CN107057300B - A kind of halogen-free flame retardants and the high molecular material using the halogen-free flame retardants - Google Patents
A kind of halogen-free flame retardants and the high molecular material using the halogen-free flame retardants Download PDFInfo
- Publication number
- CN107057300B CN107057300B CN201710276667.8A CN201710276667A CN107057300B CN 107057300 B CN107057300 B CN 107057300B CN 201710276667 A CN201710276667 A CN 201710276667A CN 107057300 B CN107057300 B CN 107057300B
- Authority
- CN
- China
- Prior art keywords
- halogen
- free flame
- polymer material
- retardant polymer
- pentaerythrite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
This application discloses a kind of halogen-free flame retardants, which is characterized in that contains component A and component B in the halogen-free flame retardants；The component A is selected from least one of the compound with chemical formula shown in Formulas I, the compound with chemical formula shown in Formula II；The component B is selected from least one of the phosphite ester of pentaerythrite, the phosphate of pentaerythrite, the carboxylate of pentaerythrite.The halogen-free flame retardants overcomes the dialkylphosphinic salts disadvantage low to engineering plastics flame retarding efficiency, and the thermal stability of dialkylphosphinic salts synergist in the prior art is not high, flame retarding efficiency is poor, narrow application range, will appear the shortcomings that reduction processing and physical property.
Description
Technical field
This application involves the high molecular materials of a kind of halogen-free flame retardants and the application halogen-free flame retardants, belong to flame-retardant high-molecular
Field of material preparation.
Background technique
Fire-resistant engineering plastics especially glass-fiber-reinforced polyamide, polyester PBT and high-temperature nylon etc. are widely used in electronics
With the receptacle in electrical apparatus industry, connector, the manufacture of the miniature electrics component such as relay.The traditionally resistance of engineering plastics
Combustion is realized by bromide fire retardant, but bromide fire retardant can generate strong carcinogenic dioxin when burning, produce simultaneously
Raw hydrogen bromide can cause secondary pollution again, therefore the use of bromide fire retardant recent years is gradually restricted.Engineering plastic
Fire-retardant thus turn to of material uses halogen-free flame retardants, and especially dialkylphosphinic salts class is widely used.But dioxane
The flame retardant effect of base phosphinates itself is limited, needs to cooperate with use together with other fire retardants.
For example, United States Patent (USP) US6207736 reports dialkylphosphinic salts and ammonium polyphosphate synergetic flame-retardant engineering plastics,
But ammonium polyphosphate non-melt influences the dispersibility of fire retardant, and its thermal stability is not high, is not able to satisfy polyamide and polyester
The high temperature process requirement of equal engineering plastics.
United States Patent (USP) US6255371 reports dialkylphosphinic salts and melamine polyphosphate cooperative flame retardant glass increases
Strong polyamide and polyester, but melamine polyphosphate non-melt, influence the dispersibility of fire retardant, and be easy to cause screw rod
Extrusion blocking.
United States Patent (USP) US6547992 reports dialkylphosphinic salts, melamine derivative and inorganic compound example
Such as zinc stannate cooperative flame retardant fiber glass reinforced polyamide and polyester.
To overcome the shortcomings of existing synergist, a large amount of new collaboration system is suggested.For example United States Patent (USP) US9481831 is mentioned
Synergist to aluminium phosphite as dialkylphosphinic salts, U.S. Patent application US20050113496 propose that phenolic resin is made
For flame retardancy synergists, using in polyamide, U.S. Patent application US2011237695 reports poly phosphonate ester as dialkyl group
Phosphinates synergist, using in polyester elastomer, U.S. Patent application US2013210968 proposition use phosphonitrile class as
Synergist, using on polyester material.
Although existing scheme improves the flame retardant property of dialkylphosphinic salts using flame retardancy synergists, in some spy
Determine collaboration system used in high molecular material and is not necessarily suitable other high molecular materials or these cooperative flame retardant systems
Cause the processing performance or physical property decline of fire proofing.Develop low-resistance and fire additive amount, is conducive to the processing of material, and
The fire-retardant collaboration system for being able to maintain the good physical property of material is still highly desirable to.
Summary of the invention
According to the one aspect of the application, a kind of halogen-free flame retardants is provided, to overcome dialkylphosphinic salts to engineering plastic
Expect the low disadvantage of flame retarding efficiency, and the thermal stability of dialkylphosphinic salts synergist in the prior art is not high, flame retarding efficiency
Difference, narrow application range will appear the shortcomings that reduction processing and physical property.
The halogen-free flame retardants, which is characterized in that contain component A and component B in the halogen-free flame retardants；
The component A is in the compound with chemical formula shown in Formulas I, the compound with chemical formula shown in Formula II
It is at least one:
In Formulas I, R1、R2Independently selected from C1~C20One of alkyl；
Mm+Metal ion is represented, m is the valence state of metal ion；
In Formula II, R3、R4Independently selected from C1~C20One of alkyl；Q is selected from C1~C20Alkylene in one
Kind；
Ln+Metal ion is represented, n is the valence state of metal ion；
Phosphite ester of the component B selected from pentaerythrite, the phosphate of pentaerythrite, in the carboxylate of pentaerythrite
It is at least one.Component B has good thermal stability, and some of them can be used as antioxidant simultaneously in high molecular material.
Preferably, in Formulas I, R1、R2Independently selected from C1~C8Alkyl, C7~C20Aralkyl, C6~C12Aryl, C7
~C20One of alkaryl.
Preferably, in Formula II, R3、R4Independently selected from C1~C8Alkyl, C7~C20Aralkyl, C6~C12Aryl,
C7~C20One of alkaryl.
Preferably, in Formula II, Q is selected from C1~C10Alkylidene, C7~C20Sub- aralkyl, C6~C12Arlydene, C7
~C20Alkarylene, C7~C20One of alkyl-aryl-group subunit.
Those skilled in the art can select the ratio of component A and component B in halogen-free flame retardants according to specific material.It is preferred that
Ground, the weight ratio of component B and component A is B:A=0.030~0.44:1 in halogen-free flame retardants.It is further preferred that Halogen hinders
The weight ratio for firing component B and component A in agent is B:A=0.045~0.35:1.
Preferably, the M in Formulas Im+, L in Formula IIn+Independently selected from divalent metal, trivalent metal cation
At least one.It is further preferred that Mm+、Ln+Independently selected from Mg2+、Ca2+、Ba2+、Fe2+、Fe3+、Al3+、Zn2+In at least
It is a kind of.
Preferably, the component A be selected from diethyl phosphinates, Methylethyl phosphinates, ethyl-butyl phosphinates,
At least one of diphenyl phosphonic acid salt, methylphenylphosphinic acid salt.It is further preferred that the component A is selected from diethyl
Phosphinic acids aluminium, diethyl phosphinic acids zinc, Methylethyl phosphinic acids aluminium, Methylethyl phosphinic acids zinc, ethyl-butyl phosphinic acids aluminium, two
At least one of aluminum phenylphosphinate, methylphenylphosphinic acid aluminium.
Preferably, the phosphite ester of the pentaerythrite is selected from one of the compound with chemical formula shown in formula III:
In formula III, R5、R6、R7、R8、R9、R5’、R6’、R7’、R8’、R9' independently selected from hydrogen, alkyl, aralkyl, aryl,
One of alkaryl.
It is further preferred that in formula III, R5、R6、R7、R8、R9、R5’、R6’、R7’、R8’、R9' independently selected from hydrogen, C1~
C8Alkyl, C7~C20Aralkyl, C6~C12Aryl, C7~C20One of alkaryl.
It is further preferred that the phosphite ester of the pentaerythrite is selected from bis- (2,4- di-tert-butyl-phenyl) pentaerythrites
Diphosphites (can be abbreviated as antioxidant 626), two (bis- p-isopropyl phenyl of 2,4-) pentaerythritol bis-phosphites (can be write a Chinese character in simplified form
For antioxidant 852), at least one of double octadecyl pentaerythritol diphosphites (antioxidant 618 can be abbreviated as).
Preferably, penta 4 alcohol phosphate is selected from one of the compound with chemical formula shown in formula IV:
In formula IV, R10、R11、R12、R13、R14、R10’、R11’、R12’、R13’、R14' independently selected from hydrogen, alkyl, aralkyl,
One of aryl, alkaryl.
It is further preferred that in formula IV, R10、R11、R12、R13、R14、R10’、R11’、R12’、R13’、R14' independently selected from
Hydrogen, C1~C8Alkyl, C7~C20Aralkyl, C6~C12Aryl, C7~C20One of alkaryl.
It is further preferred that the phosphate of the pentaerythrite is selected from bis- (2,4- di-tert-butyl-phenyl) pentaerythrites two
Phosphate, bis- (2,6- 3,5-dimethylphenyl) pentaerythritol diphosphates, bis- (2- tert-butyl-phenyl) pentaerythritol diphosphates, it is double
Phenyl pentaerythritol diphosphate, double octadecyl pentaerythritol diphosphates, two (bis- p-isopropyl phenyl of 2,4-) Ji Wusi
At least one of alcohol biphosphonate.
Preferably, the carboxylate of the pentaerythrite is selected from one of the compound with chemical formula described in Formula V:
In Formula V, R15、R16、R17、R18Independently selected from one of hydrogen, alkyl, aralkyl, aryl, alkaryl.
It is further preferred that in Formula V, R15、R16、R17、R18Independently selected from hydrogen, C1~C8Alkyl, C7~C20Aralkyl
Base, C6~C12Aryl, C7~C20One of alkaryl.
It is further preferred that the carboxylate of the pentaerythrite is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl)
Propionic acid] pentaerythritol ester, pentaerythritol tetrabenzoate, four tricaprylate of pentaerythrite, pentaerythritol tetrastearate, season penta
At least one of four oleate of tetrol, pentaerythrite and formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid
At least one of esterification products of carboxylic acid.
According to the another aspect of the application, a kind of halogen-free flame-retardant polymer material is provided, which is characterized in that contain above-mentioned
At least one of meaning halogen-free flame retardants.
Preferably, the component A in the halogen-free flame retardants is on the weight percentage in halogen-free flame-retardant polymer material
Limit be selected from 25wt%, 23wt%, 22wt%, 20wt%, 18wt%, 16wt%, 15wt%, lower limit be selected from 14wt%, 12wt%,
10wt%, 8wt%.It is further preferred that weight of the component A in halogen-free flame-retardant polymer material in the halogen-free flame retardants
Percentage composition is 8wt%~25wt%.It is further preferred that the component A in the halogen-free flame retardants is in halogen-free flameproof high score
Weight percentage in sub- material is 10wt%~20wt%.
Preferably, the component B in the halogen-free flame retardants is on the weight percentage in halogen-free flame-retardant polymer material
Limit be selected from 3.5wt%, 3.2wt%, 3wt%, 2.8wt%, 2.5wt%, 2.2wt%, 2wt%, lower limit be selected from 1.2wt%,
1wt%, 0.9wt%, 0.8wt%, 0.7wt%, 0.75wt%.In general the dosage of component B is halogen-free flame-retardant polymer material
0.75wt%~3.5wt% weight percent of material, optimal dosage depend on the specific knot of high molecular material and component B
Structure.From open source literature it is found that pentaerythritol phosphite is also commonly used for antioxidant, but as antioxidant in use, component B
Dosage is the 0.5% of material total weight or hereinafter, component B is used not as other purposes at this time.Present inventor is studying
In the process, by largely testing, be surprised to find when the dosage of component B reach 0.75% or more of total material weight when
It waits, component B presents good fire-retardant synergistic effect to dialkylphosphinic salts.Further study show that when the use of component B
Amount is higher than after the 4% of total material weight, since the phosphite ester, phosphate or carboxylate of pentaerythrite have soffening,
Lead to the generation of burning molten drop, or causes the burning of UL-94 test absorbent cotton, thus cooperative flame retardant effect declines.Therefore, institute
Stating weight percentage of the component B in halogen-free flame-retardant polymer material in halogen-free flame retardants is 0.75wt%~3.5wt%.
It is further preferred that weight percentage of the component B in halogen-free flame-retardant polymer material in the halogen-free flame retardants is
0.9wt%~3.5wt%.Again it is further preferred that the component B in the halogen-free flame retardants is in halogen-free flame-retardant polymer material
In weight percentage be 1wt%~3wt%.
Macromolecule refers to as numerous atoms or atomic group mainly with molecular weight made of Covalent bonding together 10,000 or more
Compound.It includes polyethylene, polypropylene, polystyrene, high impact polystyrene, acrylonitrile-butadiene-styrene (ABS) copolymerization
Object, Maranyl, Fypro, polyester plastics, polyester fiber, polycarbonate etc..
Preferably, the high molecular material in the halogen-free flame-retardant polymer material in thermoplastic macromolecule material extremely
Few one kind.The thermal plastic high polymer refers to the plastics with heating and softening, hardening by cooling characteristic.
It is further preferred that the high molecular material in the halogen-free flame-retardant polymer material is selected from polyamide macromolecule material
At least one of material, polyester macromolecule material.
Polyamide is also referred to as polyamide fibre or nylon, is the high molecular general name for containing-NH-C (O)-amide group in its structural unit,
Pass through one or more dicarboxylic acids and one or more diamines and/or one or more amino acid, and/or one kind
Or a variety of lactams condensations or ring-opening reaction synthesize.Polyester is high molecular containing-C (O)-O- ester linkage group in its structural unit
General name.It can be formed by polyacid and polyol condensating reaction preparation or by polyalcohol and polyester progress ester exchange reaction.
It is further preferred that high molecular material in the halogen-free flame-retardant polymer material be selected from polyethylene, polypropylene,
Polystyrene, high impact polystyrene, acrylonitrile-butadiene-styrene copolymer, polybutylene terephthalate, poly- carbonic acid
At least one of ester, polyamide.
As an implementation, in the halogen-free flame-retardant polymer material include reinforcing agent, anti-dripping agent, stabilizer,
At least one of pigment, dyestuff, char forming catalyst, fire retardant, dispersing agent, nucleating agent, antioxidant, inorganic filler.
Optionally, the reinforcing agent is glass fibre.
Optionally, the anti-dripping agent is Teflon Teflon.
Optionally, inorganic filler is selected from least one of micarex, calcium carbonate, calcium oxide, silica.
Those skilled in the art according to specific needs, select halogen-free flame-retardant polymer material in high molecular material and
Other additives (reinforcing agent, anti-dripping agent, stabilizer, pigment, dyestuff, char forming catalyst, fire retardant, dispersing agent, nucleating agent,
At least one of antioxidant, inorganic filler) dosage.The sum of all components weight percent in halogen-free flame-retardant polymer material
For 100wt%.
In the application, C1~C8、C6~C12、C7~C20Etc. the carbon atom number for referring both to group and being included.
In the application, " alkyl " is to be formed by group by losing any one hydrogen atom on alkane compound molecule.It is " sub-
Alkyl " is to be formed by group by losing any two hydrogen atom on alkane compound molecule.The alkane compound includes straight
Alkane, branched paraffin, cycloalkane, the cycloalkane with branch.
In the application, " aryl " is to lose a hydrogen atom on aromatic rings on aromatic compounds molecule to be formed by base
Group；Phenyl is formed by as lost any one hydrogen atom on phenyl ring.
In the application, " arlydene " is to lose two hydrogen atoms on aromatic rings on aromatic compound molecule to be formed by base
Group, such as:
In the application, " alkaryl " refers on aryl, at least one hydrogen atom is replaced by alkyl on aromatic rings is formed by base
Group.Replaced the p-methylphenyl to be formed by methyl as aligned hydrogen atom on phenyl.
In the application, " aralkyl " refers on alkyl that at least one hydrogen atom is substituted with aryl and is formed by group.Such as methyl
On a hydrogen atom be substituted by phenyl the benzyl to be formed.
In the application, " alkyl " is to be formed by group by losing any one hydrogen atom on hydrocarbon molecules.Hydrocarbon
Base includes alkyl, aryl, containing alkaryl, aralkyl, further include other contain double bond and/or three key by C, H-shaped at group
Deng.
In the application, " alkylene " is to be formed by group by losing any two hydrogen atom on hydrocarbon molecules,
Including alkylidene, arlydene, sub- aralkyl, alkarylene, alkyl-aryl-group subunit etc..
In the application, " sub- aralkyl " refers to that the hydrogen atom lost on any one non-aromatic ring on " aralkyl " is formed by
Group such as loses the group formed to a hydrogen atom on methyl to methylbenzyl:
In the application, " alkarylene " refers to that the hydrogen atom lost on any one aromatic rings on " alkaryl " is formed by base
Group, as p-methylphenyl loses the group that a hydrogen atom is formed on phenyl ring:
In the application, " alkyl-aryl-group subunit " refers to the hydrogen atom institute shape lost on any one aromatic rings on " aralkyl "
At group, such as:
The beneficial effect of the application includes but is not limited to:
1) halogen-free flame retardants provided herein, high to engineering plastics flame retarding efficiency, the heat of halogen-free flame retardants itself is steady
It is qualitative high, applied widely, small on the processing performance of high molecular material and physical property influence.
2) halogen-free flame-retardant polymer material provided herein, good flame retardation effect, processing performance and good physical performance.
Specific embodiment
The feature that the features described above or embodiment that the application mentions are mentioned can be in any combination.Disclosed in this case specification
All features can be used in combination with any composition form, each feature disclosed in specification, can by it is any provide it is identical,
The alternative characteristics of impartial or similar purpose replace.Therefore except there is special instruction, revealed feature is only impartial or similar spy
The general example of sign.
Below with reference to embodiment, the present invention is further explained.It should be understood that these embodiments be merely to illustrate the present invention without
For limiting the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition or
According to the normal condition proposed by manufacturer.
PA66-A (also known as polyamide 66 or nylon66 fiber): Dupont Zytel 70G30L NC010, wherein glass fibre
Content is 30wt%.
PA66-B (also known as polyamide 66 or nylon66 fiber): Dupont Zytel 70G35L NC010, wherein glass fibre
Content is 35wt%.
PA6 (also known as polyamide 6 or nylon 6): Dupont Zytel 73G30L NC010, wherein content of glass fiber be
30wt%.
PBT (also known as polybutylene terephthalate): Dupont Crastin SK605NC010, content of glass fiber are
30% weight percent.
DePAl-1: aluminum diethylphosphinate, the Zhejiang chemical inc development of evil in febrile disease Hua Yang.
DePAl-2: aluminum diethylphosphinate, German Clariant CorporationOP1230。
Antioxidant 1010: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, Sa grace chemical technology
(Shanghai) Co., Ltd..
Antioxidant 626: bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, the limited public affairs of Zhengzhou Alpha's chemical industry
Department.
Irgasfos 168: three [2,4- di-tert-butyl-phenyl] phosphite esters, Strem company, the U.S..
PTB: pentaerythritol tetrabenzoate, Tokyo Chemical Industry Co., Ltd.
Compound antioxidant: antioxidant 1010 (four [β-(3,5- di-tert-butyl-hydroxy phenyl propionic acid] pentaerythritol ester) with
Irgasfos 168 (three [2,4- di-tert-butyl-phenyl] phosphite esters) is with the mixing of 1:1 weight ratio.
In embodiment and comparative example, the flame retardant property of sample is surveyed according to the method in GB/T 2408-2008 standard
Fixed, the measurement of plastic tensile performance is measured according to method in GB/T1040.1-2006, and the measurement of plastics bending property is according to GB/
Method measures in T9341-2000.
In embodiment, using on III type magnetic resonance tool of Bruker 400MHz AVANCE to products obtained therefrom in embodiment into
Row31P-NMR characterization.Phosphorus stave levies condition as hydrogen decoupling, and pre- extension D1=10 seconds, scanning times were greater than 16 times, solvent C DCl3,
Positioning standard specimen is done using 85% phosphoric acid.
The synthesis of bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphates of embodiment 1
Bis- (2, the 4- di-tert-butyl-phenyl) pentaerythritol diphosphites of 60g (0.099mol) are dissolved in 550g toluene,
It is stirred at room temperature to whole dissolutions, is then cooled to 10 DEG C, 67.5g (0.595mol) hydrogen peroxide is added dropwise thereto in 30min
System, is warmed to room temperature by (30% mass fraction) after dripping off, the reaction was continued 7.5h.Revolving is washed with 100g isopropanol and 40g acetone
It washs, filters, wash, drying obtains bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphate 54g, yield 86%.
31P-NMR (85%H3PO4=0ppm): -13.5ppm.
Embodiment 2
By polyester PBT, antioxidant 626, DePAl-1 and compound antioxidant according to the weight ratio of 83.6:1:15:0.4,
It is mixed in the mixer that revolving speed is 50 revs/min, setting temperature is 260 DEG C, is taken out after five minutes cooling, dry.Then by it
It is filled in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.It is cut after its cooling
Sample, test.The fire-retardant rank of 1.6mm sample is UL94 V-0.
Embodiment 3
By polyester PBT, antioxidant 626, DePAl-1 and compound antioxidant according to the weight ratio of 83.6:2:14:0.4,
It is mixed in the mixer that revolving speed is 50 revs/min, setting temperature is 260 DEG C, is taken out after five minutes cooling, dry.Then by it
It is filled in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.It is cut after its cooling
Sample, test.The fire-retardant rank of 1.6mm sample is UL94 V-0.
Embodiment 4
By polyester PBT, antioxidant 626, DePAl-1 and compound flame retardant according to the weight of 83.85:0.75:15:0.4
Ratio mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes cooling, dry.So
After be filled in mold, 260 DEG C vulcanizing presses preheat 10 minutes, 10MPa pressure maintaining after five minutes, cold pressing.It is cold to its
But sample, test are cut afterwards.The fire-retardant rank of 1.6mm sample is UL94 V-0.
Embodiment 5
By polyester PBT, antioxidant 1010, DePAl-1 and compound antioxidant according to the weight ratio of 83.6:2:14:0.4
Example mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes cooling, dry.Then
It is filled in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.To its cooling
After cut sample, test.The fire-retardant rank of 1.6mm sample is UL94 V-0.
Embodiment 6
By polyester PBT, pentaerythritol tetrabenzoate, DePAl-1 and compound antioxidant according to 82.6:2:15:0.4's
Weight ratio mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes cooling, dry
It is dry.Then it is filled in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.
Sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample is UL94 V-0.
Embodiment 7
By polyester PBT, pentaerythritol tetrabenzoate, DePAl-1 and compound antioxidant according to 81.6:3:15:0.4's
Weight ratio mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes cooling, dry
It is dry.Then it is filled in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.
Sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample is UL94 V-0.
Embodiment 8
By polyamide PA6, antioxidant 626, DePAl-1 and compound antioxidant according to the weight ratio of 81.6:2:16:0.4
Example mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes cooling, dry.Then
It is filled in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.To its cooling
After cut sample, test.The fire-retardant rank of 1.6mm sample is UL94 V-0.
Embodiment 9
By polyamide PA66-B (35%GF), antioxidant 626, DePAl-1 and compound antioxidant according to 81.6:2:16:
0.4 weight ratio mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 280 DEG C, takes out after five minutes cold
But, dry.Then be filled in mold, 280 DEG C vulcanizing presses preheat 10 minutes, 10MPa pressure maintaining after five minutes,
Cold pressing.Sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample is UL94 V-0.
Embodiment 10
By polyamide PA66-A (30%GF), the product of embodiment 1, DePAl-2 and compound antioxidant according to 84.6:1:
The weight ratio of 14:0.4 mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 280 DEG C, takes out after five minutes
It is cooling, dry.Then it is filled in mold, is preheated 10 minutes, 10MPa pressure maintaining 5 minutes in 280 DEG C of vulcanizing presses
Afterwards, it is cold-pressed.Sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample is UL94 V-0.
Embodiment 11
By polyamide PA66-A (30%GF), antioxidant 626, DePAl-1 and compound antioxidant according to 75.6:2:22:
0.4 weight ratio mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 280 DEG C, takes out after five minutes cold
But, dry.Then be filled in mold, 280 DEG C vulcanizing presses preheat 10 minutes, 10MPa pressure maintaining after five minutes,
Cold pressing.Sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample is UL94 V-0.
Comparative example 1
It is 50 in revolving speed by polyester PBT, DePAl-1 and compound antioxidant according to the weight ratio of 83.6:16:0.4
Rev/min mixer in mix, setting temperature is 260 DEG C, is taken out after five minutes cooling, dry.Then it is filled in mold
In, it is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.Sample, test are cut after its cooling.
The fire-retardant rank of 1.6mm sample is UL94 V-1.
Comparative example 2
By polyester PBT, antioxidant 626, DePAl-1 and compound antioxidant according to the weight ratio of 84.1:0.5:15:0.4
Example mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes cooling, dry.Then
It is filled in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.To its cooling
After cut sample, test.The fire-retardant rank of 1.6mm sample is UL94 V-1.
Comparative example 3
By polyester PBT, antioxidant 626, DePAl-1 and compound antioxidant according to the weight ratio of 81.6:4:14:0.4,
It is mixed in the mixer that revolving speed is 50 revs/min, setting temperature is 260 DEG C, is taken out after five minutes cooling, dry.Then by it
It is filled in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.It is cut after its cooling
Sample, test.The fire-retardant rank of 1.6mm sample is UL94 V-1.
Comparative example 4
By polyester PBT, antioxidant 1010, DePAl-1 and compound antioxidant according to the weight ratio of 85.1:0.5:14:0.4
Example mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes cooling, dry.Then
It is filled in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.To its cooling
After cut sample, test.The fire-retardant rank of 1.6mm sample is UL94 V-1.
Comparative example 5
By polyester PBT, antioxidant 1010, DePAl-1 and compound antioxidant according to the weight ratio of 81.6:4:14:0.4
Example mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes cooling, dry.Then
It is filled in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.To its cooling
After cut sample, test.The fire-retardant rank of 1.6mm sample is UL94 V-2.
Comparative example 6
By polyester PBT, pentaerythritol tetrabenzoate (PTB), DePAl-1 and compound antioxidant according to 84.1:0.5:
The weight ratio of 15:0.4 mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes
It is cooling, dry.Then it is filled in mold, is preheated 10 minutes, 10MPa pressure maintaining 5 minutes in 260 DEG C of vulcanizing presses
Afterwards, it is cold-pressed.Sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample is UL94 V-1.
Comparative example 7
By polyester PBT, pentaerythritol tetrabenzoate (PTB), DePAl-1 and compound antioxidant according to 82.6:5:12:
0.4 weight ratio mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes cold
But, dry.Then be filled in mold, 260 DEG C vulcanizing presses preheat 10 minutes, 10MPa pressure maintaining after five minutes,
Cold pressing.Sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample is UL94 V-2.
Comparative example 8
It is 50 in revolving speed by polyamide PA6, DePAl-1 and compound antioxidant according to the weight ratio of 79.6:20:0.4
Rev/min mixer in mix, setting temperature is 260 DEG C, is taken out after five minutes cooling, dry.Then it is filled in mold
In, it is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.Sample, test are cut after its cooling.
The fire-retardant rank of 1.6mm sample is UL94 without rank.
Comparative example 9
By polyamide PA6, antioxidant 626, DePAl-1 and compound antioxidant according to 83.1:0.5:16:0.4 weight
Ratio mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 260 DEG C, takes out after five minutes cooling, dry.So
After be filled in mold, 260 DEG C vulcanizing presses preheat 10 minutes, 10MPa pressure maintaining after five minutes, cold pressing.It is cold to its
But sample, test are cut afterwards.The fire-retardant rank of 1.6mm sample is UL94 without rank.
Comparative example 10
By polyamide PA66-A (30%GF), DePAl-1 and compound antioxidant according to the weight ratio of 69.6:30:0.4
Example mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 280 DEG C, takes out after five minutes cooling, dry.Then
It is filled in mold, is preheated 10 minutes in 280 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.To its cooling
After cut sample, test.The fire-retardant rank of 1.6mm sample is no rank.
Comparative example 11
By polyamide PA66-B (35%GF), antioxidant 626, DePAl-2 and compound antioxidant according to 83.1:0.5:
The weight ratio of 16:0.4 mixes in the mixer that revolving speed is 50 revs/min, and setting temperature is 280 DEG C, takes out after five minutes
It is cooling, dry.Then it is filled in mold, is preheated 10 minutes, 10MPa pressure maintaining 5 minutes in 280 DEG C of vulcanizing presses
Afterwards, it is cold-pressed.Sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample is UL94 without rank.
Comparative example 12
By polyamide PA66-A, the product of embodiment 1, DePAl-2 and compound antioxidant according to 85.1:0.5:14:0.4
Weight ratio, be to be mixed in 50 revs/min of mixer in revolving speed, setting temperature is 280 DEG C, is taken out after five minutes cooling, dry
It is dry.Then it is filled in mold, is preheated 10 minutes in 280 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.
Sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample is no rank.
Comparative example 13
By polyamide PA66-B, DePAl-1 and compound antioxidant according to the weight ratio of 84.6:15:0.4, in revolving speed
To mix in 50 revs/min of mixers, setting temperature is 280 DEG C, is taken out after five minutes cooling, dry.Then be filled in
It in mold, is preheated 10 minutes in 280 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.Sample is cut after its cooling, is surveyed
Examination.The fire-retardant rank of 1.6mm sample is no rank.
It is the composition of halogen-free flame-retardant polymer material described in each embodiment and comparative example and flame retardant test result in table 1.
From table 1, the data in comparing embodiment 2 to 11 and comparative example 1 to 12 be can be seen that using the fire-retardant of technical scheme
Agent provides outstanding flame retardant property in suitable range to high molecular material.
Table 1
Embodiment 12
Respectively to the drawing of gained sample in embodiment 2, comparative example 1, embodiment 8, comparative example 8, embodiment 9 and comparative example 13
It stretches performance and bending property is measured, acquired results are as shown in table 2.
Table 2
For embodiment compared to respective comparative example, physical property is close it can be seen from 2 data of table, and in tensile elasticity
It increases in modulus and tensile stress, illustrates the addition of synergist of the present invention, not only increase the anti-flammability of high molecular material
Can, and maintain the original physical property of material.
It is upper described, it is only several embodiments of the application, any type of limitation not is done to the application, although the application
It is disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not departing from
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification be equal to it is equivalent
Case study on implementation belongs in technical proposal scope.
Claims (16)
1. a kind of halogen-free flame-retardant polymer material, which is characterized in that contain
1) high molecular material；
2) weight percentage is the component A of 8wt%~25wt%,
The component A in the compound with chemical formula shown in Formulas I, the compound with chemical formula shown in Formula II at least
It is a kind of:
In Formulas I, R1, R2 are independently selected from C1~C20One of alkyl；
Mm+Metal ion is represented, m is the valence state of metal ion；
In Formula II, R3, R4 are independently selected from C1~C20One of alkyl；Q is selected from C1~C20One of alkylene；
Ln+Metal ion is represented, n is the valence state of metal ion；
3) weight percentage be 0.75wt%~3.5wt% component B, wherein component B be selected from pentaerythrite phosphite ester,
At least one of the phosphate of pentaerythrite, carboxylate of pentaerythrite.
2. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that the component A is in halogen-free flameproof height
Weight percentage in molecular material is 10wt%~20wt%.
3. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that the component B is in halogen-free flameproof height
Weight percentage in molecular material is 0.9wt%~3.5wt%.
4. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that the component B is in halogen-free flameproof height
Weight percentage in molecular material is 1wt%~3wt%.
5. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that the component A is selected from diethyl
Phosphonate, Methylethyl phosphinates, ethyl-butyl phosphinates, diphenyl phosphonic acid salt, in methylphenylphosphinic acid salt
It is at least one.
6. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that component A is selected from diethyl phosphinic acids
Aluminium, diethyl phosphinic acids zinc, Methylethyl phosphinic acids aluminium, Methylethyl phosphinic acids zinc, ethyl-butyl phosphinic acids aluminium, diphenyl time
At least one of phosphonic acids aluminium, methylphenylphosphinic acid aluminium.
7. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that the phosphite ester of the pentaerythrite
Selected from one of the compound with chemical formula shown in formula III:
In formula III, R5、R6、R7、R8、R9、R5’、R6’、R7’、R8’、R9' independently selected from one of hydrogen, alkyl or aralkyl；
The phosphate of the pentaerythrite is selected from one of the compound with chemical formula shown in formula IV:
In formula IV, R10、R11、R12、R13、R14、R10’、R11’、R12’、R13’、R14' independently selected from hydrogen, alkyl or aralkyl
It is a kind of；
The carboxylate of the pentaerythrite is selected from one of the compound with chemical formula described in Formula V:
In Formula V, R15、R16、R17、R18Independently selected from one of hydrogen, alkyl, aralkyl, alkaryl.
8. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that the phosphite ester of the pentaerythrite
It is double sub- selected from bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, two (bis- p-isopropyl phenyl of 2,4-) pentaerythrites
At least one of phosphate, double octadecyl pentaerythritol diphosphites；
The phosphate of the pentaerythrite is selected from bis- (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphates, bis- (2,6- diformazans
Base phenyl) pentaerythritol diphosphate, bis- (2- tert-butyl-phenyl) pentaerythritol diphosphates, double phenyl pentaerythrite diphosphonic acid
Ester, double octadecyl pentaerythritol diphosphates, in two (bis- p-isopropyl phenyl of 2,4-) pentaerythrite diphosphate esters at least
It is a kind of；
The carboxylate of the pentaerythrite is selected from four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, season
Penta tetrol, four benzoic ether, four tricaprylate of pentaerythrite, pentaerythritol tetrastearate, pentaerythritol tetraoleate, season penta
In the esterification products of tetrol and at least one of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, octanoic acid, n-nonanoic acid carboxylic acid
At least one.
9. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that the halogen-free flame-retardant polymer material
In high molecular material be selected from least one of thermoplastic macromolecule material.
10. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that the halogen-free flame-retardant polymer material
High molecular material in material is selected from least one of polyamide high molecular material, polyester macromolecule material.
11. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that the halogen-free flame-retardant polymer material
High molecular material in material is selected from polyethylene, polypropylene, polystyrene, high impact polystyrene, acrylonitrile-butadiene-benzene second
At least one of alkene copolymer, polybutylene terephthalate, polycarbonate, polyamide.
12. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that the halogen-free flame-retardant polymer material
It include reinforcing agent, anti-dripping agent, stabilizer, pigment, dyestuff, char forming catalyst, fire retardant, dispersing agent, nucleating agent, antioxygen in material
One of agent, inorganic filler are a variety of.
13. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that group in the halogen-free flame retardants
The weight ratio for dividing B and component A is B:A=0.030~0.44:1.
14. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that group in the halogen-free flame retardants
The weight ratio for dividing B and component A is B:A=0.045~0.35:1.
15. halogen-free flame-retardant polymer material according to claim 1, which is characterized in that Mm+、Ln+Independently selected from divalent gold
Belong at least one of cation, trivalent metal cation.
16. halogen-free flame-retardant polymer material according to claim 13, which is characterized in that Mm+、Ln+Independently selected from Mg2+、
Ca2+、Ba2+、Fe2+、Fe3+、Al3+、Zn2+At least one of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710276667.8A CN107057300B (en) | 2017-04-25 | 2017-04-25 | A kind of halogen-free flame retardants and the high molecular material using the halogen-free flame retardants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710276667.8A CN107057300B (en) | 2017-04-25 | 2017-04-25 | A kind of halogen-free flame retardants and the high molecular material using the halogen-free flame retardants |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107057300A CN107057300A (en) | 2017-08-18 |
| CN107057300B true CN107057300B (en) | 2019-07-09 |
Family
ID=59604079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710276667.8A Active CN107057300B (en) | 2017-04-25 | 2017-04-25 | A kind of halogen-free flame retardants and the high molecular material using the halogen-free flame retardants |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107057300B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705566B (en) * | 2017-10-26 | 2021-11-19 | 中国石油化工股份有限公司 | Flame-retardant nylon 6 composition and expanded beads thereof |
| CN109265743B (en) * | 2018-09-07 | 2020-03-17 | 中国科学院宁波材料技术与工程研究所 | Flame retardant, composite flame retardant and flame-retardant polymer material containing composite flame retardant |
| US11299621B2 (en) * | 2018-12-18 | 2022-04-12 | Toray Plastics (America), Inc. | Anti-blush and chemical resistant polyester film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911485A (en) * | 2012-10-24 | 2013-02-06 | 华南理工大学 | Flame-retardant chain-extended polybutylene terephthalate composition and preparation method thereof |
| CN103897385A (en) * | 2014-03-21 | 2014-07-02 | 华南理工大学 | Flame-retardant chain-extending nylon 6 composition and preparation method thereof |
-
2017
- 2017-04-25 CN CN201710276667.8A patent/CN107057300B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911485A (en) * | 2012-10-24 | 2013-02-06 | 华南理工大学 | Flame-retardant chain-extended polybutylene terephthalate composition and preparation method thereof |
| CN103897385A (en) * | 2014-03-21 | 2014-07-02 | 华南理工大学 | Flame-retardant chain-extending nylon 6 composition and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107057300A (en) | 2017-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6113295B2 (en) | Phosphorus-containing flame retardant | |
| TWI410453B (en) | Flame retardant compositions containing mixtures of disubstituted phosphinate salts and monosubstituted phosphinate salts | |
| WO2018014443A1 (en) | Halogen-free phosphorus-containing silicon flame retardant, flame retardant transparent polycarbonate material, and preparation and use thereof | |
| CN102834458B (en) | Flame-retardant polylactide resin composition, molded object made therefrom, and manufacturing method therefor | |
| CN103168071B (en) | Flame-retardant polyester compounds | |
| CN107057300B (en) | A kind of halogen-free flame retardants and the high molecular material using the halogen-free flame retardants | |
| JP2001513839A (en) | Flame retardant polymer molding compound | |
| WO2007108202A1 (en) | Flame retardant polyamide resin composition and molding | |
| WO2006039299A1 (en) | Halogen-free flame retardant polyester | |
| CN105085984B (en) | A kind of halogen-free flame retardants and the flame retarded polymeric material containing the halogen-free flame retardants | |
| WO2018187026A1 (en) | Flame retardant thermoplastic composition | |
| JP5113678B2 (en) | Environmentally friendly thermoplastic resin composition and molded article comprising the same | |
| CN109265743B (en) | Flame retardant, composite flame retardant and flame-retardant polymer material containing composite flame retardant | |
| JPH09241395A (en) | Molded item from low frame-retardant polyester molding material | |
| DE102015209451A1 (en) | Flame-retardant polyamides | |
| CN107325329B (en) | A kind of halogen-free flame retardants and the high molecular material containing the fire retardant | |
| BR112021011696A2 (en) | METHOD FOR PREPARING FLAME RETARDANT MATERIAL CONTAINING THERMALLY STABLE PHOSPHORUS READY PROCESSED | |
| JPH04234893A (en) | Flame retardant for polymer | |
| JP6334150B2 (en) | Flame retardant resin composition and molded product thereof | |
| CN106947223B (en) | Thermoplastic polyester elastomer fire-retardant combination and preparation method thereof | |
| EP1122283B1 (en) | Flame-retardant polyketone resin composition and molded article | |
| JPH021761A (en) | Lithium phosphonate and polymer composition containing it | |
| Long et al. | Synthesis and properties of a new halogen-free flame retardant for polyethylene | |
| JP2016011327A (en) | Flame-retardant resin composition, flame-retardant master batch, molded body, and manufacturing method thereof | |
| JP2001081306A (en) | Flame retardant polyketone resin composition and molded article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |