CN105924911A - Compound flame-retardant polyethylene glycol terephthalate system and preparation method thereof - Google Patents
Compound flame-retardant polyethylene glycol terephthalate system and preparation method thereof Download PDFInfo
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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
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- 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
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- 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
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- 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
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- 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'
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- 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
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- 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
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- 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 compound flame-retardant polyethylene glycol terephthalate (PET) system and a preparation method thereof. The compound flame-retardant PET system comprises the following components in parts by weight: 100 parts of PET, 2.0-8.5 parts of a phosphorus-containing copolymerization type flame retardant, 0-0.5 part of a flame retardant synergist and 0.01-0.1 part of a stabilizer. A halogen-free flame retardant adopted in the invention has the advantages of safety, smoke suppression, no toxicity, low cost and dripping resistance, and the addition amount of the flame retardant in the PET system is low, so that mechanical properties of a material are not influenced while flame retardant effect is realized.
Description
Technical field
The present invention relates to a kind of flame retardant type polyethylene terephthalate system, especially
Relate to a kind of Firebrake ZB Composite flame-retardant polyethylene terephthalate system and system thereof
Preparation Method.
Background technology
Polyethylene terephthalate (PET) is as realizing industrial applications the earliest
Thermoplastic polymer, high comprehensive performance, apply at textile and engineering plastics
Aspect is extensive, is currently that yield in the world is the highest, consumption is maximum, purposes is widest
High molecular synthetic material.But, due to its limited oxygen index (LOI, Limited Oxygen
Index) being only about 22%, belong to combustible material, burning velocity is fast, highly exothermic,
Melt drip phenomenon is serious, and with heavy smog, has obvious fire hidden
Suffer from.Anti-dropping is modified uses copolymerization and blended two kinds of methods to realize mostly.Copolymerization method master
Using and have fire-retardant and anti-dropping function reactive flame retardant, REINFORCED PET is fire-retardant
With anti-dropping performance.Blending method is by adding such as the increased viscosity such as phyllosilicate or increasing
Add burning neat coal amout and reach the purpose of anti-dropping.For the method that blending fire retardant is modified,
Fire retardant addition is excessive, can have a negative impact PET mechanical property, and this is main
It is owing to co-mixing system is susceptible to micron-scale phase separation, destroys the mechanical property of material.
At present, flame-retarded resin many employings halogen containing flame-retardant carries out being combined or being blended, as far as possible
Improve its limited oxygen index, reduce the combustibility of material.Although the resistance of halogenated flame retardant
Fire effective, and addition is few, but its combustion product has certain bearing to environment
Face rings, as discharged toxic and corrosive hydrogen halide etc..And Halogen resistance
Combustion agent has safely, presses down cigarette, the advantage such as nontoxic, inexpensive, the exploitation of this based flame retardant
Have become as a focus of current fire retardant research field.
Based on above reason, need badly and develop that a kind of fire retardant addition is few, anti-flammability
Can strong, mechanical strength impregnable Halogen Composite flame-retardant PET.
Summary of the invention
In order to solve the problems referred to above, present inventor has performed and study with keen determination, found that
Using 2-carboxyethyl phenyl hypophosphorous acid (CEPPA) is fire retardant, Firebrake ZB (ZB)
Two antimony (Sb are aoxidized with mountain2O3) it is fire retarding synergist, i.e. join in esterification process
In polymerization reaction system, it is possible to obtain fire resistance is strong, mechanical strength is impregnable
PET system, thus complete the present invention.
It is an object of the invention to provide following aspect:
First aspect, it is provided that a kind of Composite flame-retardant PET system, this Composite flame-retardant
PET system includes the component of following weight proportion:
Second aspect, it is provided that the preparation method of a kind of Composite flame-retardant PET system, bag
Include following steps:
Step 1), weigh by weight ratio p-phthalic acid, ethylene glycol, catalyst and
Part fire retarding synergist, is placed in reactor, pressurized, heated, insulation reaction；
Step 2), in above-mentioned reaction system, add the phosphorous copolymerization of specified weight proportioning
Type fire retardant, remainder fire retarding synergist and stabilizer, continue reaction under normal pressure；
Step 3), by step 2) compound proceed to the polycondensation reaction under vacuum condition,
Until reaching predetermined melt viscosity, terminate polycondensation reaction.
A kind of Composite flame-retardant PET system provided according to the present invention and preparation side thereof
Method, has the advantages that
(1) during compared with prior art, the present invention prepares Composite flame-retardant PET system
Fire retardant and fire retarding synergist addition are little, while ensureing high fire-retardance effect,
On the mechanical property of material without impact；
(2) by fire retardant and the compounding use of fire retarding synergist, PET body is enhanced
The fire resistance of system, and smoke suppressing effect is obvious；
(3) by heat stabilizer and the compounding use of antioxidant, greatly inhibit
The degraded of PET；
(4) use halogen-free environment-friendlyflame flame retardant, meet the requirement of environment-friendly flame retardant；
(5) method that the present invention provides has easy and simple to handle, easily controllable and industrialization
The feature produced.
Accompanying drawing explanation
Fig. 1 illustrates the DSC curve figure of embodiment 1-4 and comparative example 1-4 product；
Fig. 2 illustrates layer of charcoal pattern after comparative example 1 product combustion degradation；
Fig. 3 illustrates layer of charcoal pattern after comparative example 4 product combustion degradation；
Fig. 4 illustrates layer of charcoal pattern after embodiment 1 product combustion degradation；
Fig. 5 illustrates layer of charcoal pattern after embodiment 4 product combustion degradation.
Detailed description of the invention
Below by the present invention is described in detail, the features and advantages of the invention will
Become more apparent from, clearly along with these explanations.
The most special word " exemplary " means " as example, embodiment or explanation
Property ".Here as any embodiment illustrated by " exemplary " should not necessarily be construed as being better than or
It is better than other embodiments.Although the various aspects of embodiment shown in the drawings, but
It it is unless otherwise indicated, it is not necessary to accompanying drawing drawn to scale.
According to the first aspect of the invention, it is provided that a kind of Composite flame-retardant PET system,
Component including following weight proportion:
In the present invention, described stabilizer includes heat stabilizer, antioxidant or a combination thereof.
In the present invention, phosphorous copoly type fire retardant, fire retarding synergist addition the most relatively
Few, make reaction system be not susceptible to micron-scale phase separation, to the mechanical property of material without shadow
Ring or impact is the least.
In the present invention, described phosphorous copoly type fire retardant is selected from 2-carboxyethyl phenyl time phosphorus
Acid, dicarboxylic acids ethyl-methyl phosphate ester, phosphorous acid two (4-carboxyl phenyl) ester, phosphorus
One or more in acid three (4-carboxyl phenyl) ester, preferably 2-carboxyethyl phenyl
Phosphoric acid (CEPPA).
The comprehensive comparison of phosphorus flame retardant is strong, not only can avoid by halogen flame retardant
The problems such as fiber weakness increase, color deterioration and fastness to light reduction that agent causes,
Generally also can improve dyeability and the color and luster of fiber, thus the present invention selects phosphorous common
Poly-type fire retardant is main flame retardant, preferably 2-carboxyethyl phenyl hypophosphorous acid.
Meanwhile, it is few that 2-carboxyethyl phenyl hypophosphorous acid has consumption as fire retardant, fire-retardant
Effective advantage, and there is preferable hydrolytic resistance, higher reactivity,
The existence of phenyl gives again its good heat stability and oxidation stability, to material
Mechanical performance is almost without impact.
In the present invention, described fire retarding synergist selected from Firebrake ZB, antimony oxide, five
Aoxidize two antimony, metaborate, ferrum oxide, aluminium hydroxide, magnesium hydroxide, melamine
One or more in amine, such as antimony oxide and metaborate or Firebrake ZB and trimerization
Cyanamide is compounding to be used, preferred boric acid zinc and the compounding use of antimony oxide.
The fire retardant mechanism of Firebrake ZB (ZB) can be summarized as heat absorption and diluting effect, covering
Three aspects such as effect and suppression chain reaction.ZB is inexpensive because of it, nontoxic, non-stimulated,
Less than 260 DEG C still contain hydrate water, and under high temperature, decomposable asymmetric choice net generates B2O3Solid and be attached to
Material surface, it is possible to effectively suppression imflammable gas produces and stop oxidation and thermal decomposition
Carrying out further of effect, and the intensity and heat aging performance to a lot of polymer does not has
The biggest impact, normal and other fire retardants use, to play flame retardant synergism and to press down cigarette
Function.
Antimony oxide (Sb2O3) fire retardant mechanism to belong to gas phase fire-retardant, the burning initial stage is
Melting process, at material surface formation protecting film to completely cut off air, is absorbed heat by inside
Reaction reduces ignition temperature；Sb under the condition of high temperature2O3Vaporization, in diluent air, oxygen is dense
Degree, thus play fire retardation.ZB and Sb2O3Compound and can further improve fire-retardant effect
Really, smoke suppressing effect becomes apparent from simultaneously.
ZB and Sb2O3Particle size distribution to the mechanical property of added material, application
Considerable influence can be had with outward appearance.Submicron or nanometer ZB and Sb2O3Owing to granularity is superfine
Micro-, impact strength and Toughness to polymeric material are little, can greatly improve polymerization
The mechanical property of material, owing to specific surface area is big, reactivity is high, and fire-retardant synergistic is imitated
Fruit is better than ZB and Sb of common particle diameter2O3, and consumption relatively regular grade has bigger minimizing.
In the present invention, described fire retarding synergist uses front ground process, the particle diameter of Firebrake ZB
For 0.5-5.0 μm, preferably 0.7-3.0 μm；The particle diameter of antimony oxide is 0.5-1.0 μm,
Preferably 0.6-0.8 μm.
In the present invention, Composite flame-retardant PET system also includes the catalysis of esterification
Agent, described catalyst is selected from Sb2O3, one in antimony glycol and butyl titanate
Or multiple, preferably Sb2O3。
In the present invention, described heat stabilizer is selected from ammonium phosphite, ammonium phosphate, di(2-ethylhexyl)phosphate
Hydrogen ammonium, trimethyl phosphate, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate,
One or more in triphenyl phosphite, diphenyl phosphite, preferably tricresyl phosphite
Phenyl ester；And/or
Described antioxidant is in antioxidant 1010, antioxidant 1076, antioxidant 1425
One or more, preferably antioxidant 1010.
Add heat stabilizer and antioxidant, be the effective ways of suppression PET degraded.Main
Antioxidant and auxiliary antioxidant have a synergism, and various auxiliary antioxidation
Also cooperative effect is had between agent and heat stabilizer.Triphenyl phosphite is not only thermally-stabilised
Agent, is also auxiliary antioxidant simultaneously.Therefore, in the present invention, preferably heat stabilizer
Compound with antioxidant compound use, more preferably triphenyl phosphite and antioxidant 1010 and make
With.
In the present invention, Composite flame-retardant PET system also includes with three (2-ethoxys)
Isocyanuric acid terephthalate be charcoal source/source of the gas, ammonium polyphosphate be acid source synthesis
Expansion type flame retardant.
According to the second aspect of the invention, it is provided that the preparation of Composite flame-retardant PET system
Method, the method comprises the following steps:
Step 1), weigh by weight ratio p-phthalic acid, ethylene glycol, catalyst and
Part fire retarding synergist, is placed in reactor, pressurized, heated, insulation reaction；
Step 2), in above-mentioned reaction system, add the phosphorous copolymerization of specified weight proportioning
Type fire retardant, remainder fire retarding synergist and stabilizer, continue reaction under normal pressure；
Step 3), by step 2) compound proceed to the polycondensation reaction under vacuum condition,
Until reaching predetermined melt viscosity, terminate polycondensation reaction.Nitrogen extruding and discharging, casting
Band, pelletizing.
In the present invention, step 1) in reaction temperature be 210 DEG C-260 DEG C, preferably
220℃-245℃；
The polyreaction initial stage, Stress control was at 0.2MPa-0.4MPa, was preferably
0.25-0.35MPa.Along with the carrying out of esterification, in still, pressure is gradually reduced, directly
To normal pressure.
In the present invention, step 2) in synthesis under normal pressure time 30min-90min, preferably
40min-60min；
In step 2, fire retarding synergist is identical fire-retardant synergistic with fire retarding synergist in step 1
Agent or different fire retarding synergist, be preferably different fire retarding synergist, more preferably step 1
Middle fire retarding synergist is antimony oxide, and now, antimony oxide is simultaneously as reaction
In catalyst and fire retarding synergist, step 2, fire retarding synergist is Firebrake ZB.
Embodiment
Embodiment 1
1) 700g p-phthalic acid, 327g ethylene glycol and 0.32gSb are weighed2O3, put
In 2L polymeric kettle, heating pressurization, keep in temperature 230 DEG C, in be pressed in 0.3MPa,
Along with the carrying out of esterification, in still, pressure is gradually reduced, until normal pressure；
2) 33.6g fire retardant CEPPA, 0.24g antioxidant 1010,0.24g are added
Triphenyl phosphite, synthesis under normal pressure 40min；
3) polycondensation reaction under vacuum condition is proceeded to, until power of agitator reaches rated value,
Terminate polycondensation reaction.Nitrogen extruding and discharging, Cast Strip, pelletizing.Composite flame-retardant PET
The growing amount of system is 810g, and intrinsic viscosity (dL/g) 0.687, P element quality contains
Amount (relative to pet polymer) is that 0.6wt%, ZB mass content is (relative to PET
Polymer) it is 0wt%.
Embodiment 2
1) 700g p-phthalic acid, 327g ethylene glycol and 0.32gSb are weighed2O3, put
In 2L polymeric kettle, heating pressurization, keep in temperature 230 DEG C, in be pressed in 0.3MPa,
Along with the carrying out of esterification, in still, pressure is gradually reduced, until normal pressure；
2) 34.2g fire retardant CEPPA, 0.24g antioxidant 1010,0.24g are added
Firebrake ZB after triphenyl phosphite, 0.405g ball milling dispersion process, synthesis under normal pressure
40min；
3) polycondensation reaction under vacuum condition is proceeded to, until power of agitator reaches rated value,
Terminate polycondensation reaction.Nitrogen extruding and discharging, Cast Strip, pelletizing.Composite flame-retardant PET
The growing amount of system is 811g, and intrinsic viscosity (dL/g) 0.635, P element quality contains
Amount (relative to pet polymer) 0.6wt%, ZB mass content is (relative to PET
Polymer) 0.05wt%.
Embodiment 3
1) 700g p-phthalic acid, 327g ethylene glycol and 0.32gSb are weighed2O3, put
In 2L polymeric kettle, heating pressurization, keep in temperature 230 DEG C, in be pressed in 0.3MPa,
Along with the carrying out of esterification, in still, pressure is gradually reduced, until normal pressure；
2) 34.2g fire retardant CEPPA, 0.24g antioxidant 1010,0.24g are added
Firebrake ZB after triphenyl phosphite, 0.81g ball milling dispersion process, synthesis under normal pressure
40min；
3) polycondensation reaction under vacuum condition is proceeded to, until power of agitator reaches rated value,
Terminate polycondensation reaction.Nitrogen extruding and discharging, Cast Strip, pelletizing.Composite flame-retardant PET
The growing amount of system is 811g, and intrinsic viscosity (dL/g) 0.582, P element quality contains
Amount (relative to pet polymer) 0.6wt%, ZB mass content is (relative to PET
Polymer) 0.1wt%.
Embodiment 4
1) 700g p-phthalic acid, 327g ethylene glycol and 0.32gSb are weighed2O3, put
In 2L polymeric kettle, heating pressurization, keep in temperature 230 DEG C, in be pressed in 0.3MPa,
Along with the carrying out of esterification, in still, pressure is gradually reduced, until normal pressure；
2) 34.2g fire retardant CEPPA, 0.24g antioxidant 1010,0.24g are added
Firebrake ZB after triphenyl phosphite, 1.62g ball milling dispersion process, synthesis under normal pressure
40min；
3) polycondensation reaction under vacuum condition is proceeded to, until power of agitator reaches rated value,
Terminate polycondensation reaction.Nitrogen extruding and discharging, Cast Strip, pelletizing.Composite flame-retardant PET
The growing amount of system is 812g, intrinsic viscosity (dL/g) 0.571, P element content (phase
For pet polymer) 0.6wt%, ZB content (relative to pet polymer) 0.2wt%.
Comparative example
Comparative example 1
1) 700g p-phthalic acid, 327g ethylene glycol and 0.32gSb are weighed2O3, put
In 2L polymeric kettle, heating pressurization, keep in temperature 230 DEG C, in be pressed in 0.3MPa,
Along with the carrying out of esterification, in still, pressure is gradually reduced, until normal pressure；
2) 0.24g antioxidant 1010,0.24g triphenyl phosphite, atmospheric reverse are added
Answer 40min；
3) polycondensation reaction under vacuum condition is proceeded to, until power of agitator reaches rated value,
Terminate polycondensation reaction.Nitrogen extruding and discharging, Cast Strip, pelletizing.The composite flame-proof obtained
The intrinsic viscosity (dL/g) 0.690 of type PET system, P element mass content is (relatively
In pet polymer) 0wt%, ZB mass content (relative to pet polymer) 0wt%.
Comparative example 2
1) 700g p-phthalic acid, 327g ethylene glycol and 0.32gSb are weighed2O3, put
In 2L polymeric kettle, heating pressurization, keep in temperature 230 DEG C, in be pressed in 0.3MPa,
Along with the carrying out of esterification, in still, pressure is gradually reduced, until normal pressure；
2) 0.24g antioxidant 1010,0.24g triphenyl phosphite, 0.405g are added
Firebrake ZB after ball milling dispersion process, synthesis under normal pressure 40min；
3) polycondensation reaction under vacuum condition is proceeded to, until power of agitator reaches rated value,
Terminate polycondensation reaction.Nitrogen extruding and discharging, Cast Strip, pelletizing.The composite flame-proof obtained
The intrinsic viscosity (dL/g) 0.605 of type 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 p-phthalic acid, 327g ethylene glycol and 0.32Sb are weighed2O3, put
In 2L polymeric kettle, heating pressurization, keep in temperature 230 DEG C, in be pressed in 0.3MPa,
Along with the carrying out of esterification, in still, pressure is gradually reduced, until normal pressure；
2) 0.24g antioxidant 1010,0.24g triphenyl phosphite, 0.81g are added
Firebrake ZB after ball milling dispersion process, synthesis under normal pressure 40min；
3) polycondensation reaction under vacuum condition is proceeded to, until power of agitator reaches rated value,
Terminate polycondensation reaction.Nitrogen extruding and discharging, Cast Strip, pelletizing.The composite flame-proof obtained
The intrinsic viscosity (dL/g) 0.572 of type 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 p-phthalic acid, 327g ethylene glycol and 0.32gSb are weighed2O3, put
In 2L polymeric kettle, heating pressurization, keep in temperature 230 DEG C, in be pressed in 0.3MPa,
Along with the carrying out of esterification, in still, pressure is gradually reduced, until normal pressure；
2) 0.24g antioxidant 1010,0.24g triphenyl phosphite, 1.62g are added
Firebrake ZB after ball milling dispersion process, synthesis under normal pressure 40min；
3) polycondensation reaction under vacuum condition is proceeded to, until power of agitator reaches rated value,
Terminate polycondensation reaction.Nitrogen extruding and discharging, Cast Strip, pelletizing.The composite flame-proof obtained
The intrinsic viscosity (dL/g) 0.580 of type PET system, P element mass content (relative to
Pet polymer) 0wt%, ZB mass content (relative to pet polymer) 0.2wt%.
Experimental example
The Seiko DSC-6200 type differential utilizing Seiko Instruments Inc. to produce is swept
Retouch calorimeter (DSC) and characterize the hot property of Flame-retardant PET；
Limited oxygen index (LOI): utilize the Dynisco that U.S. Dynisco Inc. produces
The LOI of type limited oxygen index analyser test sample, observes batten combustion process simultaneously
In molten drop situation.Batten a size of 80mm × 6.5mm × 3mm, at Haake
Prepare in MiniJet microspecimen injector.
Molten drop situation: use the CZF-3 type that analytical tool factory of Jiangning county produces
Level, the molten drop situation of vertical combustion instrument test sample, level clamping batten, holding
In the case of continuous flame, calculate the molten drop number (length of flame is 2cm) in 1min；And
The quality of metering drippage molten drop.Batten a size of 80mm × 6.5mm × 3mm, at Haake
Prepare in MiniJet micro sample injector.
Cone calorimetry test (CONE): use Britain Fire Testing
The standard cone calorimetry that Technology Ltd produces is tested.Sample size:
100mm×100mm×3mm.The standard formulated according to ISO5660, by the limit of sample
Edge and bottom are put in horizontal sample groove with aluminium foil parcel juxtaposition, and sample is at 35kw/m2Heat
It is heated by CONE under the conditions of radiant power and measures what analysis software obtained
The parameter such as burning time, HRR.
Surface topography: use the JSM-6030 type scanning electron microscope that NEC company produces
Observe the pattern of combustion degradation (keeping 30min at 450 DEG C) residue in Muffle furnace.
The hot property of experimental example 1 Flame-retardant PET
The product that embodiment 1-4 and comparative example 1-4 are prepared with carry out thermal performance test,
Result as it is shown in figure 1, wherein,
Curve 1 represents that comparative example 1 prepares the DSC curve of product；
Curve 2 represents that comparative example 2 prepares the DSC curve of product；
Curve 3 represents that comparative example 3 prepares the DSC curve of product；
Curve 4 represents that comparative example 4 prepares the DSC curve of product；
Curve 5 represents that embodiment 1 prepares the DSC curve of product；
Curve 6 represents that embodiment 2 prepares the DSC curve of product；
Curve 7 represents that embodiment 3 prepares the DSC curve of product；
Curve 8 represents that embodiment 4 prepares the DSC curve of product.
As shown in Figure 1, the addition of the ZB various thermal features parameters to PET, such as glass
Glass transition temperature (Tg), crystallization temperature (Tc) and melt temperature (Tm) etc.
Impact is not clearly.Because ZB deposits as just a kind of additive in system
, and interaction between polymer chain inconspicuous；And due to the copolymerization used
Type fire retardant CEPPA, the chemical reaction of generation can reduce the regular of PET macromolecular chain
Property, the crystallization to chain is unfavorable, and common manifestation is crystallization and the reduction of melting heat enthalpy.
The most on this basis, add ZB and also will not produce obvious structure influence.
Experimental example 2 limited oxygen index
The product that embodiment 1-4 and comparative example 1-4 prepare is carried out limited oxygen index survey
Fixed, result is as shown in table 1.In the experimentation of test oxygen index (OI), the most qualitative note
The ready visual contrast of record molten drop situation, the most mainly tester, the serious journey of molten drop situation
The increase of degree ☆ number is described, and number is the most, represents that molten drop situation is the most serious.
Table 1 limited oxygen index data
As can be seen from Table 1, compared with PET, adding mass fraction is the ZB of 0.05%,
Get final product the LOI of obvious raising PET system, from 23% to 27% so that it is reach resistance
The basic demand (general LOI i.e. can be described as flame-retardant polymer more than 26%) of combustion polymer；
But in test process, find still there is obvious molten drop phenomenon, when in PET, ZB contains
When amount increases to 0.2%, it is possible to find that the molten drip phenomenon of burning has weakened.The opposing party
Face, for adding the PET sample of phosphorus flame retardant, it is evident that only add resistance
Combustion agent (i.e. PET/P) can significantly improve the LOI (being 29%) of PET system equally, but
Melt drip phenomenon has degradating trend, this and the condensed phase fire retardant mechanism of phosphorus flame retardant
Relevant.Adding different amounts of ZB in PET/P system, its LOI is the most unchanged, dimension
Hold 29%, but the molten drop phenomenon of this fire-retardant PET system along with ZB addition and
Make moderate progress.
Experimental example 3 molten drop situation
The product that embodiment 1-4 and comparative example 1-4 prepare is carried out amount of molten drops and quality
Quantitative test, result is as shown in table 2.
Table 2 sample molten drop situation in combustion
As shown in Table 2, in comparative example 1-4, add the PET system of ZB and pure PET phase
Ratio, molten drop number is all reduced, and illustrates that the anti-dropping of Flame-retardant PET system is improved,
But average every drip melt drips the purer PET of quality all has increase, this is because ZB is to polymer
Carbonization have a certain promotion, increasing of carbonization amount is conducive to strengthening combustion front
Melt viscosity, thus extend the molten drop time of staying at batten combustion front, make to melt
Drip more difficult drippage.
After adding phosphorus flame retardant, the Flame-retardant PET system amount of molten drops obtained and gross weight
Amount all increases, and this is one of the approach that Phosphorous Flame-Retardant Polyester plays flame retardant effect, i.e. produces
Raw more molten drop, takes away PET combustion front by heat or flame.Same at PET/P
System is added ZB, along with the increase of ZB content, molten drop number and molten drop gross mass are equal
Reducing, this is relevant with ZB catalysis carbon-forming effect in PET combustion process.When in resistance
When adding the ZB of 0.2% in retardant polyester, amount of molten drops and gross mass all occur the most obvious
Weaken.
Therefore, in conjunction with limited oxygen index and molten drop situation two kinds test, it is believed that ZB
Can jointly improve the flame-retardant modified of PET, i.e. phosphorus flame retardant with phosphorus flame retardant to carry
The LOI of high PET, and ZB can improve remaining char amount in PET combustion process, jointly improves
The fire resistance of PET.
Experimental example 4 cone calorimetry is tested
Use the cone calorimetry of FTT company, be 35kw/m in radiant power2Condition
Under, measure ignitor firing time (TTI), HRR (HRR) and quality and damage
Stall rate (MLR)；Wherein pk-HRR, tpk-HRR, tpk-MLR refer to HRR respectively
Peak value, reach to the time required for peaking and mass loss rate peak value time
Between.Result is as shown in table 3.
Key data in the test of table 3 cone calorimetry
From comparative example 1-4, TTI, tpk-HRR and tpk-MLR of PET are respectively
79s, 136s and 126s.When add mass fraction 0.05% ZB after, PET system
TTI, tpk-HRR, tpk-MLR increase respectively to 88s, 142s and 130s.This combustion
The change of burning time parameter is on the one hand due to ZB decomposes, and the water of crystallization of release plays
Heat absorption cooling effect and the effect of dilution fuel gas；On the other hand, at high temperature ZB
Decompose and generate B2O3, it being attached on the surface of polymer form one layer of cover layer, this covers
Cap rock can suppress the generation of imflammable gas, it is possible to stops oxidation reaction and thermal decomposition to be made
With, delay or reduce the release of calory burning and polymer quality due to degraded
The speed of loss.In embodiment 1-4, at phosphorus flame retardant or ZB and phosphorous flame-retardant
In the presence of both agent are common, in taper calorimetric is tested, it is thus achieved that composite flame-proof PET
Increasing all occurs in each characteristic time parameter (TTI, tpk-HRR, tpk-MLR) of system
The trend added, illustrates ZB and the compounding use of phosphorus flame retardant, has more preferable fire-retardant effect
Really.
Experimental example 5 Flame-retardant PET degraded layer of charcoal pattern
Utilize scanning electron microscope (SEM) that embodiment 1,4 and comparative example 1,4 are prepared
The layer of charcoal produced after product combustion degradation is observed, shown in result as Fig. 2-Fig. 5.
Fig. 2 has after PET combustion degradation a large amount of bubble impression, and the most ruptures.PET
The Char Residues Structure formed after combustion degradation loosens, cause a large amount of fuel gas from hole and
Gap escapes, the burning of beneficially PET and degraded.After adding phosphorus flame retardant, as
Shown in Fig. 3, the bubble on layer of charcoal surface has reduced, and part bubble does not rupture, charcoal
Layer surface compact, the effusion to fuel gas has certain inhibitory action；According to LOI
Result shows, individually adds phosphorus flame retardant and refers to PET limit oxygen than being individually added into ZB
The raising of number becomes apparent from, and also has similar embodiment, such as Fig. 3 and Fig. 4 from layer of charcoal pattern
Shown in, i.e. the bubble more than PET/ZB-0.2 system one of PET/P diagram of system face closure
A bit, the lockedin air space burst size that certainly can reduce fuel gas；Add resistance simultaneously
After the PET system of combustion agent CEPPA and ZB is degraded in Muffle furnace, as it is shown in figure 5,
The layer of charcoal surface soundness arrived improves, and lockedin air space obvious increase, for PET body
Resistance to melt-dropping property and the smog burst size of system play an important role.
Above in association with detailed description of the invention and exemplary example, the present invention is carried out in detail
Illustrate, but these explanations can not be interpreted as limitation of the present invention.This area skill
Art personnel understand, without departing from the spirit and scope of the invention, and can be to this
Inventive technique scheme and embodiment thereof carry out multiple equivalencing, modify or improve,
These are within the scope of the present invention.Protection scope of the present invention is wanted with appended right
Ask and be as the criterion.
Claims (10)
1. a Composite flame-retardant polyethylene terephthalate system, its feature exists
In, including the component of following weight proportion:
Composite flame-retardant polyethylene terephthalate the most according to claim 1
Ester system, it is characterised in that described stabilizer selected from heat stabilizer, antioxidant or its
Combination.
Composite flame-retardant poly terephthalic acid second two the most according to claim 1 and 2
Alcohol ester system, it is characterised in that described phosphorous copoly type fire retardant is selected from 2-carboxyethyl
Phenyl hypophosphorous acid, dicarboxyethyl methyl phosphorodithioate, phosphorous acid two (4-carboxyl phenyl)
One or more in ester, tricresyl phosphate (4-carboxyl phenyl) ester, preferably 2-carboxyethyl
Phenyl hypophosphorous acid.
4. according to the Composite flame-retardant poly terephthalic acid one of claims 1 to 3 Suo Shu
Glycol ester system, it is characterised in that described fire retarding synergist selected from Firebrake ZB, three
Aoxidize two antimony, antimony pentoxide, metaborate, ferrum oxide, aluminium hydroxide, hydrogen-oxygen
Change one or more in magnesium, tripolycyanamide, such as antimony oxide and metaborate or
Firebrake ZB is compounding with tripolycyanamide to be used, and preferred boric acid zinc and antimony oxide compound and make
With.
5. according to the poly-terephthaldehyde of the Composite flame-retardant one of Claims 1-4 Suo Shu
Acid glycol ester system, it is characterised in that described fire retarding synergist is ground before using
Process, it is preferable that when Firebrake ZB and the compounding use of antimony oxide,
The particle diameter of Firebrake ZB is 0.5-5 μm, more preferably 0.7-3 μm；And/or
The particle diameter of antimony oxide is 0.5-1.0 μm, more preferably 0.6-0.8 μm.
6. according to the Composite flame-retardant poly terephthalic acid one of claim 1 to 5 Suo Shu
Glycol ester system, it is characterised in that
Described heat stabilizer is selected from ammonium phosphite, ammonium phosphate, ammonium dihydrogen phosphate, phosphoric acid
Trimethyl, dimethyl phosphate, triphenyl phosphate, diphenyl phosphate, phosphorous acid triphen
One or more in ester, diphenyl phosphite, preferably triphenyl phosphite；With/
Or
Described antioxidant is in antioxidant 1010, antioxidant 1076, antioxidant 1425
One or more, preferably antioxidant 1010；
Optionally, described heat stabilizer and the compounding use of antioxidant, it is preferable that phosphorous
Triphenyl phosphate ester and the compounding use of antioxidant 1010.
7. according to the poly-terephthaldehyde of the Composite flame-retardant one of claim 1 to 6 Suo Shu
Acid glycol ester system, it is characterised in that this Composite flame-retardant poly terephthalic acid second
Also including catalyst in diol ester system, described catalyst is selected from antimony oxide, second
One or more in glycol antimony and butyl titanate, preferably antimony oxide.
8. according to the poly-terephthaldehyde of the Composite flame-retardant one of claim 1 to 7 Suo Shu
The preparation method of acid glycol ester system, comprises the following steps:
Step 1), weigh by weight ratio p-phthalic acid, ethylene glycol, catalyst and
Part fire retarding synergist, is placed in reactor, pressurized, heated, insulation reaction；
Step 2), in above-mentioned reaction system, add the phosphorous copolymerization of specified weight proportioning
Type fire retardant, remainder fire retarding synergist and stabilizer, continue reaction under normal pressure；
Step 3), by step 2) compound proceed to carry out under vacuum condition polycondensation reaction,
Until reaching predetermined melt viscosity, terminate polycondensation reaction.
Composite flame-retardant polyethylene terephthalate the most according to claim 8
The preparation method of ester system, it is characterised in that
Step 1) in, reaction temperature is 210 DEG C-260 DEG C, preferably 220 DEG C-245 DEG C；
And/or
System pressure scope is 0.2MPa-0.4MPa, preferably 0.25-0.35MPa.
Composite flame-retardant poly terephthalic acid second the most according to claim 8 or claim 9
The preparation method of diol ester system, it is characterised in that
Step 2) in, synthesis under normal pressure time 30min-90min, preferably 40min-60min；
And/or
In described step 2, fire retarding synergist and fire retarding synergist in step 1 are identical fire-retardant
Synergist or different fire retarding synergist, be preferably different fire retarding synergist, more preferably walk
In rapid 1, fire retarding synergist is antimony oxide, and in step 2, fire retarding synergist is Firebrake ZB.
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| CN114671908A (en) * | 2022-04-22 | 2022-06-28 | 安徽大学 | Vanillyl flame-retardant plasticizer and preparation and application thereof |
| CN114957822A (en) * | 2022-05-23 | 2022-08-30 | 临沂沂光电缆有限公司 | Flame-retardant corrosion-resistant cable material and preparation method thereof |
| CN115160641A (en) * | 2021-04-02 | 2022-10-11 | 北京服装学院 | Preparation and application of flame-retardant polyester compound |
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| CN108383982A (en) * | 2018-01-23 | 2018-08-10 | 浙江省现代纺织工业研究院 | A kind of preparation method of hydridization ethylene glycol |
| CN111574698A (en) * | 2020-04-22 | 2020-08-25 | 浙江恒澜科技有限公司 | Organic microcapsule coated zinc borate in-situ polymerization flame-retardant smoke-suppression polyester and preparation method thereof |
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| CN114957822A (en) * | 2022-05-23 | 2022-08-30 | 临沂沂光电缆有限公司 | Flame-retardant corrosion-resistant cable material and preparation method thereof |
| CN114957822B (en) * | 2022-05-23 | 2023-04-14 | 临沂沂光电缆有限公司 | Flame-retardant corrosion-resistant cable material and preparation method thereof |
| CN114957822B8 (en) * | 2022-05-23 | 2023-05-23 | 临沂沂光电缆有限公司 | Flame-retardant corrosion-resistant cable material and preparation method thereof |
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