CN102532816B - Macromolecular char formation flame-retardant polyester material, polyester thin film and preparation methods thereof - Google Patents
Macromolecular char formation flame-retardant polyester material, polyester thin film and preparation methods thereof Download PDFInfo
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Abstract
The invention relates to the field of polyester materials and polyester thin films, in particular to a macromolecular char formation flame-retardant polyester material, a polyester thin film and preparation methods thereof. In order to overcome the defect of poor thin film transparency of the thin film made from the flame-retardant polyester material in the prior art, the invention provides the macromolecular char formation flame-retardant polyester material and the preparation method thereof, and the thin film made from the polyester material and the preparation method thereof. The polyester material provided by the invention comprises the following components in parts by weight: 30-50 parts of aromatic polyester, 30-50 parts of macromolecular char formation polymer, 0.01-1 part of char formation accelerant, 10-18 parts of phosphorus flame retardant and 0.1-1 part of transesterification catalyst, wherein the total amount of the components is 100 parts. The macromolecular char formation flame-retardant polyester material has excellent flame retardation; and the preparation method of the polyester material is low in production cost, has a simple process and is easy to operate. The thin film made from the polyester material provided by the invention has excellent flame retardation and transparency and high mechanical strength; and the preparation method of the thin film has a simple process and is easy to operate.
Description
Technical field
The present invention relates to polyester material and polyester film field, relate in particular to a kind of macromolecular carbon forming flame-retardant polyester material, polyester film and preparation method thereof.
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 ethylene glycol carry out copolymerization, and the section of preparation flame retardant polyester is made film by stretch processes again; The 2nd, the fire retardant of commixed type and polyester slice carry out blend, extrude and make fire-retardant master granule, and then make film by 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 l5-18 page or leaf, in " the halogen-free flameproof The Characteristics of low-melting point PET ", the technology that employing applies at the low-melting point polyester film surface, 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 Chinese patent application on August 4th, 2004), special organic and inorganic hybrid materials has been superimposed upon a kind of laminated film of the both sides formation of PET film.This structure makes film can control the inflammable gas diffusion, puts out a fire in the extremely short time, 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 PET PREPARATION, " modern plastics processed and applied ", 2002,15 (3) phases, the 12-14 page or leaf) adopts the DMT method, synthesized flame retardant type PET, and carried out the biaxially oriented film test; Application number is 200310104141.X(publication No.: CN1554703, date of publication: Chinese patent application on December 15th, 2004) has been announced polyester slice and fire retardant melt-mixing method production fire retardant mylar.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(publication No.: CN1923889, date of publication: Chinese patent application on March 7th, 2007) has been announced, adopts the method synthesizing polyester that adds organosilicate in production of polyester, makes fire retardant mylar.Wang Shuxia etc. (development of polyester for flame-retadant film and performance study [J]. " synthetic technology and application ", 2009,24(3) the phase, the 1-4 page or leaf) adopts the PTA method, by in the polyester process, adding the synthetic flame retardant polyester section of phosphonium flame retardant, and be that raw material is made 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, the adjustment of production route is big, the cost height; 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(Albright wilison company production of adding 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, the applying date is in the U.S. Patent application on May 25th, 2006, adopt 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 for film flame retardant resistance below the 350 μ m and mechanical property instability.
Number of patent application is the 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 the CN101643574(date of publication: Chinese patent application on February 10th, 2010) discloses the flame retardant resistance of improving polyester film by copolymerization and blend two-step approach, 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 phosphorous and fire retardant nitrogen, 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 at 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 fire-retardantly to carry out simultaneously from promoting compatible and strengthen, and 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 fire retardant of employing copoly type and terephthalic acid and ethylene glycol carry out the cost height of copolymerization mode, complex process, and facility investment is big; The fire retardant of commixed type and polyester slice carry out the mode of blend, because the addition of fire retardant is big, and the mechanical property instability, 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 made in the prior art film transparency difference, the invention provides a kind of macromolecular carbon forming flame-retardant polyester material and preparation method thereof and the film that makes 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 invention provides following technical proposals:
The invention provides a kind of macromolecular carbon forming flame-retardant polyester material, its feature is, described 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.Described phosphorus flame retardant comprises common aromatic series bis-phenol phenyl polyphosphonates homopolymer, as 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, poly-thio-phenyl phosphonic acids sulfobenzide ester etc., and aromatic series polyphosphonates carbonate copolymer etc.
Further, described aromatic polyester comprises PET, PBT, PTT, described macromolecular carbon forming polymkeric substance is polycarbonate or modified polycarbonate, described short char-forming agent is a sulfonate, and described phosphorus flame retardant is the polyphosphonates carbonate copolymer, and described transesterification catalyst is metal complex or metal oxide.
Further, described polyphosphonates carbonate copolymer, general structure is as follows:
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.
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.
Described phosphorus flame retardant is the phosphorous unit of polyphosphazene polymer (phosphinate or phosphoric acid ester) the carbonate copolymer fire retardant that is suitable for 260-280 ℃ of processing temperature.
Further, described macromolecular carbon forming flame-retardant polyester material also comprises oxidation inhibitor.
Further, described 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.
The limiting viscosity of described 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, described sulfonate comprises alkali metal sulfonate, alkaline earth metal sulfonate, fluoro sulfonate.Described fluoro sulfonate comprises fluorinated alkyl sulfonate, and wherein, alkyl comprises propyl group, butyl, amyl group, heptyl or octyl group.
Further, described 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, described transesterification catalyst is a metal complex, and metal 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, described 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 described method comprises the steps:
(1) with polyester, the macromolecular carbon forming agent drying; 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 described 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 described polyester film is above-mentioned macromolecular carbon forming flame-retardant polyester material.The thickness of described film is 50-200 μ m.
Further, the thickness of described film is 60-100 μ m.Perhaps, the thickness of described 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 described macromolecular carbon forming flame-retardant polyester material makes described macromolecular carbon forming fire retardant mylar by stretch processes.
Preferably, 45 parts PC and sulfonate put into for 0.1 part be prepared into matrix material in the twin screw extruder, and then and 45 parts aromatic polyester, 9.8 part phosphorus flame retardant, 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 described fire retardant mylar is preferably the flame retardant polyester melt that will make dry 2-8 hour of 120-150 ℃ of scope, after material moisture is lower than 200ppm, enters 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 is crosslinked as the easier generation in the presence of the sulfonate fire retardant of macromolecular carbon forming polymkeric substance, generates 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 the early stage charcoal layer presoma of PC and PET later stage form; formed more perfect protectiveness charcoal layer; improved the coagulation phase fire retardation of fire retardant, the carbon residue XPS by different steps obtains corresponding confirmation.
Because PC and PET are under the catalysis of transesterification catalyst (as: acetylacetone cobalt), transesterification reaction takes place in the molten state generate single Tg-100 ℃ amorphous compatible system (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, induce polyester (PET with macromolecular carbon forming agent, PBT, PTT) become charcoal, the flame retardant properties and the mechanical property of traditional fire retardant mylar goods have been improved, make that also the transparency of polyester film goods is kept, its oxygen index height, flame retardant rating height (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.Preparation method's technology of macromolecular carbon forming flame-retardant polyester material provided by the invention, polyester film is simple, easy handling.
Description of drawings
Fig. 1 is the diagrammatic cross-section of macromolecular carbon forming fire retardant mylar provided by the invention.
Wherein, 1 is the macromolecular carbon forming fire retardant mylar.
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 preparation method's preparation that 20110039987 U.S. Patent application is announced as, application reference; Perhaps adopt following preparation method.
The preparation method of phenyl-phosphonic acid sulfobenzide ester carbonate copolymer (PSPPP-co-PC):
The intermediate of polyphenylene phosphonic acids sulfobenzide ester carbonate copolymer (PSPPP-co-PC) is a polyphenylene phosphonic acids sulfobenzide ester, and the synthetic method of its preparation is as follows, and wherein polyphenylene phosphonic acids sulfobenzide ester synthesis reaction formula is:
Add the 1mol phosphenyl oxychloride in 500 milliliters of three-necked flasks of import and export of nitrogen whipping appts being housed and having, the calcium chloride of 1mol bisphenol S and 0.08mol, feed nitrogen then and under agitation heat to 250 ℃ gradually, made it frit reaction 3 hours, after question response finishes cooling, adding chloroform to reactant dissolves fully, pouring volume then into is 5 times of reactant solution volumes and above methyl alcohol, precipitation is separated out the white powder product, white powder product suction filtration from co-precipitation methyl alcohol is gone out, 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 agitator, thermometer, prolong, weighing apparatus pressure funnel are housed, add 2mol dihydroxyphenyl propane, 1mol intermediate 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 dehydrated alcohol precipitation is filtered, and uses distilled water wash 2 times, at 70 ℃ of following vacuum-drying 24h, gets the white fiber shaped polymer.
The preparation method of polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymer (PBPPP-co-PC):
The intermediate of polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymer (PBPPP-co-PC) is a polyphenylene phosphonic acids dihydroxyphenyl propane ester, and the synthetic method of its preparation is as follows, and polyphenylene phosphonic acids dihydroxyphenyl propane ester synthesis reaction formula is:
Add the 1mol phosphenyl oxychloride in 500 milliliters of three-necked flasks of import and export of nitrogen whipping appts being housed and having, the calcium chloride of 1mol dihydroxyphenyl propane and 0.08mol, feed nitrogen then and under agitation heat to 200 ℃ gradually, made it frit reaction 5 hours, improve temperature to 250 ℃ reaction 3 hours again, after question response finishes cooling, adding phenylcarbinol to reactant dissolves fully, pouring volume then into is 5 times of reactant solution volumes and above ethanol, precipitation is separated out the white powder product, white powder product suction filtration from co-precipitation ethanol is gone out, and 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 agitator, thermometer, prolong, weighing apparatus pressure funnel are housed, add 2mol dihydroxyphenyl propane, 1mol intermediate 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 dehydrated alcohol precipitation is filtered, and uses distilled water wash 2 times, at 70 ℃ of following vacuum-drying 24h, gets 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 company limited 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; as 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 company limited.
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 drying, at 250-350 ℃ and vacuumize under the 10-150Pa condition, twin screw melt extrudes, and prepares described macromolecular carbon forming flame-retardant polyester material afterwards.
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.Described oxidation inhibitor comprises oxidation inhibitor commonly used, as antioxidant 1010, and oxidation inhibitor 168.
It is standby 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
Embodiment 2:
Component content
Embodiment 3:
Component content
Embodiment 4:
Component content
Embodiment 5:
Component content
Embodiment 6:
Component content
Performance characteristics: the composition in the foregoing description is prepared into the macromolecular carbon forming flame-retardant polyester material, and further makes the macromolecular carbon forming fire retardant mylar, and the standard batten of making 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 making by 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 sulfonate KFBS0.1 part put into be prepared into matrix material in the twin screw extruder, and then and the section of 45 parts polyethylene terephthalate, 9.8 part polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymer (PBPPP-co-PC), 0.1 part methyl ethyl diketone cobalt catalyst, 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 entered 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, metal 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, metal 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), transesterification catalyst (metal complex, metal ion Rh, the part west is alkali not) 1 part.
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; metal 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 sees Table 3.
Table 3
Embodiment 14
Aromatic polyester PET35 part, 45 parts of polycarbonate, 1 part of short char-forming agent perfluoro octane sulfonate, 18 parts of the poly-thio-phenyl phosphonic acids sulfobenzide esters of phosphorus flame retardant, 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 sulfonate, 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 sulfonate, 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 sees Table 4.
Table 4
Above-mentioned table 1 to the test data in 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 preferred embodiment of the present invention only, 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.
Claims (8)
1. a macromolecular carbon forming flame-retardant polyester material is characterized in that, described 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;
Described aromatic polyester comprises PET, PBT, PTT, described macromolecular carbon forming polymkeric substance is polycarbonate or modified polycarbonate, described short char-forming agent is a sulfonate, and described phosphorus flame retardant is the polyphosphonates carbonate copolymer, and described transesterification catalyst is metal complex or metal oxide;
Described polyphosphonates carbonate copolymer, general structure is as follows:
X=O or S; Z is one of following substituting group functional group:
Wherein, R
1, R
2It is the aliphatics substituting group; R
1, R
2Be methyl or ethyl.
2. a macromolecular carbon forming flame-retardant polyester material as claimed in claim 1 is characterized in that described sulfonate comprises alkali metal sulfonate, alkaline earth metal sulfonate, basic metal sulfonic fluoropolymer salt, alkaline-earth metal sulfonic fluoropolymer salt.
3. a macromolecular carbon forming flame-retardant polyester material as claimed in claim 1 is characterized in that, described phosphorus flame retardant is polyphenylene phosphonic acids sulfobenzide ester carbonate copolymer or polyphenylene phosphonic acids dihydroxyphenyl propane ester carbonate copolymer.
4. a macromolecular carbon forming flame-retardant polyester material as claimed in claim 1 is characterized in that described transesterification catalyst is a metal complex, and metal ion comprises Ti, Sb, and Rh, Co, part comprises methyl ethyl diketone, the west is alkali not.
5. the preparation method as the described macromolecular carbon forming flame-retardant polyester material of one of claim 1 to 4 is characterized in that, described method comprises the steps:
(1) with polyester, the macromolecular carbon forming agent drying;
(2) polyester and phosphorus flame retardant high-speed stirring are mixed;
(3) with step 2 products therefrom and dried macromolecular carbon forming agent, short char-forming agent, transesterification catalyst, high-speed stirring;
(4) step 3 products therefrom is melt extruded under the condition of vacuumizing, promptly get described macromolecular carbon forming flame-retardant polyester material.
6. a macromolecular carbon forming fire retardant mylar is characterized in that, the material of described polyester film is the described macromolecular carbon forming flame-retardant polyester material of one of claim 1 to 4.
7. one kind as macromolecular carbon forming fire retardant mylar as described in the claim 6, it is characterized in that described film is the single thin film of stretch processes preparation, and its thickness is 50-200 μ m.
8. the preparation method of a macromolecular carbon forming fire retardant mylar as claimed in claim 6 is characterized in that, described macromolecular carbon forming flame-retardant polyester material makes described macromolecular carbon forming fire retardant mylar by stretch processes.
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| CN103254577A (en) * | 2013-05-06 | 2013-08-21 | 常熟市永祥机电有限公司 | Flame-retardant polyethylene glycol terephthalate moulded plastic |
| CN105133074A (en) * | 2015-09-22 | 2015-12-09 | 旷达科技集团股份有限公司 | Fire-retardant modified and enhanced polyester for vehicle and production method of polyester |
| CN106084718A (en) * | 2016-06-14 | 2016-11-09 | 江苏金发科技新材料有限公司 | High-temp resistant fire-retarding polycarbonate compositions and preparation method thereof |
| CN109251319A (en) * | 2018-10-12 | 2019-01-22 | 江苏万润塑料制品有限公司 | A kind of polyester PET fire retardant and its synthetic method |
| CN109535410A (en) * | 2018-11-14 | 2019-03-29 | 成都其其小数科技有限公司 | A kind of polycarbonate/polyphenylene phosphonic acids diphenyl sulphone (DPS) ester fire proofing and preparation method |
| CN111698798B (en) * | 2020-06-17 | 2023-02-03 | 浙江南洋科技有限公司 | Preparation method of heat-resistant and flame-retardant polyester film for electrothermal film |
| CN115806771B (en) * | 2022-11-30 | 2024-03-22 | 国网安徽省电力有限公司亳州供电公司 | Special anti-corrosion flame-retardant paint for power equipment and preparation method thereof |
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