CN106947223B - Thermoplastic polyester elastomer fire-retardant combination and preparation method thereof - Google Patents
Thermoplastic polyester elastomer fire-retardant combination and preparation method thereof Download PDFInfo
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- CN106947223B CN106947223B CN201710259973.0A CN201710259973A CN106947223B CN 106947223 B CN106947223 B CN 106947223B CN 201710259973 A CN201710259973 A CN 201710259973A CN 106947223 B CN106947223 B CN 106947223B
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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
- 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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- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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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Abstract
The invention discloses a kind of thermoplastic polyester elastomer fire-retardant combinations, the composition includes thermoplastic polyester elastomer (TPEE) and unimolecule intumescent alkyl phosphinate fire retardant, in terms of the TPEE fire-retardant combination of 100 mass parts, unimolecule intumescent alkyl phosphinate is 10~40 mass parts, remaining is TPEE, and unimolecule intumescent alkyl phosphinate is the unimolecule intumescent alkylphosphinic acid metal salts for integrating acid source, carbon source, gas source.The invention also discloses the preparation methods of thermoplastic polyester elastomer fire-retardant combination.The present invention is re-dubbed composition using unimolecule intumescent alkyl phosphinate and TPEE, enhance the flame retardant property of TPEE in composition, when the additive amount of unimolecule intumescent alkyl phosphinate is mass parts 15~25, it can make the excellent flame retardancy of composition, vertical combustion grade reaches UL-94V-0 grades, does not need in addition to use nitrogenous synergist；In the structure of unimolecule intumescent alkyl phosphinate preferable compatibility can be generated with TPEE containing carboxylate structure.
Description
Technical field
The invention belongs to technical field of macromolecules, specifically a kind of thermoplastic polyester elastomer fire-retardant combination and its preparation
Method.
Background technique
Thermoplastic polyester elastomer (TPEE) is the linear multiblock of a kind of polyester hard section and aliphatic polyester or polyester soft segment
Copolymer, had both rubber elasticity and thermoplastic processable characteristic, be widely used in wire and cable, household electrical appliance,
The fields such as auto manufacturing, medical treatment.Flame retardant property as thermoplastic elastomer (TPE) an important indicator and be concerned, have it is excellent
The thermoplastic polyester elastomer of different flame retardant property is widely studied.In existing research have numerous studies be with halogenated flame retardant into
Row TPEE is flame-retardant modified, however its feature of environmental protection is poor, thus developing halogen-free flame retardants it is flame-retardant modified to carry out TPEE is inexorable trend, phosphorus
Flame retardant due to its low toxicity, low cigarette, flame retarding efficiency is high and is widely used in all kinds of synthetic materials, based on phosphorus flame retardant
The expansion type flame retardant for wanting component is a kind of composite flame-retardant agent that multielement cooperates with, the spy high with flame retarding efficiency, additive amount is few
Point, the flame retardance of polymer especially suitable for anaerobic or few oxygen are modified.
German Clariant company is dedicated to the research of this novel phosphorus flame retardant, finds phosphinates and with phosphinates
Based on fire retardant can be used for thermoplastic, such as PA (polyamide, polyamide), PBT (polybutylene
Terephthalate, polybutylene terephthalate (PBT)), fiber and textile it is fire-retardant, especially containing oxygen element and nitrogen member
There is excellent flame retardant property in the presence of the polymeric system of element.German patent DE-A-4430932 discloses dialkyl phosphinic acid
The preparation of alkali metal salt/thermoplastic polyester fire proofing, used in dialkylphosphinic salts be mainly diethyl phosphinic acids
Aluminium, when fire retardant additive amount is 30%, material has preferable flame retardant property.German patent DE-A-2447727 discloses benefit
With the metal alkyl phosphinates of Section II main group and Section III main group, Flameproof polyamide moulding article is prepared.In above-mentioned patent
In the fire-retardant polymerization system of alkyl phosphinate, need to add containing nitrogen compound as synergist, dialkylphosphinic salts are containing
Its fire retardation could be effectively played in the presence of nitrogen compound (such as melamine), these are containing nitrogen compound with individual group
Divide together with alkyl phosphinate, be added by way of blending, and additional amount is also bigger, these nitrogenous synergists are added
After be difficult to be uniformly dispersed, the poor compatibility with synthetic material and between fire retardant deteriorates the mechanical performance of material, fire-retardant effect
Rate can not give full play to, and furthermore also make troubles the process of composite material.
Summary of the invention
The object of the present invention is to provide a kind of thermoplastic polyester elastomer fire-retardant combinations, using the list for integrating three sources
Molecule intumescent alkyl phosphinate fire retardant is modified, the flame retardant property of the TPEE composition of the less compounding of fire retardant additive amount
Excellent, the vertical combustion grade for testing composition reaches V-0 grades of UL-94, and both fire retardant and polymer TPEE are compatible when compounding
Property is good.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of thermoplastic polyester elastomer fire-retardant combination,
The composition includes thermoplastic polyester elastomer (TPEE) and unimolecule intumescent alkyl phosphinate fire retardant, with 100 matter
The TPEE fire-retardant combination meter of part is measured, the unimolecule intumescent alkyl phosphinate is 10~40 mass parts.
Specifically, the unimolecule intumescent alkyl phosphinate is 1,3,5- tri- (2- ethoxy) isocyanuric acid ester methyl
The combination of one or more of six ester phosphinates of three ester phosphinates of propionic acid or hexamethylolmelamine methylpropanoic acid,
In, the three ester phosphinic acids of unimolecule intumescent alkyl phosphinate 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid
Salt, the structure with general formula I:
The six ester phosphinates of unimolecule intumescent alkyl phosphinate hexamethylolmelamine methylpropanoic acid, has
The structure of general formula II:
In general formula I and general formula II, M is the metal Be, Mg, Ca, Sr of the second main group in the periodic table of elements, the gold of third main group
Belong to Al, Ga, In, Ge, Sn, the Pb of the 4th main group, As, Sb, the Bi of the 5th main group, or Ti, V, Cr, Fe, Co, Ni, the Cu of subgroup,
Zn,Y,Zr,Nb,Mo,Tc,Ru,Rh,Pd,Ag,Cd；M for metal be in ionic condition when it is electrically charged.
Preferably, the unimolecule intumescent alkyl phosphinate is 1,3,5- tri- (2- ethoxy) isocyanuric acid ester methyl
Three ester phosphinic acids aluminium of propionic acid/magnesium/zinc/calcium, one in six ester phosphinic acids aluminium of hexamethylolmelamine methylpropanoic acid/magnesium/zinc/calcium
Kind or several combinations.
Further, the partial size of the unimolecule intumescent alkyl phosphinate is 5~10 μm.
Preferably, unimolecule intumescent alkyl phosphinate additive amount is 15~25 parts in the composition.
A kind of preparation method based on above-mentioned thermoplastic polyester elastomer fire-retardant combination, comprising the following steps:
1) it pre-processes: unimolecule intumescent alkyl phosphinate is dried；By thermoplastic polyester elastomer into
Row is dried；It is 5~10 μm that unimolecule intumescent alkyl phosphinate, which is ground to partial size with high speed ball mill,；
2) mixing granulation: mixing mass ratio is the unimolecule intumescent alkyl phosphinate of 10:90~40:60 at room temperature
With thermoplastic polyester elastomer, continue to be uniformly mixed simultaneously extruding pelletization in double screw extruder.
Further, the drying process in the step 1) refer to temperature be 70~100 DEG C, vacuum drying time be 3~
24h。
Further, at 200~240 DEG C, revolving speed is for each area's temperature control of the double screw extruder in the step 2)
40~100 revs/min.
Preferably, the preparation method of the thermoplastic polyester elastomer fire-retardant combination is by 1,3,5- tri- (2- ethoxy)
Three ester phosphinic acids aluminium of chlorinated isocyanurates methylpropanoic acid is dried at 80 DEG C；Thermoplastic polyester elastomer is carried out at 80 DEG C
It is dried；Three ester phosphinic acids aluminium of 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid is ground to high speed ball mill
Partial size is 5~10 μm；At room temperature by three ester phosphinic acids aluminium of 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid and heat
Plasticity polyester elastomer with mass ratio be 15:85 mixing, continue in double screw extruder be uniformly mixed and at 220 DEG C, with 60
Rev/min revolving speed extruding pelletization be made thermoplastic polyester elastomer fire-retardant combination.
Preferably, the preparation method of the thermoplastic polyester elastomer fire-retardant combination is by hexamethylolmelamine first
Six ester phosphinic acids aluminium of base propionic acid is dried at 100 DEG C；Thermoplastic polyester elastomer is dried at 100 DEG C；
It is 5~10 μm that six ester phosphinic acids aluminium of hexamethylolmelamine methylpropanoic acid, which is ground to partial size with high speed ball mill,；In room temperature
It is lower by three ester phosphinic acids aluminium of 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid and thermoplastic polyester elastomer with quality
Than for 20:80 mixing, continue in double screw extruder be uniformly mixed and at 240 DEG C, with 100 revs/min of revolving speed extruding pelletization
Thermoplastic polyester elastomer fire-retardant combination is made.
1) present invention is re-dubbed composition using unimolecule intumescent alkyl phosphinate and TPEE, enhance in composition
The flame retardant property of TPEE, when the addition mass parts of unimolecule intumescent alkyl phosphinate are at 15~25 parts, so that it may make to combine
The excellent flame retardancy of object, the vertical combustion grade for testing composition reach V-0 grades of UL-94；2) unimolecule intumescent alkyl
Preferable compatibility can be generated with TPEE containing carboxylate structure in the structure of phosphonate, mechanical performance will not severe exacerbation；3)
It can be realized expandable flame retardant containing acid source, carbon source, gas source in unimolecule intumescent alkyl phosphinate molecular structure, do not need to make
With nitrogenous synergist.
Specific embodiment
Below with reference to preferred embodiment, invention is further described in detail, convenient for more clearly understanding this
Invention, but the present invention is not limited to following specific embodiments.
Concrete operating principle of the invention are as follows: TPEE and unimolecule intumescent alkyl phosphinate fire retardant compounded combination
Afterwards, if meet fiery temperature more than burning is started after critical value, in three sources in unimolecule intumescent alkyl phosphinate fire retardant
Carbon containing more structure charcoal is dehydrated under the catalytic action of methyl-prop acidic group phosphinic acids and metal ion, and containing N structure point
Solution be bulk gas percussion under, layer of charcoal formed bulk multi-hole structure, prevent heat in the base further release and
Diffusion, moreover it is possible to which blocking oxygen slows down fire spreading of the TPEE after kindling.
The unimolecule intumescent alkyl phosphinate fire retardant used in the present invention, general structure indicate are as follows:
Molecular structure is in star, and n corresponds to the hydroxyl and number of amino groups of nitrogenous polyol, and M is the gold that chemical valence is m
Category or semimetal.The preparation method for the unimolecule intumescent alkyl phosphinate fire retardant that the present invention uses, comprising the following steps:
1) it hydrolyzes relieving haperacidity: 2- methyl -2,5- dioxy -1,2- oxygen phospholane being hydrolyzed to obtain methyl-prop acidic group time phosphine
Acid；Solvent when hydrolysis is using water or the mixed liquor of acetone or water and acetone；The temperature of hydrolysis is 40~100 DEG C,
Reaction time is 0.5~3h；
2) esterification or esterification and amidation process: by methyl-prop acidic group phosphinic acids and nitrogenous polyol
Esterification or esterification and amidation process are carried out, nitrogenous ester-containing alkyl phosphinic acid is obtained；It is wherein nitrogenous polyhydroxylated
Closing object is that hydroxy number is at least one of two compound, wherein nitrogen moiety can be amino or other nitrogenous bases
Group；Nitrogenous polyol can be 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates, trishydroxymethylaminomethane, trihydroxy methyl
Nitromethane, 2- amino-2-methyl -1,3 propylene glycol, triisopropanolamine, triethanolamine, one in hexamethylolmelamine
Kind, preferably 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates or hexamethylolmelamine；The solvent of reaction can for hexamethylene,
One of toluene, dimethylbenzene, benzene；The temperature of esterification is 100~160 DEG C, and reaction time of esterification is 2~8h；
3) it adjusts pH: at normal temperature, NaOH solution is added dropwise to pH=7.0 in nitrogenous ester-containing alkyl phosphinic acid solution,
Obtain nitrogenous ester-containing alkyl phosphinic acid sodium salt solution；
4) metal is at salt: nitrogenous ester-containing alkyl phosphinic acid sodium salt solution being heated to 60~100 DEG C, metal salt is added
Aqueous solution is stirred at reflux 2~4 hours, obtains unimolecule intumescent alkyl phosphinate fire retardant；Metal salt is water-soluble
Metal salt, is the second main group Be, Mg, Ca, Sr in the periodic table of elements, Al, Ga, the In of third main group, Ge, the Sn of the 4th main group,
Pb, the As of the 5th main group, Sb, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, the Pd of Bi or subgroup,
The metal water soluble salt of Ag, Cd, preferably Al, Mg, Zn, Ca.
A kind of preparation method of thermoplastic polyester elastomer fire-retardant combination of the present invention, comprising the following steps:
1) it pre-processes: by unimolecule intumescent alkyl phosphinate and thermoplastic polyester elastomer respectively at 70~100 DEG C
Carry out vacuum drying treatment, vacuum drying time be 3~for 24 hours；By unimolecule intumescent alkyl phosphinate high speed ball mill
Being ground to partial size is 5~10 μm；Wherein unimolecule intumescent alkyl phosphinate can be 1,3,5- tri- (2- ethoxy) isocyanide
Three ester phosphinic acids aluminium of urate methylpropanoic acid/magnesium/calcium/zinc, six ester phosphinic acids aluminium of hexamethylolmelamine methylpropanoic acid/magnesium/
The combination of one or more of calcium/zinc.
2) mixing granulation: mixing mass ratio is the unimolecule intumescent alkyl phosphinate of 10:90~40:60 at room temperature
With thermoplastic polyester elastomer, continue to be uniformly mixed in double screw extruder and controlled at 200~240 DEG C, revolving speed is
40~100 revs/min of extruding pelletizations.
Embodiment 1
By three ester of unimolecule intumescent alkyl phosphinate 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid
Phosphonic acids aluminium, thermoplastic polyester elastomer are dried in vacuo 8 hours at 80 DEG C respectively, and it is stand-by to place room temperature；By (the 2- hydroxyl of 1,3,5- tri-
Ethyl) chlorinated isocyanurates methylpropanoic acid three ester phosphinic acids aluminium with high speed ball mill be milled to 5~10 μm；Take 85.0g thermoplastic poly
Three ester phosphinic acids aluminium of ester elastomer (TPEE) and 15.0g 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid, in room
With it is uniformly mixed under temperature, using double screw extruder, each area's temperature control at 220 DEG C, with 60 turns/
By the composition extruding pelletization under the revolving speed divided, composition 1 is obtained；
Obtained thermoplastic polyester elastomer fire-retardant combination 1 uses GB/T2406-2008 " Plastics Combustion performance test
Method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " come assess characterization,
After tested, which is 28.2, and vertical combustion grade reaches V-0 grades of UL-94.
Embodiment 2
By three ester of unimolecule intumescent alkyl phosphinate 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid
Phosphonic acids magnesium, thermoplastic polyester elastomer are dried in vacuo 12 hours at 70 DEG C respectively, and it is stand-by to place room temperature；By tri- (2- of 1,3,5-
Ethoxy) chlorinated isocyanurates methylpropanoic acid three ester phosphinic acids magnesium with high speed ball mill be milled to 5~10 μm；Take 75.0g thermoplasticity
Three ester phosphinic acids magnesium of polyester elastomer (TPEE) and 25.0g 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid,
It was uniformly mixed it with mechanical stirring 5 minutes at room temperature, using double screw extruder, each area's temperature control is at 230 DEG C, with 80
Rev/min revolving speed under by the composition extruding pelletization, obtain composition 2；
Obtained thermoplastic polyester elastomer fire-retardant combination 2 uses GB/T2406-2008 " Plastics Combustion performance test
Method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " come assess characterization,
After tested, which is 26.4, and vertical combustion grade reaches V-0 grades of UL-94.
Embodiment 3
By three ester of unimolecule intumescent alkyl phosphinate 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid
Zinc phosphonate, thermoplastic polyester elastomer are dried in vacuo 6 hours at 90 DEG C respectively, and it is stand-by to place room temperature；By (the 2- hydroxyl of 1,3,5- tri-
Ethyl) chlorinated isocyanurates methylpropanoic acid three ester phosphinic acids zinc with high speed ball mill be milled to 5~10 μm；Take 70.0g thermoplastic poly
Three ester phosphinic acids zinc of ester elastomer (TPEE) and 30.0g 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid, in room
With it is uniformly mixed under temperature, using double screw extruder, each area's temperature control at 210 DEG C, with 40 turns/
By the composition extruding pelletization under the revolving speed divided, composition 3 is obtained；
Obtained thermoplastic polyester elastomer fire-retardant combination 3 uses GB/T2406-2008 " Plastics Combustion performance test
Method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " come assess characterization,
After tested, which is 29.3, and vertical combustion grade reaches V-0 grades of UL-94.
Embodiment 4
By three ester of unimolecule intumescent alkyl phosphinate 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid
Phosphonic acids calcium, thermoplastic polyester elastomer are dried in vacuo 3 hours at 100 DEG C respectively, and it is stand-by to place room temperature；By tri- (2- of 1,3,5-
Ethoxy) chlorinated isocyanurates methylpropanoic acid three ester phosphinic acids calcium with high speed ball mill be milled to 5~10 μm；Take 65.0g thermoplasticity
Three ester phosphinic acids calcium of polyester elastomer (TPEE) and 35.0g 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid,
It was uniformly mixed it with mechanical stirring 5 minutes at room temperature, using double screw extruder, each area's temperature control is at 200 DEG C, with 50
Rev/min revolving speed under by the composition extruding pelletization, obtain composition 4；
Obtained thermoplastic polyester elastomer fire-retardant combination 4 uses GB/T2406-2008 " Plastics Combustion performance test
Method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " come assess characterization,
After tested, which is 27.4, and vertical combustion grade reaches V-0 grades of UL-94.
Embodiment 5
By six ester phosphinic acids aluminium of unimolecule intumescent alkyl phosphinate hexamethylolmelamine methylpropanoic acid, thermoplasticity
Polyester elastomer is dried in vacuo 3 hours at 100 DEG C respectively, and it is stand-by to place room temperature；By hexamethylolmelamine methylpropanoic acid
Six ester phosphinic acids aluminium are milled to 5~10 μm with high speed ball mill；Take 80.0g thermoplastic polyester elastomer (TPEE) and 20.0g six
Six ester phosphinic acids aluminium of melamine methylol methylpropanoic acid was uniformly mixed it with mechanical stirring 5 minutes at room temperature, using double
Screw extruder, each area's temperature control is at 240 DEG C, by the composition extruding pelletization, to be combined under 100 revs/min of revolving speed
Object 5；
Obtained thermoplastic polyester elastomer fire-retardant combination 5 uses GB/T2406-2008 " Plastics Combustion performance test
Method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " come assess characterization,
After tested, which is 30.2, and vertical combustion grade reaches V-0 grades of UL-94.
Embodiment 6
By six ester phosphinic acids magnesium of unimolecule intumescent alkyl phosphinate hexamethylolmelamine methylpropanoic acid, thermoplasticity
Polyester elastomer is dried in vacuo 24 hours at 70 DEG C respectively, and it is stand-by to place room temperature；By hexamethylolmelamine methylpropanoic acid
Six ester phosphinic acids magnesium are milled to 5~10 μm with high speed ball mill；Take 75.0g thermoplastic polyester elastomer (TPEE) and 25.0g six
Six ester phosphinic acids magnesium of melamine methylol methylpropanoic acid was uniformly mixed it with mechanical stirring 5 minutes at room temperature, using double
Screw extruder, each area's temperature control is at 220 DEG C, by the composition extruding pelletization, to obtain composition under 70 revs/min of revolving speed
6；
Obtained thermoplastic polyester elastomer fire-retardant combination 6 uses GB/T2406-2008 " Plastics Combustion performance test
Method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " come assess characterization,
After tested, which is 25.8, and vertical combustion grade reaches V-0 grades of UL-94.
Embodiment 7
By six ester phosphinic acids zinc of unimolecule intumescent alkyl phosphinate hexamethylolmelamine methylpropanoic acid, thermoplasticity
Polyester elastomer is dried in vacuo 24 hours at 70 DEG C respectively, and it is stand-by to place room temperature；By hexamethylolmelamine methylpropanoic acid
Six ester phosphinic acids zinc are milled to 5~10 μm with high speed ball mill；Take 70.0g thermoplastic polyester elastomer (TPEE) and 30.0g six
Six ester phosphinic acids zinc of melamine methylol methylpropanoic acid was uniformly mixed it with mechanical stirring 5 minutes at room temperature, using double
Screw extruder, each area's temperature control is at 220 DEG C, by the composition extruding pelletization, to obtain composition under 70 revs/min of revolving speed
7；
Obtained thermoplastic polyester elastomer fire-retardant combination 7 uses GB/T2406-2008 " Plastics Combustion performance test
Method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " come assess characterization,
After tested, which is 28.6, and vertical combustion grade reaches V-0 grades of UL-94.
Embodiment 8
By six ester phosphinic acids calcium of unimolecule intumescent alkyl phosphinate hexamethylolmelamine methylpropanoic acid, thermoplasticity
Polyester elastomer is dried in vacuo 24 hours at 70 DEG C respectively, and it is stand-by to place room temperature；By hexamethylolmelamine methylpropanoic acid
Six ester phosphinic acids calcium are milled to 5~10 μm with high speed ball mill；Take 65.0g thermoplastic polyester elastomer (TPEE) and 35.0g six
Six ester phosphinic acids calcium of melamine methylol methylpropanoic acid was uniformly mixed it with mechanical stirring 5 minutes at room temperature, using double
Screw extruder, each area's temperature control is at 220 DEG C, by the composition extruding pelletization, to obtain composition under 70 revs/min of revolving speed
8；
Obtained thermoplastic polyester elastomer fire-retardant combination 8 uses GB/T2406-2008 " Plastics Combustion performance test
Method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " come assess characterization,
After tested, which is 26.2, and vertical combustion grade reaches V-0 grades of UL-94.
Embodiment 9
By six ester phosphinic acids aluminium of unimolecule intumescent alkyl phosphinate hexamethylolmelamine methylpropanoic acid and six hydroxyls
Vacuum drying 24 is small at 70 DEG C respectively for six ester phosphinic acids calcium of methyl melamine methylpropanoic acid and thermoplastic polyester elastomer
When, it is stand-by to place room temperature；By six ester phosphinic acids aluminium of hexamethylolmelamine methylpropanoic acid and hexamethylolmelamine methyl
Six ester phosphinic acids calcium of propionic acid is milled to 5-10 μm with high speed ball mill respectively；75.0g thermoplastic polyester elastomer (TPEE) is taken,
Six ester of six ester phosphinic acids aluminium of 10.0g hexamethylolmelamine methylpropanoic acid and 15.0g hexamethylolmelamine methylpropanoic acid
Phosphinic acids calcium was uniformly mixed it with mechanical stirring 5 minutes at room temperature, and using double screw extruder, each area's temperature control exists
230 DEG C, by the composition extruding pelletization, to obtain composition 9 under 50 revs/min of revolving speed；
Obtained thermoplastic polyester elastomer fire-retardant combination 9 uses GB/T2406-2008 " Plastics Combustion performance test
Method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " come assess characterization,
After tested, which is 29.3, and vertical combustion grade reaches V-0 grades of UL-94.
Embodiment 10
By three ester of unimolecule intumescent alkyl phosphinate 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid
Phosphonic acids aluminium and 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid, three ester phosphinic acids zinc and thermoplastic polyester elastomer
It is dried in vacuo 24 hours at 70 DEG C respectively, it is stand-by to place room temperature；By 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methyl-prop
Sour three ester phosphinic acids aluminium and 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid, three ester phosphinic acids zinc use clipping the ball respectively
Grinding machine is milled to 5-10 μm；It takes 75.0g thermoplastic polyester elastomer (TPEE), 15.0g1,3,5- tri- (2- ethoxy) isocyanides urine
Three ester phosphinic acids aluminium of acid esters methylpropanoic acid and 10.0g 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid three ester time phosphine
Sour zinc was uniformly mixed it with mechanical stirring 5 minutes at room temperature, and using double screw extruder, each area's temperature control is 240
DEG C, by the composition extruding pelletization, to obtain composition 10 under 40 revs/min of revolving speed；
Obtained thermoplastic polyester elastomer fire-retardant combination 10 is using GB/T2406-2008 " Plastics Combustion performance examination
Proved recipe method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " assess table
Sign, after tested, the composite material limit oxygen index are 31.5, and vertical combustion grade reaches V-0 grades of UL-94.
Embodiment 11
By three ester of unimolecule intumescent alkyl phosphinate 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid
Phosphonic acids aluminium and six ester phosphinic acids zinc of hexamethylolmelamine methylpropanoic acid and thermoplastic polyester elastomer are respectively at 70 DEG C
It is stand-by to place room temperature for vacuum drying 24 hours；By 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid, three ester phosphinic acids
Aluminium and six ester phosphinic acids zinc of hexamethylolmelamine methylpropanoic acid are milled to 5-10 μm with high speed ball mill respectively；Take 75.0g
Thermoplastic polyester elastomer (TPEE), 15.0g, 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid, three ester phosphinic acids aluminium
With six ester phosphinic acids zinc of 10.0g hexamethylolmelamine methylpropanoic acid, kept its mixing equal with mechanical stirring 5 minutes at room temperature
It is even, using double screw extruder, the control of each area's temperature at 220 DEG C, under 70 revs/min of revolving speed by the composition extruding pelletization,
Obtain composition 11；
Obtained thermoplastic polyester elastomer fire-retardant combination 11 is using GB/T2406-2008 " Plastics Combustion performance examination
Proved recipe method-oxygen index method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " assess table
Sign, after tested, the composite material limit oxygen index are 28.9, and vertical combustion grade reaches V-0 grades of UL-94.
Comparative example 1
Thermoplastic polyester elastomer is dried in vacuo 8 hours at 80 DEG C, it is stand-by to place room temperature；Take thermoplastic polyester elastomer
Body (TPEE) 100.0g, using double screw extruder, the control of each area's temperature at 220 DEG C, under 60 revs/min of revolving speed by thermoplasticity
Polyester elastomer extruding pelletization is not added the thermoplastic polyester elastomer of unimolecule intumescent alkyl phosphinate；
Obtained thermoplastic polyester elastomer uses GB/T2406-2008 " Plastics Combustion method for testing performance-oxygen index (OI)
Method " and GB/T 2408-2008 " measurement of Plastics Combustion performance: Horizontal Bridgman Method and normal beam technique " assess characterization, after tested, this is multiple
Condensation material limit oxygen index be 16.2, vertical combustion grade without.
The test of the flame retardant property of thermoplastic polyester elastomer fire-retardant combination and comparative example 1 obtained by embodiment 1~11
As a result summarize as shown in rear table 1.
Table 1
Embodiment 1~11 shows that unimolecule intumescent alkyl phosphinate used in the present composition can be 1,
3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid, three ester phosphinic acids aluminium/magnesium/calcium/zinc, hexamethylolmelamine methyl
One or more of combinations, is not added with compared to comparative example 1 fire-retardant as shown in Table 1 in six ester phosphinic acids aluminium of propionic acid/magnesium/calcium/zinc
The flame retardant property test of the TPEE of agent, TPEE fire-retardant combination has passed through the V0 grade of UL-94, adds especially in TPEE a small amount of
Three ester phosphinic acids aluminium of 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid or hexamethylolmelamine methylpropanoic acid
Six ester phosphinic acids aluminium, that is, can reach excellent flame retardant property.
It is and existing in conclusion the fire retardant in composition provided by the invention is a kind of novel efficient halogen-free anti-inflaming agent
The structure of some dialkyl phosphinic acids, dialkyl phosphinic acid ester and dialkyl metal phosphinate based flame retardant is different, due to
Introduced in alkyl it is nitrogenous and containing ester group, it can be achieved that unimolecule expandable flame retardant, and additive amount is few, flame retarding efficiency is high.
In addition, thermoplastic polyester elastomer (TPEE) fire-retardant combination of the invention during the preparation process, can be according to difference
Different additives is targetedly added in fire-retardant combination and is modified for purposes, such as inorganic or organic filler.
Unspecified content is the prior art known to a person of ordinary skill in the art in this specification.
Above-described specific embodiment is only schematical, and used technical term is limited in the present invention
Qualifier is only for convenience of description of the invention, and those skilled in the art are at fire-retardant group of thermoplastic polyester elastomer of the present invention
Under the enlightenment for closing object and preparation method thereof, without breaking away from the scope protected by the purposes and claims of the present invention, may be used also
Many forms are derived, these are within the scope of the present invention.
Claims (9)
1. a kind of thermoplastic polyester elastomer fire-retardant combination, it is characterised in that: the composition includes thermoplastic polyester elastomer
Body (TPEE) and unimolecule intumescent alkyl phosphinate fire retardant, in terms of the TPEE fire-retardant combination of 100 mass parts, institute
Stating unimolecule intumescent alkyl phosphinate is 10~40 mass parts, and the unimolecule intumescent alkyl phosphinate is 1,3,5-
Three (2- ethoxy) chlorinated isocyanurates methylpropanoic acids, three ester phosphinates or hexamethylolmelamine methylpropanoic acid six ester time phosphine
The combination of one or more of hydrochlorate, wherein the unimolecule intumescent alkyl phosphinate is 1,3,5- tri- (2- hydroxyl second
Base) chlorinated isocyanurates methylpropanoic acid three ester phosphinates general structure I are as follows:
The general formula II of the six ester phosphinates of hexamethylolmelamine methylpropanoic acid are as follows:
In general structure I and general formula II, M is the metal Be, Mg, Ca, Sr of the second main group in the periodic table of elements, third main group
Metal Al, Ga, In, Ge, Sn, the Pb of the 4th main group, the Bi of the 5th main group, or Ti, V, Cr, Fe, Co, Ni, the Cu of subgroup,
Zn,Y,Zr,Nb,Mo,Tc,Ru,Rh,Pd,Ag,Cd；M for metal be in ionic condition when it is electrically charged.
2. thermoplastic polyester elastomer fire-retardant combination according to claim 1, it is characterised in that: the unimolecule expansion
Type alkyl phosphinate is three ester phosphinic acids aluminium of 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid/magnesium/calcium/zinc or six
The combination of one or more of six ester phosphinic acids aluminium of melamine methylol methylpropanoic acid/magnesium/calcium/zinc.
3. thermoplastic polyester elastomer fire-retardant combination according to claim 2, it is characterised in that: the unimolecule expansion
The partial size of type alkyl phosphinate is 5~10 μm.
4. thermoplastic polyester elastomer fire-retardant combination according to claim 1, it is characterised in that: single in the composition
Molecule intumescent alkyl phosphinate additive amount is 15~25 parts.
5. a kind of preparation method of thermoplastic polyester elastomer fire-retardant combination, which comprises the following steps:
1) it pre-processes: unimolecule intumescent alkyl phosphinate is dried；Thermoplastic polyester elastomer is done
Dry processing；It is 5~10 μm that unimolecule intumescent alkyl phosphinate, which is ground to partial size with high speed ball mill,；
2) mixing granulation: the unimolecule intumescent alkyl phosphinate and heat that mixing mass ratio is 10:90~40:60 at room temperature
Plasticity polyester elastomer continues to be uniformly mixed in double screw extruder simultaneously extruding pelletization；Wherein, the unimolecule intumescent alkane
Base phosphinates be in thermoplastic polyester elastomer fire-retardant combination as described in any one of claim 1,2,3,4 used in
Unimolecule intumescent alkyl phosphinate.
6. the preparation method of thermoplastic polyester elastomer fire-retardant combination according to claim 5, it is characterised in that: described
Drying process in step 1) refer to temperature be 70~100 DEG C, vacuum drying time be 3~for 24 hours.
7. the preparation method of thermoplastic polyester elastomer fire-retardant combination according to claim 5, it is characterised in that: described
At 200~240 DEG C, revolving speed is 40~100 revs/min for each area's temperature control of double screw extruder in step 2).
8. the preparation method of thermoplastic polyester elastomer fire-retardant combination according to any one of claim 5~7, special
Sign is: three ester phosphinic acids aluminium of 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid is dried at 80 DEG C；
Thermoplastic polyester elastomer is dried at 80 DEG C；By 1,3,5- tri- (2- ethoxy) chlorinated isocyanurates methylpropanoic acid three
It is 5~10 μm that ester phosphinic acids aluminium, which is ground to partial size with high speed ball mill,；(2- ethoxy) isocyanide of 1,3,5- tri- is urinated at room temperature
Three ester phosphinic acids aluminium of acid esters methylpropanoic acid is that 15:85 is mixed with mass ratio with thermoplastic polyester elastomer, in double screw extruder
In continue be uniformly mixed and at 220 DEG C, with 60 revs/min of revolving speed extruding pelletization be made thermoplastic polyester elastomer flame retardant combination
Object.
9. the preparation method of thermoplastic polyester elastomer fire-retardant combination according to any one of claim 5~7, special
Sign is: six ester phosphinic acids aluminium of hexamethylolmelamine methylpropanoic acid is dried at 100 DEG C；By thermoplastic polyester
Elastomer is dried at 100 DEG C；By six ester phosphinic acids aluminium high speed ball mill of hexamethylolmelamine methylpropanoic acid
Being ground to partial size is 5~10 μm；At room temperature by six ester phosphinic acids aluminium of hexamethylolmelamine methylpropanoic acid and thermoplastic poly
Ester elastomer with mass ratio be 20:80 mixing, continue in double screw extruder be uniformly mixed and at 240 DEG C, with 100 revs/min
Revolving speed extruding pelletization be made thermoplastic polyester elastomer fire-retardant combination.
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