CN102634174A - Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine - Google Patents

Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine Download PDF

Info

Publication number
CN102634174A
CN102634174A CN2012100949559A CN201210094955A CN102634174A CN 102634174 A CN102634174 A CN 102634174A CN 2012100949559 A CN2012100949559 A CN 2012100949559A CN 201210094955 A CN201210094955 A CN 201210094955A CN 102634174 A CN102634174 A CN 102634174A
Authority
CN
China
Prior art keywords
phosphorus
flame
fluosilicic
mass parts
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2012100949559A
Other languages
Chinese (zh)
Other versions
CN102634174B (en
Inventor
李建学
胡俊祥
梁倩倩
唐安斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SICHUAN DONGFANG INSULATING MATERIAL CO Ltd
Original Assignee
SICHUAN DONGFANG INSULATING MATERIAL CO Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SICHUAN DONGFANG INSULATING MATERIAL CO Ltd filed Critical SICHUAN DONGFANG INSULATING MATERIAL CO Ltd
Priority to CN201210094955.9A priority Critical patent/CN102634174B/en
Publication of CN102634174A publication Critical patent/CN102634174A/en
Application granted granted Critical
Publication of CN102634174B publication Critical patent/CN102634174B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • 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
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • 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
    • 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
    • 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
    • B29C2948/92923—Calibration, after-treatment or cooling zone

Abstract

The invention discloses a preparation method of a flame-retardant copolyester film of phosphorus, silicon and fluorine. The preparation method is characterized by comprising the steps of: preparing flame-retardant copolyester sections of phosphorus, silicon and fluorine from maleic anhydride, dihydroxy fluorine silicone, DOPO (9-10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide), terephthalic acid and ethylene glycol by addition, esterification and polycondensation reaction in the presence of an esterification catalyst, a polycondensation catalyst and a stabilizing agent; and mixing the prepared flame-retardant copolyester sections of phosphorus, silicon and fluorine with a polyester section, carrying out melt extrusion by an extruder and preparing the flame-retardant copolyester film product of phosphorus, silicon and fluorine by longitudinally drawing, laterally drawing and hot setting treatment. The preparation method disclosed by the invention is simple in reaction process, strong in operability, easy in technological condition control and low in production cost, and shortens the production time and cycle of multivariate copolymerization synthesis; and the flame-retardant property of the product can be up to VTM-0 level.

Description

A kind of preparation method of phosphorus fluosilicic fire-resistant copolyesters ester film
Technical field
The invention belongs to the preparation of organic high molecular compound, relate to a kind of preparation method of phosphorus fluosilicic fire-resistant copolyesters ester film.The phosphorus fluosilicic fire-resistant copolyesters ester film that adopts the present invention to make is applicable to electric insulation, decorates fields such as painting advertisement, various IC-card magnetic cards.
Background technology
In the prior art, the fire-retardant common employing physics of polyester adds fire retardant or reactive flame retardant dual mode.Chinese patent ZL200910058655.3 discloses the phosphor-containing flame-proof polyethylene terephthalate.And one Chinese patent application 200610041495.8 disclosed " having polyester of excellent fire-retardancy and preparation method thereof " adopts silicon-containing monomer and polyethylene terephthalate copolymerization to obtain a kind of nothing drippage flame retardant polyester.Because a large amount of phosphorous, pasc reaction type fire retardants are introduced the regularity that has destroyed original polyester macromolecule, molecular weight and molecular weight is bigger, and material melting point reduces, the heat deflection performance change is fairly obvious, unsuitable processed polyesters film and the trevira of being used for.
Usually, DOPO (9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound) and verivate thereof use as curing agent for epoxy resin, or produce the epoxy resin of purposes of the various differentiation of various band DOPO structures.In the prior art, DOPO adopts the physics addition manner in polyester material, to use, because no crosslinked and easy the migration, flame retardant effect is bad, and large usage quantity, influences the proper property of polyester material.Also find phosphorus fluosilicic flame-proof copolyester resin and film product thereof with DOPO structure.
Summary of the invention
The object of the invention is intended to overcome above-mentioned deficiency of the prior art, and a kind of preparation method of phosphorus fluosilicic fire-resistant copolyesters ester film is provided.
Content of the present invention is: a kind of preparation method of phosphorus fluosilicic fire-resistant copolyesters ester film is characterized in that comprising the following steps:
A, preparation phosphorus fluosilicic flame-proof copolyester slice:
The first step: under 60～120 rev/mins speed stir; With 2000mol MALEIC ANHYDRIDE, the dihydroxyl fluorosilicone (that is: in the dihydroxyl fluorosilicone of adding that contains 3200～4000mol amount of hydroxyl groups; The hydroxyl amount is 3200～4000mol), the DOPO of 2020mol (that is: 9; The 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound), in the disposable reactor drum that joins band condensate fractionation device of 10000～11000mol terephthalic acid, 18000～25000mol terepthaloyl moietie, 0.3～2.0kg esterifying catalyst, 0.4～1.6kg polycondensation catalyst and 0.1～0.9kg stablizer; Mixed 10～20 minutes; Be heated to 100～190 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour; Be warming up to 245～260 ℃ of completion reactions of quickening esterifications again, finish reaction when above, get reacting rear material when aquifer yield reaches 96% of theoretical aquifer yield;
Second step: said reacting rear material is put in the polycondensation reactor, stirred, in 0.5～1 hour, make temperature rise to 265～280 ℃ with 15～60 rev/mins speed; Under pressure 0.1～0.2Mpa;, be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie after 0.5～1 hour through copolycondensation again, stirring velocity is reduced to 10～30 rev/mins; Under pressure 0～100Pa again through 2～4 hours copolycondensations; When the limiting viscosity of reaction mass reaches 0.60～0.65g/dl, stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice;
The quality percentage composition that described dihydroxyl fluorosilicone is a hydroxyl is 5%～16% and dihydroxyl fluorosilicone with following substruction:
Figure 2012100949559100002DEST_PATH_IMAGE001
，
In the formula: R is C 1～C 3Chain-like alkyl, R 1Be methyl, ethyl or phenyl, n is 1～3;
Described esterifying catalyst is one or more the mixture in antimony acetate, sodium-acetate, manganese acetate, Cobaltous diacetate, the magnesium acetate;
Described polycondensation catalyst is one or more a mixture of Antimony Trioxide: 99.5Min, antimony glycol, tetrabutyl titanate;
Described stablizer is one or more a mixture of phosphorous acid dihydroxyphenyl propane ester, triphenyl phosphite, trimethyl phosphite 99, triphenylphosphate, pyrocatechol SULPHOSUCCINIC ACID ESTER, triethyl phosphate.
B, preparation phosphorus fluosilicic fire-resistant copolyesters ester film:
With phosphorus fluosilicic flame-proof copolyester slice 100 mass parts that make with after PET Resin/Poyester Chips Bottle Grade 5～30 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm; Join in the forcing machine, after the smart filtration of 260～310 ℃ of fusions, 150～300 order strainer coarse filtrations and 500～1500 order strainers, extrude from cross-head; Cooling casting sheet on 15～30 ℃ of cold drums; Handle through 2.5～5.0 times of 2.5～5.0 times, 110～160 ℃ following cross directional stretchs of 75～105 ℃ of following longitudinal stretchings and 180～235 ℃ of following heat setting types, cut through rolling again, promptly make phosphorus fluosilicic flame-proof copolyester film product.
In the content of the present invention: the PET Resin/Poyester Chips Bottle Grade described in the step b is one or more the mixture in polyethylene terephthalate, PEN, PTT and the polybutylene terephthalate section.
In the content of the present invention: the MALEIC ANHYDRIDE described in the step a can also replace with the mixture of itaconic anhydride or MALEIC ANHYDRIDE and itaconic anhydride.
In the content of the present invention: the terephthalic acid described in the step a can also replace with terephthalic acid and 2, the mixture of 6-naphthalic acid.
In the content of the present invention: the reactor drum described in the step a can also be a flow reactor.
Adopt the phosphorus fluosilicic flame-proof copolyester of the present invention's preparation, contain following basic segmented structure:
Figure 136970DEST_PATH_IMAGE002
，
Or
Figure 2012100949559100002DEST_PATH_IMAGE003
Or contain above two kinds of basic segments; In above-mentioned two structural formulas: R is C 1～C 3Chain-like alkyl, R 1Be identical or different methyl, ethyl, phenyl, m is 5～15, and n is 1～3.
Compared with prior art, the present invention has following characteristics and beneficial effect:
(1) the present invention carries out addition and esterification simultaneously with auxiliary agents such as MALEIC ANHYDRIDE, dihydroxyl fluorosilicone, DOPO, terephthalic acid, terepthaloyl moietie and catalyzer in a reactor drum; And then in polycondensation reactor, carry out copolycondensation, and reaction process is simplified, and is workable, and processing condition are easy to control, have shortened multi-component copolymer synthetic PT and cycle, greatly reduce production cost;
(2) adopt the present invention; Though phosphorus fluosilicic fire-resistant copolyesters ester film contains phosphorus, silicon, fluorine element; And in the polyester macromolecule main chain, formed the polyester copolymer that contains heteroatoms silicon, but do not change original substrate polyester basically---mechanics, electricity and the chemical property of polyethylene terephthalate (PET) or PEN (PNE) or PTT (PTT) or polybutylene terephthalate (PBT) bulk material; Also, promote charring rate effectively, increased substantially thermoplastic polyester material's flame retardant properties owing to phosphorus, silicon, fluorine element synergistic fire retardation; Its P content is dropped in polyester material below the 16000ppm, still reach flame retardant effect preferably; Its film product can reach the performance requriements of VTM-0 level film;
(3) the present invention is because the introducing of element silicon; Bring certain organosilicon characteristic to polyester macromolecule, also improved the polyester matrix polyester---the resistance toheat and the thermostability of polyethylene terephthalate (PET) or PEN (PNE) or PTT (PTT) or polybutylene terephthalate (PBT) bulk material;
(4) the present invention has certain anti-drippage performance owing to have a large amount of side chain and fluorine elements introducings than macrostructure in the resin material of phosphorus fluosilicic fire-resistant copolyesters ester film;
(5) matrix resin that adopts the present invention to make film is polyethylene terephthalate (PET), or contains one or more mixtures in PEN (PNE), PTT (PTT), the polybutylene terephthalate (PBT);
(6) product preparation process of the present invention is simple, and operation is easy, and operation is practical easily.
Embodiment
Embodiment given below intends so that the present invention is described further; But can not be interpreted as it is restriction to protection domain of the present invention; The technician in this field to some nonessential improvement and adjustment that the present invention makes, still belongs to protection scope of the present invention according to the content of the invention described above.
The preparation of phosphorus fluosilicic flame-proof copolyester slice (embodiment 1～9)
Embodiment 1:
The first step: stir down with 60～120 rev/mins speed; With the 2000mol MALEIC ANHYDRIDE, contain the dihydroxyl fluorosilicone (content 5% of hydroxyl quality) of 3200mol amount of hydroxyl groups, DOPO, 10000mol terephthalic acid, 18000mol terepthaloyl moietie, 0.3kg esterifying catalyst antimony acetate, 1.6kg polycondensation catalyst tetrabutyl titanate and the 0.6kg stablizer of 2020mol (phosphorous acid dihydroxyphenyl propane ester: the reactor drum of the disposable adding band condensate fractionation device mass ratio of triphenyl phosphite: triethyl phosphate=1:2:1); Making beating mixed 10～20 minutes; Be heated to 105 ± 5 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour; Be warming up to 250 ± 5 ℃ of completion of quickening esterifications again, finish to react when above when aquifer yield reaches 96% of theoretical aquifer yield.
Second step: the reaction mass of the first step is put in the polycondensation reactor; Stir with 15～60 rev/mins speed, in 0.5～1 hour, make to be warming up to 270 ± 5 ℃, pressure under 0.1Mpa, again through copolycondensation 0.5～1 hour; Be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie; Stirring velocity is reduced to 10～30 rev/mins, pressure under the high vacuum of 0～100Pa again through 2～4 hours copolycondensations, when limiting viscosity reaches 0.60～0.65g/dl; Stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice.
Embodiment 2:
The first step: stir down with 60～120 rev/mins speed; With the 2000mol MALEIC ANHYDRIDE, contain the dihydroxyl fluorosilicone (content 7% of hydroxyl quality) of 3600mol amount of hydroxyl groups, DOPO, 10500mol terephthalic acid, 22000mol terepthaloyl moietie, 0.8kg esterifying catalyst (mass ratio of Cobaltous diacetate: sodium-acetate=2:1), 0.6kg polycondensation catalyst antimony glycol and the 0.9kg stablizer of 2020mol (phosphorous acid dihydroxyphenyl propane ester: the reactor drum of the disposable adding band condensate fractionation device mass ratio of pyrocatechol SULPHOSUCCINIC ACID ESTER: triethyl phosphate=2:1:4); Making beating mixed 10～20 minutes; Be heated to 125 ± 5 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour; Be warming up to 255 ± 5 ℃ of completion of quickening esterifications again, finish to react when above when aquifer yield reaches 96% of theoretical aquifer yield.
Second step: the reaction mass of the first step is put in the polycondensation reactor; Stir with 15～60 rev/mins speed, in 0.5～1 hour, make to be warming up to 275 ± 5 ℃, pressure under 0.15Mpa, again through copolycondensation 0.5～1 hour; Be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie; Stirring velocity is reduced to 10～30 rev/mins, pressure under the high vacuum of 0～100Pa again through 2～4 hours copolycondensations, when limiting viscosity reaches 0.60～0.65g/dl; Stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice.
Embodiment 3:
The first step: stir down with 60～120 rev/mins speed; With the 2000mol MALEIC ANHYDRIDE, contain dihydroxyl fluorosilicone (content 8% of hydroxyl quality), the DOPO of 2020mol, the 11000mol terephthalic acid and 2 of 4000mol amount of hydroxyl groups; The mixture of 6-naphthalic acid (terephthalic acid: 2; The mol ratio of 6-naphthalic acid=6:1), the reactor drum of the disposable adding band condensate fractionation device mass ratio of 25000mol terepthaloyl moietie, 1.0kg esterifying catalyst (mass ratio of Cobaltous diacetate: sodium-acetate: manganese acetate=1:1:1), 0.9 kg polycondensation catalyst Antimony Trioxide: 99.5Min and 0.1kg stablizer trimethyl phosphite 99, triphenylphosphate=1:1); Making beating mixed 10～20 minutes; Be heated to 145 ± 5 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour; Be warming up to 250 ± 5 ℃ of completion of quickening esterifications again, finish to react when above when aquifer yield reaches 96% of theoretical aquifer yield.
Second step: the reaction mass of the first step is put in the polycondensation reactor; Stir with 15～60 rev/mins speed, in 0.5～1 hour, make to be warming up to 270 ± 5 ℃, pressure under 0.2Mpa, again through copolycondensation 0.5～1 hour; Be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie; Stirring velocity is reduced to 10～30 rev/mins, pressure under the high vacuum of 0～100Pa again through 2～4 hours copolycondensations, when limiting viscosity reaches 0.60～0.65g/dl; Stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice.
Embodiment 4:
The first step: stir down with 60～120 rev/mins speed; With the 2000mol itaconic anhydride, contain the dihydroxyl fluorosilicone (content 9% of hydroxyl quality) of 3200mol amount of hydroxyl groups, DOPO, 10000mol terephthalic acid, 18000mol terepthaloyl moietie, 1.2kg esterifying catalyst (mass ratio of Cobaltous diacetate: antimony acetate=1:1), 0.4kg polycondensation catalyst (mass ratio of Antimony Trioxide: 99.5Min: antimony glycol=1:1) and the 0.4kg stablizer of 2020mol (phosphorous acid dihydroxyphenyl propane ester: the reactor drum of the disposable adding band condensate fractionation device mass ratio of pyrocatechol SULPHOSUCCINIC ACID ESTER=3:1); Making beating mixed 10～20 minutes; Be heated to 165 ± 5 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour; Be warming up to 255 ± 5 ℃ of completion of quickening esterifications again, finish to react when above when aquifer yield reaches 96% of theoretical aquifer yield.
Second step: the reaction mass of the first step is put in the polycondensation reactor; Stir with 15～60 rev/mins speed, in 0.5～1 hour, make to be warming up to 275 ± 5 ℃, pressure under 0.1Mpa, again through copolycondensation 0.5～1 hour; Be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie; Stirring velocity is reduced to 10～30 rev/mins, pressure under the high vacuum of 0～100Pa again through 2～4 hours copolycondensations, when limiting viscosity reaches 0.60～0.65g/dl; Stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice.
Embodiment 5:
The first step: stir down with 60～120 rev/mins speed; Reactor drum with DOPO, 10500mol terephthalic acid, 22000mol terepthaloyl moietie, 0.7kg esterifying catalyst (mass ratio of sodium-acetate: manganese acetate: Cobaltous diacetate=3:1:2), 0.8kg polycondensation catalyst antimony glycol and the disposable adding band of the 0.3kg stablizer triphenyl phosphite condensate fractionation device of 2000mol itaconic anhydride, the dihydroxyl fluorosilicone (content 10% of hydroxyl quality) that contains the 3600mol amount of hydroxyl groups, 2020mol; Making beating mixed 10～20 minutes; Be heated to 185 ± 5 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour; Be warming up to 250 ± 5 ℃ of completion of quickening esterifications again, finish to react when above when aquifer yield reaches 96% of theoretical aquifer yield.
Second step: the reaction mass of the first step is put in the polycondensation reactor; Stir with 15～60 rev/mins speed, in 0.5～1 hour, make to be warming up to 270 ± 5 ℃, pressure under 0.15Mpa, again through copolycondensation 0.5～1 hour; Be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie; Stirring velocity is reduced to 10～30 rev/mins, pressure under the high vacuum of 0～100Pa again through 2～4 hours copolycondensations, when limiting viscosity reaches 0.60～0.65g/dl; Stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice.
Embodiment 6:
The first step: stir down with 60～120 rev/mins speed; With the 2000mol itaconic anhydride, contain dihydroxyl fluorosilicone (content 12% of hydroxyl quality), the DOPO of 2020mol, the 11000mol terephthalic acid and 2 of 4000mol amount of hydroxyl groups; The mixture of 6-naphthalic acid (terephthalic acid: 2; The mol ratio of 6-naphthalic acid=10:1), the reactor drum of 25000mol terepthaloyl moietie, 1.5kg esterifying catalyst antimony acetate, 1.1kg polycondensation catalyst Antimony Trioxide: 99.5Min and the disposable adding band of 0.5kg stablizer phosphorous acid dihydroxyphenyl propane ester condensate fractionation device; Making beating mixed 10～20 minutes; Be heated to 165 ± 5 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour, be warming up to 255 ± 5 ℃ of completion of quickening esterifications again, finish to react when above when aquifer yield reaches 96% of theoretical aquifer yield.
Second step: the reaction mass of the first step is put in the polycondensation reactor; Stir with 15～60 rev/mins speed, in 0.5～1 hour, make to be warming up to 275 ± 5 ℃, pressure under 0.2Mpa, again through copolycondensation 0.5～1 hour; Be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie; Stirring velocity is reduced to 10～30 rev/mins, pressure under the high vacuum of 0～100Pa again through 2～4 hours copolycondensations, when limiting viscosity reaches 0.60～0.65g/dl; Stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice.
Embodiment 7:
The first step: stir down with 60～120 rev/mins speed; With the DOPO of the mixture (mol ratio of MALEIC ANHYDRIDE: itaconic anhydride=5:1) of 2000mol MALEIC ANHYDRIDE and itaconic anhydride, the dihydroxyl fluorosilicone (content 13% of hydroxyl quality) that contains the 3200mol amount of hydroxyl groups, 2020mol, 10000mol terephthalic acid, 18000mol terepthaloyl moietie, 0.9kg esterifying catalyst (manganese acetate: Cobaltous diacetate: magnesium acetate=1:1:4), 1.3kg polycondensation catalyst (mass ratio of antimony glycol: tetrabutyl titanate=1:4) and 0.3kg stablizer (phosphorous acid dihydroxyphenyl propane ester: the reactor drum of the disposable adding band condensate fractionation device mass ratio of triphenylphosphate=1:5); Making beating mixed 10～20 minutes; Be heated to 145 ± 5 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour; Be warming up to 250 ± 5 ℃ of completion of quickening esterifications again, finish to react when above when aquifer yield reaches 96% of theoretical aquifer yield.
Second step: the reaction mass of the first step is put in the polycondensation reactor; Stir with 15～60 rev/mins speed, in 0.5～1 hour, make to be warming up to 270 ± 5 ℃, pressure under 0.1Mpa, again through copolycondensation 0.5～1 hour; Be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie; Stirring velocity is reduced to 10～30 rev/mins, pressure under the high vacuum of 0～100Pa again through 2～4 hours copolycondensations, when limiting viscosity reaches 0.60～0.65g/dl; Stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice.
Embodiment 8:
The first step: stir down with 60～120 rev/mins speed; Reactor drum with DOPO, 10500mol terephthalic acid, 22000mol terepthaloyl moietie, 2.0kg esterifying catalyst Cobaltous diacetate, 0.7kg polycondensation catalyst (mass ratio of Antimony Trioxide: 99.5Min: tetrabutyl titanate=1:2) and the disposable adding band condensate fractionation device of 0.4kg stablizer (mass ratio of phosphorous acid dihydroxyphenyl propane ester, triphenyl phosphite=1:3) of the mixture (mol ratio of MALEIC ANHYDRIDE: itaconic anhydride=3:1) of 2000mol MALEIC ANHYDRIDE and itaconic anhydride, the dihydroxyl fluorosilicone (content 14% of hydroxyl quality) that contains the 3600mol amount of hydroxyl groups, 2020mol; Making beating mixed 10～20 minutes; Be heated to 125 ± 5 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour; Be warming up to 255 ± 5 ℃ of completion of quickening esterifications again, finish to react when above when aquifer yield reaches 96% of theoretical aquifer yield.
Second step: the reaction mass of the first step is put in the polycondensation reactor; Stir with 15～60 rev/mins speed, in 0.5～1 hour, make to be warming up to 275 ± 5 ℃, pressure under 0.15Mpa, again through copolycondensation 0.5～1 hour; Be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie; Stirring velocity is reduced to 10～30 rev/mins, pressure under the high vacuum of 0～100Pa again through 2～4 hours copolycondensations, when limiting viscosity reaches 0.60～0.65g/dl; Stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice.
Embodiment 9:
The first step: stir down with 60～120 rev/mins speed; With the mixture (mol ratio of MALEIC ANHYDRIDE: itaconic anhydride=2:1) of 2000mol MALEIC ANHYDRIDE and itaconic anhydride, contain dihydroxyl fluorosilicone (content 16% of hydroxyl quality), the DOPO of 2020mol, the 11000mol terephthalic acid and 2 of 4000mol amount of hydroxyl groups; The mixture of 6-naphthalic acid (terephthalic acid: 2; The mol ratio of 6-naphthalic acid=4:1), 25000mol terepthaloyl moietie, 0.7kg esterifying catalyst (mass ratio of Cobaltous diacetate: antimony acetate=1:3), 1.0kg polycondensation catalyst (mass ratio of Antimony Trioxide: 99.5Min, antimony glycol, tetrabutyl titanate=1:1:1) and 0.9kg stablizer (phosphorous acid dihydroxyphenyl propane ester: the reactor drum of the disposable adding band condensate fractionation device mass ratio of triphenyl phosphite: trimethyl phosphite 99: triphenylphosphate=1:1:1:1); Making beating mixed 10～20 minutes; Be heated to 105 ± 5 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour; Be warming up to 250 ± 5 ℃ of completion of quickening esterifications again, finish to react when above when aquifer yield reaches 96% of theoretical aquifer yield.
Second step: the reaction mass of the first step is put in the polycondensation reactor; Stir with 15～60 rev/mins speed, in 0.5～1 hour, make to be warming up to 270 ± 5 ℃, pressure under 0.2Mpa, again through copolycondensation 0.5～1 hour; Be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie; Stirring velocity is reduced to 10～30 rev/mins, pressure under the high vacuum of 0～100Pa again through 2～4 hours copolycondensations, when limiting viscosity reaches 0.60～0.65g/dl; Stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice.
The preparation (embodiment 10～58) of phosphorus fluosilicic fire-resistant copolyesters ester film
Embodiment 10:
Embodiment 1 synthetic phosphorus fluosilicic flame-proof copolyester slice 100 mass parts and polyester PET are cut into slices after 10 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 11:
Embodiment 1 synthetic phosphorus fluosilicic flame-proof copolyester slice 100 mass parts and polyester PET are cut into slices after 20 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums is handled through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 12:
Embodiment 1 synthetic phosphorus fluosilicic flame-proof copolyester slice 100 mass parts and polyester PET are cut into slices after 30 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums is handled through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 13:
Embodiment 1 synthetic phosphorus fluosilicic flame-proof copolyester slice 100 mass parts and polyester PNE are cut into slices after 5 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 14:
Embodiment 2 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 5 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 15:
Embodiment 2 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 30 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums is handled through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 16:
Embodiment 2 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 20 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums is handled through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 17:
Embodiment 2 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PNE are cut into slices after 10 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 18:
Embodiment 3 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 10 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 19:
Embodiment 3 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 30 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums is handled through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 20:
Embodiment 3 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 20 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums is handled through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 21:
Embodiment 3 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PTT are cut into slices after 5 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm; Join in the forcing machine, after the smart filtration of 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers, extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums; Handle through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cut through rolling again, promptly make phosphorus fluosilicic flame-proof copolyester film product.
Embodiment 22:
Embodiment 4 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 20 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 23:
Embodiment 4 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 10 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums is handled through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 24:
Embodiment 4 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 30 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums is handled through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 25:
Embodiment 4 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PBT are cut into slices after 15 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 26:
Embodiment 5 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 5 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 27:
Embodiment 5 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 15 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums is handled through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 28:
Embodiment 5 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 30 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm; Join in the forcing machine, after the smart filtration of 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers, extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums; Handle through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cut through rolling again, promptly make phosphorus fluosilicic flame-proof copolyester film product.
Embodiment 29:
Embodiment 5 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PNE are cut into slices after 10 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 30:
Embodiment 6 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 8 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 31:
Embodiment 6 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 16 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums is handled through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 32:
Embodiment 6 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 30 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums is handled through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 33:
Embodiment 6 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PTT are cut into slices after 20 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 34:
Embodiment 7 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 9 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 35:
Embodiment 7 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 24 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums is handled through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 36:
Embodiment 7 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 30 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums is handled through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 37:
Embodiment 7 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PTT are cut into slices after 12 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 38:
Embodiment 8 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 5 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 39:
Embodiment 8 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 14 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums is handled through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 40:
Embodiment 8 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 30 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums is handled through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 41:
Embodiment 8 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PBT are cut into slices after 20 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 42:
Embodiment 9 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 5 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 43:
Embodiment 9 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 10 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums is handled through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 44:
Embodiment 9 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PET are cut into slices after 30 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums is handled through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 45:
Embodiment 9 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester PBT are cut into slices after 18 mass parts mix; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 46:
After embodiment 1 synthetic phosphorus fluosilicic flame-proof copolyester slice 100 mass parts and polyester (mass ratio of PTT:PET=1:8) section 5 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums is handled through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 47:
After embodiment 2 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester (mass ratio of PTT:PET=1:4) section 25 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 48:
After embodiment 3 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester (mass ratio of PTT:PET=2:5) section 30 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 295 ± 2 ℃ of fusions, 250 order strainer coarse filtrations and 800 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 49:
After embodiment 4 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester (mass ratio of PBT:PET=1:3) section 8 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 29 ± 1 ℃ of cold drums is handled through 5.0 times of 5.0 times, 158 ± 2 ℃ following cross directional stretchs of 103 ± 2 ℃ of following longitudinal stretchings and 235 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 50:
After embodiment 5 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester (mass ratio of PBT:PTT:PET=1:1:4) section 22 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm; Join in the forcing machine, after the smart filtration of 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers, extrude from head; Cooling casting sheet on 20 ± 1 ℃ of cold drums; Handle through 3.0 times of 3.0 times, 125 ± 2 ℃ following cross directional stretchs of 87 ± 2 ℃ of following longitudinal stretchings and 200 ℃ of following heat setting types, cut through rolling again, promptly make phosphorus fluosilicic flame-proof copolyester film product.
Embodiment 51:
After embodiment 6 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester (mass ratio of PBT:PTT:PET=1:1:4) section 18 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums is handled through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 52:
After embodiment 7 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester (mass ratio of PTT:PET:PBT:PNE=1:3:2:2) section 11 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 280 ± 2 ℃ of fusions, 200 order strainer coarse filtrations and 600 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 53:
After embodiment 8 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester (mass ratio of PBT:PET=1:7) section 13 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 308 ± 2 ℃ of fusions, 300 order strainer coarse filtrations and 1500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 25 ± 1 ℃ of cold drums is handled through 4.0 times of 4.0 times, 145 ± 2 ℃ following cross directional stretchs of 97 ± 2 ℃ of following longitudinal stretchings and 220 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 54:
After embodiment 9 synthetic phosphorus fluosilicic flame-proof copolyester slices 100 mass parts and polyester (mass ratio of PTT:PNE:PET=1:2:4) section 6 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm, join in the forcing machine, through 262 ± 2 ℃ of fusions, 150 order strainer coarse filtrations and 500 order strainers are smart filter after; Extrude from head; Cooling casting sheet on 16 ± 1 ℃ of cold drums is handled through 2.5 times of 2.5 times, 112 ± 2 ℃ following cross directional stretchs of 77 ± 2 ℃ of following longitudinal stretchings and 180 ℃ of following heat setting types, cuts through rolling again; Promptly make phosphorus fluosilicic flame-proof copolyester film product, its flame retardant properties reaches the VTM-0 level.
Embodiment 55:
A kind of preparation method of phosphorus fluosilicic fire-resistant copolyesters ester film comprises the following steps:
A, preparation phosphorus fluosilicic flame-proof copolyester slice:
The first step: under 60～120 rev/mins speed stir; In the disposable reactor drum that joins band condensate fractionation device of DOPO, 10000～11000mol terephthalic acid, 18000～25000mol terepthaloyl moietie, 0.3～2.0kg esterifying catalyst, 0.4～1.6kg polycondensation catalyst and the 0.1～0.9kg stablizer of 2000mol MALEIC ANHYDRIDE, the dihydroxyl fluorosilicone that contains 3200～4000mol amount of hydroxyl groups, 2020mol; Mixed 10～20 minutes; Be heated to 100～190 ℃ and carry out two reactions of while addition and esterification 0.5～1 hour; Be warming up to 245～260 ℃ of completion reactions of quickening esterification again; Finish reaction when above when aquifer yield reaches 96% of theoretical aquifer yield, reacting rear material;
Second step: said reacting rear material is put in the polycondensation reactor, stirred, in 0.5～1 hour, make temperature rise to 265～280 ℃ with 15～60 rev/mins speed; Under pressure 0.1～0.2Mpa;, be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie after 0.5～1 hour through copolycondensation again, stirring velocity is reduced to 10～30 rev/mins; Under pressure 0～100Pa again through 2～4 hours copolycondensations; When the limiting viscosity of reaction mass reaches 0.60～0.65g/dl, stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice;
The quality percentage composition that described dihydroxyl fluorosilicone is a hydroxyl is 5%～16% and dihydroxyl fluorosilicone with following substruction:
Figure 979024DEST_PATH_IMAGE004
，
In the formula: R is C 1～C 3Chain-like alkyl, R 1Be methyl, ethyl or phenyl, n is 1～3;
Described esterifying catalyst is one or more the mixture in antimony acetate, sodium-acetate, manganese acetate, Cobaltous diacetate, the magnesium acetate;
Described polycondensation catalyst is one or more a mixture of Antimony Trioxide: 99.5Min, antimony glycol, tetrabutyl titanate;
Described stablizer is one or more a mixture of phosphorous acid dihydroxyphenyl propane ester, triphenyl phosphite, trimethyl phosphite 99, triphenylphosphate, pyrocatechol SULPHOSUCCINIC ACID ESTER, triethyl phosphate.
B, preparation phosphorus fluosilicic fire-resistant copolyesters ester film:
With phosphorus fluosilicic flame-proof copolyester slice 100 mass parts that make with after PET Resin/Poyester Chips Bottle Grade 5～30 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm; Join in the forcing machine, after the smart filtration of 260～310 ℃ of fusions, 150～300 order strainer coarse filtrations and 500～1500 order strainers, extrude from cross-head; Cooling casting sheet on 15～30 ℃ of cold drums; Handle through 2.5～5.0 times of 2.5～5.0 times, 110～160 ℃ following cross directional stretchs of 75～105 ℃ of following longitudinal stretchings and 180～235 ℃ of following heat setting types, cut through rolling again, promptly make phosphorus fluosilicic flame-proof copolyester film product.
Embodiment 56:
A kind of preparation method of phosphorus fluosilicic fire-resistant copolyesters ester film comprises the following steps:
A, preparation phosphorus fluosilicic flame-proof copolyester slice:
The first step: under 80 rev/mins speed stir; In the disposable reactor drum that joins band condensate fractionation device of DOPO, 10500mol terephthalic acid, 21500mol terepthaloyl moietie, 1.1kg esterifying catalyst, 1kg polycondensation catalyst and the 0.5kg stablizer of 2000mol MALEIC ANHYDRIDE, the dihydroxyl fluorosilicone that contains the 3600mol amount of hydroxyl groups, 2020mol; Mixed 15 minutes; Be heated to 150 ℃ and carry out two reactions of while addition and esterification 0.7 hour; Be warming up to 245～260 ℃ of completion reactions of quickening esterifications again, finish reaction when above, get reacting rear material when aquifer yield reaches 96% of theoretical aquifer yield;
Second step: said reacting rear material is put in the polycondensation reactor, stirred, in 0.7 hour, make temperature rise to 265～280 ℃ with 36 rev/mins speed; Under pressure 0.1～0.2Mpa;, be depressurized to vacuumize under the 120pa and remove unreacted terepthaloyl moietie after 0.7 hour through copolycondensation again, stirring velocity is reduced to 20 rev/mins; Under pressure 0～100Pa again through 2～4 hours copolycondensations; When the limiting viscosity of reaction mass reaches 0.60～0.65g/dl, stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice;
The quality percentage composition that described dihydroxyl fluorosilicone is a hydroxyl is 5%～16% and dihydroxyl fluorosilicone with embodiment 55 said substructions;
In the formula: R is C 1～C 3Chain-like alkyl, R 1Be methyl, ethyl or phenyl, n is 1～3;
Described esterifying catalyst is one or more the mixture in antimony acetate, sodium-acetate, manganese acetate, Cobaltous diacetate, the magnesium acetate;
Described polycondensation catalyst is one or more a mixture of Antimony Trioxide: 99.5Min, antimony glycol, tetrabutyl titanate;
Described stablizer is one or more a mixture of phosphorous acid dihydroxyphenyl propane ester, triphenyl phosphite, trimethyl phosphite 99, triphenylphosphate, pyrocatechol SULPHOSUCCINIC ACID ESTER, triethyl phosphate.
B, preparation phosphorus fluosilicic fire-resistant copolyesters ester film:
With phosphorus fluosilicic flame-proof copolyester slice 100 mass parts that make with after PET Resin/Poyester Chips Bottle Grade 17 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm; Join in the forcing machine, after the smart filtration of 260～310 ℃ of fusions, 150～300 order strainer coarse filtrations and 500～1500 order strainers, extrude from cross-head; Cooling casting sheet on 15～30 ℃ of cold drums; Handle through 2.5～5.0 times of 2.5～5.0 times, 110～160 ℃ following cross directional stretchs of 75～105 ℃ of following longitudinal stretchings and 180～235 ℃ of following heat setting types, cut through rolling again, promptly make phosphorus fluosilicic flame-proof copolyester film product.
Embodiment 57:
A kind of preparation method of phosphorus fluosilicic fire-resistant copolyesters ester film comprises the following steps:
A, preparation phosphorus fluosilicic flame-proof copolyester slice:
The first step: under 60～120 rev/mins speed stir; In the disposable reactor drum that joins band condensate fractionation device of DOPO, 10000mol terephthalic acid, 18000mol terepthaloyl moietie, 0.3kg esterifying catalyst, 0.4kg polycondensation catalyst and the 0.1kg stablizer of 2000mol MALEIC ANHYDRIDE, the dihydroxyl fluorosilicone that contains the 3200mol amount of hydroxyl groups, 2020mol; Mixed 10 minutes; Be heated to 100 ℃ and carry out two reactions of while addition and esterification 1 hour; Be warming up to 245～260 ℃ of reactions again, finish reaction when above when aquifer yield reaches 96% of theoretical aquifer yield, reacting rear material;
Second step: said reacting rear material is put in the polycondensation reactor, stirred, in 0.5 hour, make temperature rise to 265～280 ℃ with 15 rev/mins speed; Under pressure 0.1～0.2Mpa;, be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie after 0.5 hour through copolycondensation again, stirring velocity is reduced to 10 rev/mins; Under pressure 0～100Pa again through 2～4 hours copolycondensations; When the limiting viscosity of reaction mass reaches 0.60～0.65g/dl, stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice;
The quality percentage composition that described dihydroxyl fluorosilicone is a hydroxyl is 5%～16% and dihydroxyl fluorosilicone with embodiment 55 said substructions;
In the formula: R is C 1～C 3Chain-like alkyl, R 1Be methyl, ethyl or phenyl, n is 1～3;
Described esterifying catalyst is one or more the mixture in antimony acetate, sodium-acetate, manganese acetate, Cobaltous diacetate, the magnesium acetate;
Described polycondensation catalyst is one or more a mixture of Antimony Trioxide: 99.5Min, antimony glycol, tetrabutyl titanate;
Described stablizer is one or more a mixture of phosphorous acid dihydroxyphenyl propane ester, triphenyl phosphite, trimethyl phosphite 99, triphenylphosphate, pyrocatechol SULPHOSUCCINIC ACID ESTER, triethyl phosphate.
B, preparation phosphorus fluosilicic fire-resistant copolyesters ester film:
With phosphorus fluosilicic flame-proof copolyester slice 100 mass parts that make with after PET Resin/Poyester Chips Bottle Grade 5 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm; Join in the forcing machine, after the smart filtration of 260～310 ℃ of fusions, 150～300 order strainer coarse filtrations and 500～1500 order strainers, extrude from cross-head; Cooling casting sheet on 15～30 ℃ of cold drums; Handle through 2.5～5.0 times of 2.5～5.0 times, 110～160 ℃ following cross directional stretchs of 75～105 ℃ of following longitudinal stretchings and 180～235 ℃ of following heat setting types, cut through rolling again, promptly make phosphorus fluosilicic flame-proof copolyester film product.
Embodiment 58:
A kind of preparation method of phosphorus fluosilicic fire-resistant copolyesters ester film comprises the following steps:
A, preparation phosphorus fluosilicic flame-proof copolyester slice:
The first step: under 60～120 rev/mins speed stir; In the disposable reactor drum that joins band condensate fractionation device of DOPO, 11000mol terephthalic acid, 25000mol terepthaloyl moietie, 2.0kg esterifying catalyst, 1.6kg polycondensation catalyst and the 0.9kg stablizer of 2000mol MALEIC ANHYDRIDE, the dihydroxyl fluorosilicone that contains the 4000mol amount of hydroxyl groups, 2020mol; Mixed 20 minutes; Be heated to 100～190 ℃ and carry out two reactions of while addition and esterification 1 hour; Be warming up to 245～260 ℃ of completion reactions of quickening esterifications again, finish reaction when above, get reacting rear material when aquifer yield reaches 96% of theoretical aquifer yield;
Second step: said reacting rear material is put in the polycondensation reactor, stirred, in 1 hour, make temperature rise to 265～280 ℃ with 60 rev/mins speed; Under pressure 0.1～0.2Mpa;, be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie after 1 hour through copolycondensation again, stirring velocity is reduced to 30 rev/mins; Under pressure 0～100Pa again through 2～4 hours copolycondensations; When the limiting viscosity of reaction mass reaches 0.60～0.65g/dl, stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice;
The quality percentage composition that described dihydroxyl fluorosilicone is a hydroxyl is 5%～16% and dihydroxyl fluorosilicone with embodiment 55 said substructions;
In the formula: R is C 1～C 3Chain-like alkyl, R 1Be methyl, ethyl or phenyl, n is 1～3;
Described esterifying catalyst is one or more the mixture in antimony acetate, sodium-acetate, manganese acetate, Cobaltous diacetate, the magnesium acetate;
Described polycondensation catalyst is one or more a mixture of Antimony Trioxide: 99.5Min, antimony glycol, tetrabutyl titanate;
Described stablizer is one or more a mixture of phosphorous acid dihydroxyphenyl propane ester, triphenyl phosphite, trimethyl phosphite 99, triphenylphosphate, pyrocatechol SULPHOSUCCINIC ACID ESTER, triethyl phosphate.
B, preparation phosphorus fluosilicic fire-resistant copolyesters ester film:
With phosphorus fluosilicic flame-proof copolyester slice 100 mass parts that make with after PET Resin/Poyester Chips Bottle Grade 30 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm; Join in the forcing machine, after the smart filtration of 260～310 ℃ of fusions, 150～300 order strainer coarse filtrations and 500～1500 order strainers, extrude from cross-head; Cooling casting sheet on 15～30 ℃ of cold drums; Handle through 2.5～5.0 times of 2.5～5.0 times, 110～160 ℃ following cross directional stretchs of 75～105 ℃ of following longitudinal stretchings and 180～235 ℃ of following heat setting types, cut through rolling again, promptly make phosphorus fluosilicic flame-proof copolyester film product.
In the foregoing description 55-58: the PET Resin/Poyester Chips Bottle Grade described in the step b is one or more the mixture in polyethylene terephthalate, PEN, PTT and the polybutylene terephthalate section.
In the foregoing description 55-58: the MALEIC ANHYDRIDE described in the step a can also replace with the mixture of itaconic anhydride or MALEIC ANHYDRIDE and itaconic anhydride.
In the foregoing description 55-58: the terephthalic acid described in the step a can also replace with terephthalic acid and 2, the mixture of 6-naphthalic acid.
In the foregoing description 55-58: the reactor drum described in the step a can also be a flow reactor.
Adopt the phosphorus fluosilicic flame-proof copolyester of the foregoing description 55-58 preparations, contain following basic segmented structure:
Figure 2012100949559100002DEST_PATH_IMAGE005
，
Or
Figure 187283DEST_PATH_IMAGE006
,
Or contain above two kinds of basic segments; In above-mentioned two structural formulas: R is C 1～C 3Chain-like alkyl, R 1Be identical or different methyl, ethyl, phenyl, m is 5～15, and n is 1～3.
In the foregoing description: each raw material that is adopted is the commercially available prod.
In the foregoing description: in the percentage that is adopted, do not indicate especially, be weight (quality) percentage; Said weight (quality) part can all be gram or kilogram.
In the foregoing description: the processing parameter in each step (temperature, time, concentration etc.) and each amounts of components numerical value etc. are scope, and any point is all applicable.
The invention is not restricted to the foregoing description, content of the present invention is said all can implement and have said good result.

Claims (5)

1. the preparation method of a phosphorus fluosilicic fire-resistant copolyesters ester film is characterized in that comprising the following steps:
A, preparation phosphorus fluosilicic flame-proof copolyester slice:
The first step: under 60～120 rev/mins speed stir; With the 2000mol MALEIC ANHYDRIDE, contain in the disposable reactor drum that joins band condensate fractionation device of DOPO, 10000～11000mol terephthalic acid, 18000～25000mol terepthaloyl moietie, 0.3～2.0kg esterifying catalyst, 0.4～1.6kg polycondensation catalyst and the 0.1～0.9kg stablizer of dihydroxyl fluorosilicone 2020mol of 3200～4000mol amount of hydroxyl groups; Mixed 10～20 minutes; Be heated to 100～190 ℃ of reactions 0.5～1 hour; Be warming up to 245～260 ℃ of reactions again, finish reaction when above when aquifer yield reaches 96% of theoretical aquifer yield, reacting rear material;
Second step: said reacting rear material is put in the polycondensation reactor, stirred, in 0.5～1 hour, make temperature rise to 265～280 ℃ with 15～60 rev/mins speed; Under pressure 0.1～0.2Mpa;, be depressurized to vacuumize under 100～150pa and remove unreacted terepthaloyl moietie after 0.5～1 hour through copolycondensation again, stirring velocity is reduced to 10～30 rev/mins; Under pressure 0～100Pa again through 2～4 hours copolycondensations; When the limiting viscosity of reaction mass reaches 0.60～0.65g/dl, stop to stir and charging into the nitrogen discharging, promptly make phosphorus fluosilicic flame-proof copolyester slice;
The quality percentage composition that described dihydroxyl fluorosilicone is a hydroxyl is 5%～16% and dihydroxyl fluorosilicone with following substruction:
Figure 667599DEST_PATH_IMAGE001
，
In the formula: R is C 1～C 3Chain-like alkyl, R 1Be methyl, ethyl or phenyl, n is 1～3;
Described esterifying catalyst is one or more the mixture in antimony acetate, sodium-acetate, manganese acetate, Cobaltous diacetate, the magnesium acetate;
Described polycondensation catalyst is one or more a mixture of Antimony Trioxide: 99.5Min, antimony glycol, tetrabutyl titanate;
Described stablizer is one or more a mixture of phosphorous acid dihydroxyphenyl propane ester, triphenyl phosphite, trimethyl phosphite 99, triphenylphosphate, pyrocatechol SULPHOSUCCINIC ACID ESTER, triethyl phosphate;
B, preparation phosphorus fluosilicic fire-resistant copolyesters ester film:
With phosphorus fluosilicic flame-proof copolyester slice 100 mass parts that make with after PET Resin/Poyester Chips Bottle Grade 5～30 mass parts are mixed; When under 150～180 ℃, being dried to water ratio and being lower than 50ppm; Join in the forcing machine, after the smart filtration of 260～310 ℃ of fusions, 150～300 order strainer coarse filtrations and 500～1500 order strainers, extrude from cross-head; Cooling casting sheet on 15～30 ℃ of cold drums; Handle through 2.5～5.0 times of 2.5～5.0 times, 110～160 ℃ following cross directional stretchs of 75～105 ℃ of following longitudinal stretchings and 180～235 ℃ of following heat setting types, cut through rolling again, promptly make phosphorus fluosilicic flame-proof copolyester film product.
2. by the preparation method of the described phosphorus fluosilicic of claim 1 fire-resistant copolyesters ester film, it is characterized in that: the PET Resin/Poyester Chips Bottle Grade described in the step b is one or more the mixture in polyethylene terephthalate, PEN, PTT and the polybutylene terephthalate section.
3. by the preparation method of claim 1 or 2 described phosphorus fluosilicic fire-resistant copolyesters ester films, it is characterized in that: the MALEIC ANHYDRIDE described in the step a replaces with the mixture of itaconic anhydride or MALEIC ANHYDRIDE and itaconic anhydride.
4. by the preparation method of claim 1 or 2 described phosphorus fluosilicic fire-resistant copolyesters ester films, it is characterized in that: the terephthalic acid described in the step a replaces with terephthalic acid and 2, the mixture of 6-naphthalic acid.
5. by the preparation method of claim 1 or 2 described phosphorus fluosilicic fire-resistant copolyesters ester films, it is characterized in that: the reactor drum described in the step a is a flow reactor.
CN201210094955.9A 2012-03-31 2012-03-31 Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine Active CN102634174B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210094955.9A CN102634174B (en) 2012-03-31 2012-03-31 Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210094955.9A CN102634174B (en) 2012-03-31 2012-03-31 Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine

Publications (2)

Publication Number Publication Date
CN102634174A true CN102634174A (en) 2012-08-15
CN102634174B CN102634174B (en) 2014-01-08

Family

ID=46618758

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210094955.9A Active CN102634174B (en) 2012-03-31 2012-03-31 Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine

Country Status (1)

Country Link
CN (1) CN102634174B (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105542137A (en) * 2016-01-22 2016-05-04 四川东方绝缘材料股份有限公司 Multipolymer resin, multipolymer compound base film and preparation method of multipolymer compound base film
CN105860044A (en) * 2016-06-17 2016-08-17 苍南县宝丰印业有限公司 Thermoplastic polyester for films and preparation method thereof
CN105860043A (en) * 2016-06-17 2016-08-17 苍南县宝丰印业有限公司 Thermoplastic polyester for antibacterial film and preparation method of thermoplastic polyester
CN106005656A (en) * 2016-06-17 2016-10-12 苍南县宝丰印业有限公司 Cake packaging box
CN106432898A (en) * 2016-06-17 2017-02-22 苍南县宝丰印业有限公司 Cast film with high barrier property
CN106565943A (en) * 2016-11-08 2017-04-19 四川东材科技集团股份有限公司 Fluorosilicone copolyester resin and preparing method thereof
CN106750328A (en) * 2016-11-23 2017-05-31 厦门大学 A kind of fluorine silicon polyphosphate and its preparation method and application
CN110628179A (en) * 2019-08-30 2019-12-31 厦门大学 Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof
CN110746753A (en) * 2019-10-16 2020-02-04 苏州市新广益电子有限公司 PET film blowing bag and preparation method thereof
WO2023044692A1 (en) * 2021-09-24 2023-03-30 郑荣志 Thermoplastic polyester used for thin film, and preparation method therefor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000212266A (en) * 1999-01-26 2000-08-02 Nippon Ester Co Ltd Preparation of flame-retardant polyester
CN102391488A (en) * 2011-09-26 2012-03-28 四川东方绝缘材料股份有限公司 Preparation method for fluorine silicon phosphorus-containing anti-dropping flame-retardant polyethylene terephthalate

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000212266A (en) * 1999-01-26 2000-08-02 Nippon Ester Co Ltd Preparation of flame-retardant polyester
CN102391488A (en) * 2011-09-26 2012-03-28 四川东方绝缘材料股份有限公司 Preparation method for fluorine silicon phosphorus-containing anti-dropping flame-retardant polyethylene terephthalate

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105542137A (en) * 2016-01-22 2016-05-04 四川东方绝缘材料股份有限公司 Multipolymer resin, multipolymer compound base film and preparation method of multipolymer compound base film
CN105860044B (en) * 2016-06-17 2018-08-28 台州市黄岩腾迪日用品有限公司 A kind of thermoplastic polyester and preparation method thereof for film
CN105860044A (en) * 2016-06-17 2016-08-17 苍南县宝丰印业有限公司 Thermoplastic polyester for films and preparation method thereof
CN105860043A (en) * 2016-06-17 2016-08-17 苍南县宝丰印业有限公司 Thermoplastic polyester for antibacterial film and preparation method of thermoplastic polyester
CN106005656A (en) * 2016-06-17 2016-10-12 苍南县宝丰印业有限公司 Cake packaging box
CN106432898A (en) * 2016-06-17 2017-02-22 苍南县宝丰印业有限公司 Cast film with high barrier property
CN105860043B (en) * 2016-06-17 2018-06-19 汕头市金立方包装实业有限公司 A kind of thermoplastic polyester of antibacterial film and preparation method thereof
CN106565943A (en) * 2016-11-08 2017-04-19 四川东材科技集团股份有限公司 Fluorosilicone copolyester resin and preparing method thereof
CN106750328A (en) * 2016-11-23 2017-05-31 厦门大学 A kind of fluorine silicon polyphosphate and its preparation method and application
CN106750328B (en) * 2016-11-23 2019-07-30 厦门大学 A kind of fluorine silicon polyphosphate and its preparation method and application
US11046816B2 (en) 2016-11-23 2021-06-29 Xiamen University Method for preparing fluorine-silicon-containing polyphosphate ester and flame retardant epoxy resin
CN110628179A (en) * 2019-08-30 2019-12-31 厦门大学 Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof
CN110628179B (en) * 2019-08-30 2020-11-17 厦门大学 Low-dielectric-constant flame-retardant electronic packaging material and preparation method thereof
CN110746753A (en) * 2019-10-16 2020-02-04 苏州市新广益电子有限公司 PET film blowing bag and preparation method thereof
WO2023044692A1 (en) * 2021-09-24 2023-03-30 郑荣志 Thermoplastic polyester used for thin film, and preparation method therefor

Also Published As

Publication number Publication date
CN102634174B (en) 2014-01-08

Similar Documents

Publication Publication Date Title
CN102634174B (en) Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine
WO2013017044A1 (en) New biodegradable masterbatch and preparation method thereof
CN103044673B (en) Preparation method of reaction type halogen-free phosphorous flame retardant polyester polyol
CN102660010B (en) Preparation method of reactive polyester flame-retardant additive
CN105585701A (en) A continuous preparing method for polyether modified copolyester
CN103739832B (en) A kind of manufacture method of cationic dye capable of dyeing fire retardant polyester resin
CN101508770A (en) Method for preparing phosphor system halogen-free flame-proof copolymerization polyester
CN102660009B (en) Preparation method of flame-retardant linear copolyester resin
CN104262596B (en) A kind of high-functionality polyester polyol and preparation method thereof
CN102295761A (en) Method for preparing polyester for foaming
CN103554497A (en) Method for preparing flame-retardant thermoplastic polyimide resin
CN106928490B (en) A kind of inorganic-organic hybridization nano compound, preparation method and its flame-proof polylactic acid with the fire-retardant synergistic effect of chain extension-
TW201422662A (en) Continuous preparation method of biodegradable aliphatic/aromatic polyester copolymer
CN104119380A (en) Halogen-free oligomerization phosphonate flame retardant and synthesis method thereof
CN103275309A (en) Phosphorous flame-retardant unsaturated polyester resin and preparation method thereof
CN103030796A (en) Preparation method of molten-drop-resistant halogen-free flame-retardant PTT (polytrimethylene terephthalate) polyester resin
CN106496536A (en) The preparation method of containing phosphorus silicon fire retardant polyethylene terephthalate
CN107325270A (en) A kind of fire-retardant sulphonate-base PEPA of Halogen copoly type and preparation method thereof
KR101992392B1 (en) Method for continuous production of biodegradable aliphatic/aromatic polyester copolymer
TW201422663A (en) Continuous preparation method of biodegradable aliphatic/aromatic polyester copolymer
CN103804666B (en) A kind of preparation method of liquid crystalline polymers
CN103897162B (en) A kind of high molecular weight liquid crystal polyester and its preparation method and application
CN103724606A (en) Copolyester and preparation method thereof
CN102010586A (en) Phosphate flame retardant for urethane foams and synthesis method of phosphate flame retardant
CN109734891A (en) Modified aromatic race liquid-crystal polyester resin with less anisotropy and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C53 Correction of patent of invention or patent application
CB02 Change of applicant information

Address after: Samsung road 621000 Mianyang city of Sichuan province Youxian District No. 188

Applicant after: Sichuan Dongfang Insulating Material Co., Ltd.

Address before: 621000 Mianyang City, Sichuan province Youxian District No. 6 Dongxing Road

Applicant before: Sichuan Dongfang Insulating Material Co., Ltd.

C14 Grant of patent or utility model
GR01 Patent grant