CN105924911B - A kind of Composite flame-retardant polyethylene terephthalate system and preparation method thereof - Google Patents

A kind of Composite flame-retardant polyethylene terephthalate system and preparation method thereof Download PDF

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CN105924911B
CN105924911B CN201610546819.7A CN201610546819A CN105924911B CN 105924911 B CN105924911 B CN 105924911B CN 201610546819 A CN201610546819 A CN 201610546819A CN 105924911 B CN105924911 B CN 105924911B
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retardant
fire
pet
composite flame
polyethylene terephthalate
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CN105924911A (en
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朱志国
王锐
董振峰
魏丽菲
靳昕怡
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Beijing Institute Fashion Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • C08G63/86—Germanium, antimony, or compounds thereof
    • C08G63/866—Antimony or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Abstract

The invention discloses a kind of Composite flame-retardant polyethylene terephthalate (PET) systems and preparation method thereof, Composite flame-retardant PET system includes the component of following weight proportion: PET100 parts by weight, phosphorous copoly type fire retardant 2.0-8.5 parts by weight, fire retarding synergist 0-0.5 parts by weight, stabilizer 0.01-0.1 parts by weight.The halogen-free flame retardants used in the present invention has many advantages, such as safety, suppression cigarette, nontoxic, inexpensive, anti-dropping, and fire retardant additive amount is few in PET system, while playing fire retardation, on the mechanical property of material without influence.

Description

A kind of Composite flame-retardant polyethylene terephthalate system and preparation method thereof
Technical field
The present invention relates to a kind of flame retardant type polyethylene terephthalate system, in particular to a kind of compound resistance of zinc borate Combustion type polyethylene terephthalate system and preparation method thereof.
Background technique
Polyethylene terephthalate (PET) is comprehensive as the earliest thermoplastic polymer for realizing industrial applications Can be excellent, it is extensive in textile and engineering plastics application aspect, be currently yield highest, dosage be maximum in the world, purposes most Extensive high molecular synthetic material.But since its limited oxygen index (LOI, Limited Oxygen Index) is only 22% left side The right side belongs to combustible material, and burning velocity is fast, highly exothermic, and melt drip phenomenon is serious, and with heavy smog, have compared with Apparent fire hazard.Anti-dropping is modified to be mostly used greatly copolymerization and two methods realization is blended.Copolymerization method is mainly using with resistance The reactive flame retardant of combustion and anti-dropping function, REINFORCED PET is fire-retardant and anti-dropping performance.Blending method passes through addition such as laminar silicic acid The increased viscosities such as salt or increase burning neat coal amout achieve the purpose that anti-dropping.For the modified method of blending fire retardant, fire retardant adds Dosage is excessive, can have an adverse effect to PET mechanical property, and this is mainly due to co-mixing systems to be easy to happen micron-scale phase separation, Destroy the mechanical property of material.
Currently, flame-retarded resin mostly uses halogen containing flame-retardant to carry out compound or be blended, its limit oxygen index is improved as far as possible, is reduced The combustibility of material.Although the good flame retardation effect of halogenated flame retardant, and additive amount is few, its combustion product has one to environment Fixed negative effect, such as release toxic and corrosive hydrogen halide.And halogen-free flame retardants have safety, suppression cigarette, The exploitation of the advantages that nontoxic, inexpensive, this based flame retardant have become a hot spot of current fire retardant research field.
Based on the above reasons, need to develop that a kind of fire retardant additive amount is few, flame retardant property is strong, mechanical strength is unaffected Halogen Composite flame-retardant PET.
Summary of the invention
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that using 2- carboxyethyl phenyl time phosphorus Sour (CEPPA) is fire retardant, and zinc borate (ZB) and mountain aoxidize two antimony (Sb2O3) it is fire retarding synergist, it is added in esterification process Into polymerization reaction system, it can obtain that flame retardant property is strong, the impregnable PET system of mechanical strength, so as to complete this hair It is bright.
The purpose of the present invention is to provide following aspect:
In a first aspect, providing a kind of Composite flame-retardant PET system, Composite flame-retardant PET system includes that following weight is matched The component of ratio:
Second aspect provides a kind of preparation method of Composite flame-retardant PET system, comprising the following steps:
Step 1) weighs terephthalic acid (TPA), ethylene glycol, catalyst and part fire retarding synergist by weight ratio, is placed in anti- It answers in kettle, pressurized, heated, insulation reaction；
Phosphorous copoly type fire retardant, the rest part resistance of specified weight proportion are added in Xiang Shangshu reaction system for step 2) Fire synergist and stabilizer, the reaction was continued under normal pressure；
The mixture of step 2) is transferred to the polycondensation reaction under vacuum condition by step 3), until it is viscous to reach scheduled melt Degree terminates polycondensation reaction.
A kind of Composite flame-retardant PET system provided according to the present invention and preparation method thereof, has the advantages that
(1) compared with prior art, fire retardant and fire retarding synergist addition in Composite flame-retardant PET system is made in the present invention Amount is seldom, while guaranteeing high fire-retardance effect, on the mechanical property of material without influence；
(2) being used in compounding by fire retardant and fire retarding synergist enhances the flame retardant property of PET system, and presses down cigarette effect Fruit is obvious；
(3) being used in compounding by heat stabilizer and antioxidant, greatly inhibits the degradation of PET；
(4) halogen-free environment-friendlyflame flame retardant is used, the requirement of environment-friendly flame retardant is met；
(5) method provided by the invention has the characteristics that easy to operate, easily controllable and industrialized production.
Detailed description of the invention
Fig. 1 shows the DSC curve figure of embodiment 1-4 and comparative example 1-4 product；
Fig. 2 shows layer of charcoal patterns after 1 product combustion degradation of comparative example；
Fig. 3 shows layer of charcoal pattern after 4 product combustion degradation of comparative example；
Fig. 4 shows layer of charcoal pattern after 1 product combustion degradation of embodiment；
Fig. 5 shows layer of charcoal pattern after 4 product combustion degradation of embodiment.
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations It is clear, clear.
Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.Here as " exemplary " Illustrated any embodiment should not necessarily be construed as preferred or advantageous over other embodiments.Although each of embodiment is shown in the attached drawings In terms of kind, but unless otherwise indicated, it is not necessary to attached drawing drawn to scale.
According to the first aspect of the invention, a kind of Composite flame-retardant PET system, the group including following weight proportion are provided Point:
In the present invention, the stabilizer includes heat stabilizer, antioxidant or combinations thereof.
In the present invention, phosphorous copoly type fire retardant, the additive amount of fire retarding synergist are less, are not susceptible to reaction system Micron-scale phase separation without influence or influences very little to the mechanical property of material.
In the present invention, the phosphorous copoly type fire retardant is selected from 2- carboxyethyl phenyl hypophosphorous acid, dicarboxylic acids ethyl-methyl phosphorus One of acid esters, phosphorous acid two (4- carboxyl phenyl) ester, tricresyl phosphate (4- carboxyl phenyl) ester are a variety of, preferably 2- carboxyethyl benzene Base hypophosphorous acid (CEPPA).
The comprehensive comparison of phosphorus flame retardant is strong, can not only increase to avoid the fiber weakness as caused by halogen flame Add, the problems such as color deteriorates and fastness to light reduces, usually can also improve the dyeability and color of fiber, thus the present invention Selecting phosphorous copoly type fire retardant is main flame retardant, preferably 2- carboxyethyl phenyl hypophosphorous acid.
Meanwhile 2- carboxyethyl phenyl hypophosphorous acid has dosage few as fire retardant, the advantage of good flame retardation effect, and has Preferable hydrolytic resistance, higher reactivity, the presence of phenyl assigns its good thermal stability and oxidation stability again, right The mechanical performance of material is almost without influence.
In the present invention, the fire retarding synergist is selected from zinc borate, antimony oxide, antimony pentoxide, metaborate, oxidation One of iron, aluminium hydroxide, magnesium hydroxide, melamine are a variety of, as antimony oxide and metaborate or zinc borate with Melamine is used in compounding, and preferred boric acid zinc and antimony oxide are used in compounding.
The fire retardant mechanism of zinc borate (ZB) can be summarized as heat absorption and diluting effect, covering effect and inhibit the tripartites such as chain reaction Face.ZB is nontoxic because its is inexpensive, non-stimulated, and hydrate water is still contained at 260 DEG C or less, can decompose under high temperature and generate B2O3Solid and it is attached In material surface, can effectively inhibit imflammable gas to generate and prevent oxidation and thermal decomposition effect further progress, and It does not have much affect to the intensity and heat aging performance of many polymer, is often used in combination with other fire retardants, to play fire-retardant synergistic Effect and suppression hood.
Antimony oxide (Sb2O3) fire retardant mechanism category gas phase it is fire-retardant, burning initial stage is melting process, on the surface of the material shape At protective film to completely cut off air, ignition temperature is reduced by the internal endothermic reaction；Sb under the condition of high temperature2O3Vaporization, diluent air Middle oxygen concentration, to play fire retardation.ZB and Sb2O3Compounding can further improve flame retardant effect, while smoke suppressing effect is brighter It is aobvious.
ZB and Sb2O3Size distribution have larger impact to the mechanical property of material be added, application performance and appearance.It is sub- Micron or nanometer ZB and Sb2O3It is small on the impact strength of polymeric material and toughness influence since granularity is superfine micro-, it can greatly mention The mechanical property of high polymerization material, due to large specific surface area, reactivity is high, fire-retardant synergistic effect better than common partial size ZB and Sb2O3, and dosage has larger reduction compared with regular grade.In the present invention, the fire retarding synergist uses preceding ground processing, zinc borate Partial size be 0.5-5.0 μm, preferably 0.7-3.0 μm；The partial size of antimony oxide is 0.5-1.0 μm, preferably 0.6-0.8 μm.
It further include the catalyst of esterification in the present invention, in Composite flame-retardant PET system, the catalyst is selected from Sb2O3, one of antimony glycol and butyl titanate or a variety of, preferably Sb2O3。
In the present invention, the heat stabilizer is selected from ammonium phosphite, ammonium phosphate, ammonium dihydrogen phosphate, trimethyl phosphate, di(2-ethylhexyl)phosphate One of methyl esters, triphenyl phosphate, diphenyl phosphate, triphenyl phosphite, diphenyl phosphite are a variety of, preferably phosphorous acid Triphenylmethyl methacrylate；And/or
The antioxidant is selected from one of antioxidant 1010, antioxidant 1076, antioxidant 1425 or a variety of, preferably antioxygen Agent 1010.
Heat stabilizer and antioxidant are added, is the effective ways for inhibiting PET degradation.Main anti-oxidant and auxiliary antioxidant Also there is synergistic effect with synergistic effect, and between various auxiliary antioxidants and heat stabilizer.Triphenyl phosphite is not only It is heat stabilizer, while is also auxiliary antioxidant.Therefore, in the present invention, preferably heat stabilizer and antioxidant are used in combination, more It is preferred that triphenyl phosphite and antioxidant 1010 are used in compounding.
It further include with three (2- ethoxy) isocyanuric acid terephthalates in the present invention, in Composite flame-retardant PET system It is the expansion type flame retardant of acid source synthesis for charcoal source/gas source, ammonium polyphosphate.
According to the second aspect of the invention, the preparation method of Composite flame-retardant PET system is provided, this method includes following step It is rapid:
Step 1) weighs terephthalic acid (TPA), ethylene glycol, catalyst and part fire retarding synergist by weight ratio, is placed in anti- It answers in kettle, pressurized, heated, insulation reaction；
Phosphorous copoly type fire retardant, the rest part resistance of specified weight proportion are added in Xiang Shangshu reaction system for step 2) Fire synergist and stabilizer, the reaction was continued under normal pressure；
The mixture of step 2) is transferred to the polycondensation reaction under vacuum condition by step 3), until it is viscous to reach scheduled melt Degree terminates polycondensation reaction.Nitrogen extruding and discharging, Cast Strip, pelletizing.
In the present invention, reaction temperature is 210 DEG C -260 DEG C, preferably 220 DEG C -245 DEG C in step 1)；
Polymerization reaction initial stage pressure is controlled in 0.2MPa-0.4MPa, preferably 0.25-0.35MPa.With esterification It carries out, pressure is gradually reduced in kettle, until normal pressure.
In the present invention, synthesis under normal pressure time 30min-90min, preferably 40min-60min in step 2)；
Fire retarding synergist and fire retarding synergist in step 1 are identical fire retarding synergist or different fire retarding synergists in step 2, Preferably different fire retarding synergists, fire retarding synergist is antimony oxide in more preferable step 1, at this point, antimony oxide is simultaneously As catalysts and fire retarding synergist, fire retarding synergist is zinc borate in step 2.
Embodiment
Embodiment 1
1) 700g terephthalic acid (TPA), 327g ethylene glycol and 0.32gSb are weighed2O3, it is placed in 2L polymeric kettle, heating pressurization is protected Hold 230 DEG C of interior temperature, it is interior be pressed in 0.3MPa, with the progress of esterification, pressure is gradually reduced in kettle, until normal pressure；
2) 33.6g fire retardant CEPPA, 0.24g antioxidant 1010,0.24g triphenyl phosphite, synthesis under normal pressure is added 40min；
3) polycondensation reaction being transferred under vacuum condition terminates polycondensation reaction until power of agitator reaches rated value.Nitrogen squeezes Extrude material, Cast Strip, pelletizing.The production quantity of Composite flame-retardant PET system is 810g, intrinsic viscosity (dL/g) 0.687, P element matter Measuring content (relative to pet polymer) is 0.6wt%, and ZB mass content (relative to pet polymer) is 0wt%.
Embodiment 2
1) 700g terephthalic acid (TPA), 327g ethylene glycol and 0.32gSb are weighed2O3, it is placed in 2L polymeric kettle, heating pressurization is protected Hold 230 DEG C of interior temperature, it is interior be pressed in 0.3MPa, with the progress of esterification, pressure is gradually reduced in kettle, until normal pressure；
2) 34.2g fire retardant CEPPA, 0.24g antioxidant 1010,0.24g triphenyl phosphite, 0.405g ball milling point is added Dissipate treated zinc borate, synthesis under normal pressure 40min；
3) polycondensation reaction being transferred under vacuum condition terminates polycondensation reaction until power of agitator reaches rated value.Nitrogen squeezes Extrude material, Cast Strip, pelletizing.The production quantity of Composite flame-retardant PET system is 811g, intrinsic viscosity (dL/g) 0.635, P element matter Measure content (relative to pet polymer) 0.6wt%, ZB mass content (relative to pet polymer) 0.05wt%.
Embodiment 3
1) 700g terephthalic acid (TPA), 327g ethylene glycol and 0.32gSb are weighed2O3, it is placed in 2L polymeric kettle, heating pressurization is protected Hold 230 DEG C of interior temperature, it is interior be pressed in 0.3MPa, with the progress of esterification, pressure is gradually reduced in kettle, until normal pressure；
2) 34.2g fire retardant CEPPA, 0.24g antioxidant 1010,0.24g triphenyl phosphite, 0.81g ball milling point is added Dissipate treated zinc borate, synthesis under normal pressure 40min；
3) polycondensation reaction being transferred under vacuum condition terminates polycondensation reaction until power of agitator reaches rated value.Nitrogen squeezes Extrude material, Cast Strip, pelletizing.The production quantity of Composite flame-retardant PET system is 811g, intrinsic viscosity (dL/g) 0.582, P element matter Measure content (relative to pet polymer) 0.6wt%, ZB mass content (relative to pet polymer) 0.1wt%.
Embodiment 4
1) 700g terephthalic acid (TPA), 327g ethylene glycol and 0.32gSb are weighed2O3, it is placed in 2L polymeric kettle, heating pressurization is protected Hold 230 DEG C of interior temperature, it is interior be pressed in 0.3MPa, with the progress of esterification, pressure is gradually reduced in kettle, until normal pressure；
2) 34.2g fire retardant CEPPA, 0.24g antioxidant 1010,0.24g triphenyl phosphite, 1.62g ball milling point is added Dissipate treated zinc borate, synthesis under normal pressure 40min；
3) polycondensation reaction being transferred under vacuum condition terminates polycondensation reaction until power of agitator reaches rated value.Nitrogen squeezes Extrude material, Cast Strip, pelletizing.The production quantity of Composite flame-retardant PET system is 812g, and intrinsic viscosity (dL/g) 0.571, P element contains Measure (relative to pet polymer) 0.6wt%, ZB content (relative to pet polymer) 0.2wt%.
Comparative example
Comparative example 1
1) 700g terephthalic acid (TPA), 327g ethylene glycol and 0.32gSb are weighed2O3, it is placed in 2L polymeric kettle, heating pressurization is protected Hold 230 DEG C of interior temperature, it is interior be pressed in 0.3MPa, with the progress of esterification, pressure is gradually reduced in kettle, until normal pressure；
2) 0.24g antioxidant 1010,0.24g triphenyl phosphite, synthesis under normal pressure 40min is added；
3) polycondensation reaction being transferred under vacuum condition terminates polycondensation reaction until power of agitator reaches rated value.Nitrogen squeezes Extrude material, Cast Strip, pelletizing.The intrinsic viscosity (dL/g) 0.690 of obtained Composite flame-retardant PET system, P element mass content (relative to pet polymer) 0wt%, ZB mass content (relative to pet polymer) 0wt%.
Comparative example 2
1) 700g terephthalic acid (TPA), 327g ethylene glycol and 0.32gSb are weighed2O3, it is placed in 2L polymeric kettle, heating pressurization is protected Hold 230 DEG C of interior temperature, it is interior be pressed in 0.3MPa, with the progress of esterification, pressure is gradually reduced in kettle, until normal pressure；
2) zinc borate after 0.24g antioxidant 1010,0.24g triphenyl phosphite, 0.405g ball milling decentralized processing is added, Synthesis under normal pressure 40min；
3) polycondensation reaction being transferred under vacuum condition terminates polycondensation reaction until power of agitator reaches rated value.Nitrogen squeezes Extrude material, Cast Strip, pelletizing.The intrinsic viscosity (dL/g) 0.605 of obtained Composite flame-retardant PET system, P element mass content (relative to pet polymer) 0wt%, ZB mass content (relative to pet polymer) 0.05wt%.
Comparative example 3
1) 700g terephthalic acid (TPA), 327g ethylene glycol and 0.32Sb are weighed2O3, it is placed in 2L polymeric kettle, heating pressurization is protected Hold 230 DEG C of interior temperature, it is interior be pressed in 0.3MPa, with the progress of esterification, pressure is gradually reduced in kettle, until normal pressure；
2) zinc borate after 0.24g antioxidant 1010,0.24g triphenyl phosphite, 0.81g ball milling decentralized processing is added, Synthesis under normal pressure 40min；
3) polycondensation reaction being transferred under vacuum condition terminates polycondensation reaction until power of agitator reaches rated value.Nitrogen squeezes Extrude material, Cast Strip, pelletizing.The intrinsic viscosity (dL/g) 0.572 of obtained Composite flame-retardant PET system, P element mass content (relative to pet polymer) 0wt%, ZB mass content (relative to pet polymer) 0.1wt%.
Comparative example 4
1) 700g terephthalic acid (TPA), 327g ethylene glycol and 0.32gSb are weighed2O3, it is placed in 2L polymeric kettle, heating pressurization is protected Hold 230 DEG C of interior temperature, it is interior be pressed in 0.3MPa, with the progress of esterification, pressure is gradually reduced in kettle, until normal pressure；
2) zinc borate after 0.24g antioxidant 1010,0.24g triphenyl phosphite, 1.62g ball milling decentralized processing is added, Synthesis under normal pressure 40min；
3) polycondensation reaction being transferred under vacuum condition terminates polycondensation reaction until power of agitator reaches rated value.Nitrogen squeezes Extrude material, Cast Strip, pelletizing.The intrinsic viscosity (dL/g) 0.580 of obtained Composite flame-retardant PET system, P element mass content (relative to pet polymer) 0wt%, ZB mass content (relative to pet polymer) 0.2wt%.
Experimental example
Seiko DSC-6200 type differential scanning calorimeter (DSC) table produced using Seiko Instruments Inc. Levy the hot property of Flame-retardant PET；
Limit oxygen index (LOI): it is surveyed using the Dynisco type limit oxygen index analyzer of U.S. Dynisco Inc. production The LOI of test agent, while observing the molten drop situation in batten combustion process.Batten having a size of 80mm × 6.5mm × 3mm, It is prepared in Haake MiniJet microspecimen injector.
Molten drop situation: horizontal, the Vertical combustion instrument test specimens using the CZF-3 type of analysis instrument factory, Jiangning county production The molten drop situation of product, level clamping batten, in the case where Persistence flame, (length of flame is the molten drop number for calculating in 1min 2cm)；And measure the quality of drippage molten drop.Batten is having a size of 80mm × 6.5mm × 3mm, in Haake MiniJet micro sample It is prepared in injector.
Cone calorimetry tests (CONE): the standard cone produced using Britain Fire Testing Technology Ltd Shape calorimeter is tested.Sample size: 100mm × 100mm × 3mm.According to the standard that ISO5660 is formulated, by the side of sample Edge and bottom wrap up juxtaposition with aluminium foil and are put in horizontal sample slot, and sample is in 35kw/m2It is heated by under heat radiation power condition The parameters such as burning time, the heat release rate that CONE measurement analysis software obtains.
Surface topography: it is burnt in Muffle furnace drop using the JSM-6030 type scanning electron microscopic observation that Japan Electronics Corporation produces Solve the pattern of (keeping 30min at 450 DEG C) residue.
The hot property of 1 Flame-retardant PET of experimental example
By product made from embodiment 1-4 and comparative example 1-4 and thermal performance test is carried out, as a result as shown in Figure 1, wherein
Curve 1 indicates that the DSC curve of product is made in comparative example 1；
Curve 2 indicates that the DSC curve of product is made in comparative example 2；
Curve 3 indicates that the DSC curve of product is made in comparative example 3；
Curve 4 indicates that the DSC curve of product is made in comparative example 4；
Curve 5 indicates that the DSC curve of product is made in embodiment 1；
Curve 6 indicates that the DSC curve of product is made in embodiment 2；
Curve 7 indicates that the DSC curve of product is made in embodiment 3；
Curve 8 indicates that the DSC curve of product is made in embodiment 4.
As shown in Figure 1, the addition of ZB is to the various thermal features parameters of PET, such as glass transition temperature (Tg), crystallization The influences such as temperature (Tc) and melting temperature (Tm) are not apparent.Because ZB is deposited in system as just a kind of additive The interaction between polymer chain is not obvious；And due to the copoly type fire retardant CEPPA of use, the chemistry of generation Reaction can reduce the regularity of PET macromolecular chain, unfavorable to the crystallization of chain, and common manifestation be to crystallize and melting heat enthalpy subtracts It is small.Equally on this basis, apparent structure influence will not be generated by adding ZB also.
2 limit oxygen index of experimental example
Product made from embodiment 1-4 and comparative example 1-4 is subjected to limit oxygen index measurement, the results are shown in Table 1.It is surveying In the experimentation for trying oxygen index (OI), while qualitative record molten drop situation, the i.e. mainly ready visual contrast of tester, molten drop situation Severity is described with the increase of ☆ number, and number is more, indicates that molten drop situation is more serious.
1 limit oxygen index data of table
As can be seen from Table 1, compared with PET, the ZB that addition mass fraction is 0.05% can obvious raising PET body The LOI of system, from 23% to 27%, reach flame-retardant polymer basic demand (general LOI be more than 26% can be described as it is fire-retardant Polymer)；But during the test, discovery still has apparent molten drop phenomenon, when ZB content increases to 0.2% in PET, energy Enough molten drip phenomenons of discovery burning are weakened.On the other hand, for adding the PET sample of phosphorus flame retardant, it is evident that Only addition fire retardant (i.e. PET/P) can equally significantly improve the LOI (for 29%) of PET system, but melt drip phenomenon has deterioration Trend, this is related with the condensed phase fire retardant mechanism of phosphorus flame retardant.Different amounts of ZB is added in PET/P system, LOI is basic It is unchanged, 29% is maintained, but the molten drop phenomenon of fire-retardant PET system makes moderate progress with the addition of ZB.
3 molten drop situation of experimental example
Product made from embodiment 1-4 and comparative example 1-4 is carried out to the quantitative test of amount of molten drops and quality, as a result such as table Shown in 2.
The molten drop situation of 2 sample of table in combustion
As shown in Table 2, in comparative example 1-4, the PET system of ZB is added compared with pure PET, molten drop number is reduced, explanation The anti-dropping of Flame-retardant PET system is improved, but average every drip melt drop purer PET of quality has increase, this is because ZB pairs The charing of polymer has certain promotion, and the increase of charing amount is conducive to the melt viscosity in strengthen burning forward position, to extend Residence time of the molten drop in batten combustion front, make the more difficult drippage of molten drop.
After adding phosphorus flame retardant, obtained Flame-retardant PET system amount of molten drops and total weight increases, this is phosphorous flame-retardant Polyester plays one of the approach of flame retardant effect, that is, generates more molten drop, heat or flame are taken away PET combustion front.Equally ZB is added in PET/P system, with the increase of ZB content, molten drop number and molten drop gross mass are reduced, this and ZB are fired in PET Catalysis carbon-forming effect during burning is related.As the ZB of addition 0.2% in flame retardant polyester, amount of molten drops and gross mass go out It is now more apparent to weaken.
Therefore, it is tested in conjunction with limit oxygen index and two kinds of molten drop situation, it is believed that ZB and phosphorus flame retardant can be common Improve the flame-retardant modified of PET, the i.e. LOI of phosphorus flame retardant raising PET, and remaining char amount in PET combustion process can be improved in ZB, altogether With the flame retardant property for improving PET.
The test of 4 cone calorimetry of experimental example
It is 35kw/m in radiant power using the cone calorimetry of FTT company2Under conditions of, measure ignitor firing time (TTI), heat release rate (HRR) and mass loss rate (MLR)；Wherein pk-HRR, tpk-HRR, tpk-MLR are respectively referred to The peak value of HRR, the time for reaching peak value to time required for reach to peak value and mass loss rate.The results are shown in Table 3.
Key data in the test of 3 cone calorimetry of table
By comparative example 1-4 it is found that TTI, tpk-HRR and tpk-MLR of PET are 79s, 136s and 126s respectively.Work as addition After the ZB of mass fraction 0.05%, TTI, tpk-HRR, tpk-MLR of PET system increase respectively to 88s, 142s and 130s.This The variation of kind burning time parameter is on the one hand since ZB is thermally decomposed, and the crystallization water of release plays heat absorption cooling effect and dilution can The effect of combustion gas body；On the other hand, ZB is decomposed and is generated B at high temperature2O3, it is attached on the surface of polymer and forms one layer of covering Layer, this coating can inhibit the generation of imflammable gas, and oxidation reaction and thermal decomposition can also be prevented to act on, delay or reduce combustion The rate that the release for the amount of heating and polymerization weight are lost due to degradation.In embodiment 1-4, in phosphorus flame retardant or ZB With both phosphorus flame retardants it is common in the presence of, in taper calorimetric test, each characteristic time of the composite flame-proof PET system of acquisition There is increased trend in parameter (TTI, tpk-HRR, tpk-MLR), illustrates that ZB and phosphorus flame retardant are used in compounding, and has more preferable Flame retardant effect.
5 Flame-retardant PET of experimental example degradation layer of charcoal pattern
Using scanning electron microscope (SEM) to the layer of charcoal generated after product combustion degradation made from embodiment 1,4 and comparative example 1,4 It is observed, as a result as shown in Fig. 2-Fig. 5.
There are a large amount of bubble impressions in Fig. 2 after PET combustion degradation, and has ruptured.The layer of charcoal knot formed after PET combustion degradation Structure is loose, causes a large amount of fuel gas to escape from hole and gap, is conducive to the burning and degradation of PET.Add phosphorus flame retardant Afterwards, as shown in figure 3, the bubble of charcoal layer surface is reduced, and part bubble does not rupture, layer of charcoal surface compact, to combustible gas The evolution of body has certain inhibiting effect；According to LOI the result shows that, phosphorus flame retardant is individually added than being individually added into ZB pairs The raising of PET limited oxygen index is more obvious, also there is similar embodiment from layer of charcoal pattern, as shown in Figure 3 and Figure 4, i.e. PET/P system The bubble ratio PET/ZB-0.2 system of surface-closed is more, and closed bubble can reduce the release of fuel gas certainly Amount；While after the PET system for adding fire retardant CEPPA and ZB is degraded in Muffle furnace, as shown in figure 5, obtained charcoal layer surface Compactness improves, and closed bubble is obviously increased, played an important role for the resistance to melt-dropping property and smog burst size of PET system.
It is described the invention in detail above in conjunction with detailed description and exemplary example, but these explanations are simultaneously It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention, Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention In the range of.Scope of protection of the present invention is subject to the appended claims.

Claims (3)

1. a kind of preparation method of Composite flame-retardant polyethylene terephthalate system, which is characterized in that
The Composite flame-retardant polyethylene terephthalate system includes the component of following weight proportion:
The fire retarding synergist is zinc borate and antimony oxide；
The stabilizer is the combination of heat stabilizer and antioxidant, and the heat stabilizer is triphenyl phosphite；The antioxidant For antioxidant 1010；
The phosphorous copoly type fire retardant is 2- carboxyethyl phenyl hypophosphorous acid；
The partial size of zinc borate is 0.7-3 μm；The partial size of antimony oxide is 0.6-0.8 μm；
It further include catalyst in the Composite flame-retardant polyethylene terephthalate system, the catalyst is three oxidations two Antimony,
The preparation method comprises the following steps:
Step 1) weighs terephthalic acid (TPA), ethylene glycol, catalyst and part fire retarding synergist by weight ratio, is placed in reaction kettle In, pressurized, heated, insulation reaction, reaction temperature is 220 DEG C -245 DEG C；System pressure range is 0.25-0.35MPa；
Phosphorous copoly type fire retardant, the fire-retardant association of rest part of specified weight proportion are added in Xiang Shangshu reaction system for step 2) Imitate agent and stabilizer, the reaction was continued under normal pressure；
The mixture of step 2) is transferred under vacuum condition and carries out polycondensation reaction by step 3), until reach scheduled melt viscosity, Terminate polycondensation reaction,
Wherein, fire retarding synergist and fire retarding synergist in step 1) are different fire retarding synergists in the step 2).
2. the preparation method of Composite flame-retardant polyethylene terephthalate system according to claim 1, feature It is,
In step 2), synthesis under normal pressure time 30min-90min.
3. the preparation method of Composite flame-retardant polyethylene terephthalate system according to claim 2, feature It is,
In step 2), the synthesis under normal pressure time is 40min-60min；
Fire retarding synergist is antimony oxide in step 1), and fire retarding synergist is zinc borate in step 2).
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