonic acids sulfobenzide ester carbonate copolymers (PSPPP-co-PC)
0.1 part of the short char-forming agent of KSS
0.1 part of acetylacetone cobalt (II)
0.6 part in oxidation inhibitor
41.2 parts of polycarbonate (PC)
Embodiment 6:
Component content
41.5 parts of PTTs (PTT)
13.5 parts of polyphenylene phosphonic acids sulfobenzide ester carbonate copolymers (PSPPP-co-PC)
0.1 part of the short char-forming agent of STB
The west of polymkeric substance load is 0.1 part of alkali cobalt complex not
0.6 part in oxidation inhibitor
44.2 parts of polycarbonate (PC)
Performance characteristics: the composition in the foregoing description is prepared into the macromolecular carbon forming flame-retardant polyester material, and further processes the macromolecular carbon forming fire retardant mylar, and the standard batten of processing carries out mechanics and flame retardant properties test.Below table 1 be the performance test project of fire retardant mylar and the detection method of foundation.
The salient features target of table 1 fire retardant mylar (the thick film of processing through two-way stretch with example 6 prepared macromolecular carbon forming flame-retardant polyester materials of 80 μ m is an example)
Detection method shown in the employing table 1 is tested the polyester film that the foregoing description makes, and its test result is as shown in table 2.
Table 2
Comparative example 1 in the table 2 is the product of resin Shanghai trade Co., Ltd of Mitsubishi, and product type is FR02, transparent film; Comparative example 2 is products of Jiangsu Yuxing Film Science and Technology Co., Ltd, and product type is 6023T, transparent film.
Embodiment 7
45 parts PC and sulphonate KFBS put into for 0.1 part be prepared into matrix material in the twin screw extruder; And then with the section of 45 parts polyethylene terephthalate; 9.8 part polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymer (PBPPP-co-PC), 0.1 part of methyl ethyl diketone cobalt catalyst is at temperature 250-300 ℃; Pressure is under the vacuum condition of 10-150Pa and melt extrudes, and makes flame-retardant polyester material.
The flame retardant polyester melt that makes dry 2-8 hour of 120-150 ℃ of scope, after material moisture is lower than 200ppm, is got into extruder system,, make fire retardant mylar then through biaxial oriented stretch.
Embodiment 8
Aromatic polyester PET30 part, 50 parts of polycarbonate, 1 part of short char-forming agent N-methyl N-phenyl benzenesulfonamides sodium salt (NaBSMP), 18 parts of polyphenylene phosphonic acids sulfobenzide esters, 1 part of transesterification catalyst (metal complex, metals ion Ti, part are methyl ethyl diketones).
Embodiment 9
Aromatic polyester PTT50 part, 30 parts of polycarbonate, 1 part of short char-forming agent perfluoro butyl potassium sulfonate (PPFBS); 18 parts of phosphorus flame retardant polyphenylene phosphonic acids sulfobenzide ester carbonate copolymers (PSPPP-co-PC); 1 part of transesterification catalyst (metal complex, metals ion Sb, part methyl ethyl diketone).
Embodiment 10
Aromatic polyester PBT40 part, 40 parts of modified polycarbonates, short char-forming agent 2; 4,1 part of 5-trichlorobenzene sodium sulfonate (STB), 18 parts of phosphorus flame retardant polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymers (PBPPP-co-PC); 1 part of transesterification catalyst (the part west is alkali not for metal complex, metals ion Rh).
Embodiment 11
Aromatic polyester PBT40 part; 49.89 parts of modified polycarbonates; 0.01 part in short char-forming agent benzenesulfonyl Phenylsulfonic acid potassium (KSS), 10 parts of phosphorus flame retardant polyphenylene phosphonic acids sulfobenzide ester carbonate copolymers (PSPPP-co-PC), transesterification catalyst (metal complex; Metals ion Co, the part west is alkali not) 0.1 part.
Embodiment 12
Aromatic polyester PET45 part, 40.4 parts of polycarbonate, 0.1 part in short char-forming agent benzenesulfonyl Phenylsulfonic acid potassium (KSS), 14 parts of phosphorus flame retardant polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymers (PBPPP-co-PC), transesterification catalyst Ti (OPr)
40.5 part.
Embodiment 13
Aromatic polyester PTT35 part, 49 parts of polycarbonate, 0.5 part of short char-forming agent perfluoro octane sulfonate, 15 parts of phosphorus flame retardant phenolphthalein phenyl poly phosphonic acid esters, transesterification catalyst Ti (OMe)
40.5 part.
Embodiment 7 to 13 prepared flame-retardant polyester materials further make fire retardant mylar, and its performance perameter is seen table 3.
Table 3
Embodiment 14
Aromatic polyester PET35 part, 45 parts of polycarbonate, 1 part of short char-forming agent perfluoro octane sulfonate, phosphorus flame retardant gathers 18 parts of thio-phenyl phosphonic acids sulfobenzide esters, transesterification catalyst Ti (OPr)
41 part.
Embodiment 15
Aromatic polyester PET45 part, 35 parts of polycarbonate, 1 part in short char-forming agent perfluorinated sulfonic acid sodium (NaFBS), 18 parts of phosphorus flame retardant dihydroxyphenyl propane phenyl poly phosphonic acid esters, 1 part of transesterification catalyst.
Embodiment 16
Aromatic polyester PET40 part, 40 parts of polycarbonate, 1 part of short char-forming agent N-methyl N-phenyl benzenesulfonamides sodium salt (NaBSMP), 18 parts of phosphorus flame retardant dihydroxyphenyl propane phenyl poly phosphonic acid esters, transesterification catalyst Ti (OPr)
41 part.
Embodiment 17
Aromatic polyester PTT38 part, 44 parts of polycarbonate, short char-forming agent 2,4,0.01 part of 5-trichlorobenzene sodium sulfonate (STB), 17.89 parts of phosphorus flame retardant polyphenylene phosphonic acids bisphenol S esters, transesterification catalyst Ti (OBu)
40.1 part.
Embodiment 18
Aromatic polyester PTT44 part, 39 parts of polycarbonate, 0.5 part in short char-forming agent perfluorinated butane sulphonate, 16 parts of phosphorus flame retardant polyphenylene phosphonic acids bisphenol S esters, transesterification catalyst Ti (OBu)
40.5 part.
Embodiment 19
Aromatic polyester PBT45 part, 44 parts of modified polycarbonates, 0.5 part in short char-forming agent perflenapent sulphonate, 10 parts of phosphorus flame retardant polyphenylene phosphonic acids sulfobenzide ester carbonate copolymers (PSPPP-co-PC), transesterification catalyst Ti (OMe)
40.5 part.
Embodiment 20
Aromatic polyester PBT42 part, 42 parts of modified polycarbonates, 0.6 part in short char-forming agent perfluorinated sulfonic acid potassium (KFBS), 15 parts of phosphorus flame retardant polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymers (PBPPP-co-PC), 0.4 part of transesterification catalyst acetylacetone cobalt.
Embodiment 14 to 20 prepared flame-retardant polyester materials further make fire retardant mylar, and its performance perameter is seen table 4.
Table 4
Test data in above-mentioned table 1 to the table 4 shows that the flame retardant resistance and the light transmission of macromolecular carbon forming fire retardant mylar provided by the invention are better, and mechanical property is also relatively good.
The above is merely preferred embodiment of the present invention, is not to be used to limit protection scope of the present invention.Every equalization that content is done according to the present invention changes and modifies, and all is encompassed in the claim of the present invention.