CN107325329B - A kind of halogen-free flame retardants and the high molecular material containing the fire retardant - Google Patents
A kind of halogen-free flame retardants and the high molecular material containing the fire retardant Download PDFInfo
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- 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
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- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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- C08K5/51—Phosphorus bound to oxygen
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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Abstract
This application discloses a kind of halogen-free flame retardants and containing the high molecular material of the fire retardant, the halogen-free flame retardants includes compound A and compound B；Wherein, the compound A selects at least one of the nonacid metal salt that at least one hydroxyl loses the acid radical anion of hydrogen atom formation in free compound C and metal cation is formed；The compound C is selected from least one of the compound with the chemical formula as shown in formula (I)；The compound B is selected from least one of the compound with chemical formula shown in formula (II), compound with chemical formula shown in formula (III).The halogen-free flame retardants overcomes deficiency of the existing alkyl phosphonate as fire retardant, especially overcomes the problems, such as that alkyl phosphonate causes the degradation of high molecular material and the xanthochromia of high molecular material in the prior art.
Description
Technical field
This application involves a kind of halogen-free flame retardants and containing the high molecular material of the fire retardant, belong to flame retarded polymeric material
Preparation field.
Background technique
Flame retarded polymeric material especially glass-fiber-reinforced polyamide, polyester PBT and high-temperature nylon etc. is widely used in electricity
Receptacle in son and electrical apparatus industry, connector, the manufacture of the miniature electrics component such as relay.Traditionally high molecular material
It is fire-retardant realized by bromide fire retardant, but bromide fire retardant can generate strong carcinogenic dioxin when burning, together
When the hydrogen bromide that generates can cause secondary pollution again.Therefore, the use of bromide fire retardant recent years is gradually restricted, high
Fire-retardant thus turn to of molecular material uses halogen-free flame retardants.
In halogen-free flame retardants, phosphorus flame retardant is even more to cause numerous concerns due to its diversified fire retardant mechanism.
But the characteristics of organic phosphorus flame retardant generally has thermal stability low, and volatility is big and poor chemical stability, is not able to satisfy height
The processing and requirement of molecular material.To improve heat-resisting and chemical-resistant stability, phosphate flame retardants result in development.
But phosphate flame retardants are flammable simultaneously in reduction high molecular material, under the physical property for usually causing high molecular material
Drop, leads to that the practicability is poor.
For example, United States Patent (USP) US3894986 reports alkali metal acidity phosphonate, such phosphonate volatility is low, and heat is steady
Qualitative height, good flame retardation effect, but they contain acid phosphorus hydroxyl group, easily cause polyamide-based and polycarbonate-based macromolecule
The degradation of material, while alkali metal phosphonate is soluble easily in water, is easy to be precipitated in high molecular material, is not suitable for being used for a long time.
United States Patent (USP) US4972011 describes alkoxy (or acid) alkyl phosphonic acid aluminium, and the water solubility of aluminium salt compares alkali metal
Salt is low, but the presence of alkoxy reduces the thermal stability of alkyl phosphonic acid aluminium, is not able to satisfy the high temperature process requirement of engineering plastics.
Although its example B has enumerated acidic alkyl phosphonic acids aluminium, the presence of phosphorus-hydroxyl can cause the degradation of the classes such as polyamide.
United States Patent (USP) US8026303 describes alkoxyalkyl phosphonic acids aluminium, but its thermal stability is not high, is not able to satisfy polyamides
Amine engineering plastics high temperature process requirement, polyamide-based engineering plastics usually need 300 DEG C even more than process.
United States Patent (USP) US4180495 describes dialkylphosphinic salts, such salt has good thermal stability, but to glass
The flame retardant effect of glass fiber reinforced polyester and polyamide is undesirable.
United States Patent (USP) US6547992 reports dialkylphosphinic salts and mixes application with inorganic metal salt to improve fire-retardant effect
Rate, but with the poor compatibility of high molecular material, and in test, discovery inorganic metal salt causes high molecular material to inorganic metal salt
Degradation.
WO2016014113 reports alkyl acidity phosphonate after high-temperature process, has obtained having good thermal stability
Alkyl pyrophosphonate, and mix application with dialkylphosphinic salts and improve flame retarding efficiency, but the chemistry of alkyl pyrophosphonate
Stability is poor, is easy hydrolysis.
Aminomethylphosphonic acid or its alkali metal salt are well-known as metal-chelator, for example United States Patent (USP) US3234124
It reports aminotrimethylenephosphonic acid and its alkali metal salt is used as iron, copper, the chelating agent of manganese ion, as water treatment agent.
United States Patent (USP) US3257479 reports alkylamino dimethylene-phosphonic acid alkali metal salt or alkali salt, is used as
Surfactant or deflocculant have no and refer to and using as fire retardant.
United States Patent (USP) US4054544 reports aminotrimethylenephosphonic acid bromo Arrcostab as well as polyurethane foam
Fire retardant, but the thermal stability of phosphonic acids bromo Arrcostab is poor, and contains bromine atom, and the feature of environmental protection is low.
Summary of the invention
According to the one aspect of the application, a kind of halogen-free flame retardants is provided, which overcomes existing alkylphosphines
Deficiency of the hydrochlorate as fire retardant especially overcomes alkyl phosphonate in the prior art to cause degradation and the high score of high molecular material
The problem of xanthochromia of sub- material.
The halogen-free flame retardants includes compound A and compound B；
Wherein, the compound A selects at least one hydroxyl in free compound C to lose the acid radical anion that hydrogen atom is formed
At least one of the nonacid metal salt formed with metal cation；
The compound C is selected from least one of the compound with the chemical formula as shown in formula (I):
In formula (I), R1, R2, R3, R4Independently selected from hydrogen, C1~C8Alkyl and C6~C12One of aryl；x+y+
Z=3；And x=0,1 or 2, y=0,1 or 2, z=1,2 or 3；
The compound B is selected from the compound with chemical formula shown in formula (II), the change with chemical formula shown in formula (III)
Close at least one of object:
In formula (II), R5、R6Independently selected from C1~C8Alkyl, one of aryl；
Mm+Metal ion is represented, m is the valence state of metal M；
In formula (III), A is selected from C1~C10Alkylene, C6~C10Arylene, alkyl replace arylene, aryl
Replace one of alkylene；
R7、R8Independently selected from C1~C8Alkyl, one of aryl；
Lp+Metal ion is represented, p is the valence state of metal L.
Preferably, the mass ratio of the compound A and compound B is 1~30:1~20.
Preferably, the mass ratio of the compound A and compound B is 2~15:3~18.
Preferably, the mass ratio of the compound A and compound B is 1~30:5~20.
Preferably, the mass ratio of the compound A and compound B is 10~30:5~10.
Preferably, the mass ratio of the compound A and compound B is 20~30:1~5.
Preferably, the compound C is selected from compound with chemical formula shown in formula (I-1), with formula (I-2) shownization
The compound of formula, the compound with chemical formula shown in formula (I-4), has the compound with chemical formula shown in formula (I-3)
At least one of the compound of chemical formula shown in formula (I-5):
After at least one hydroxyl loses a H in the compound C, due to the presence of amino, the acid of second hydroxyl
Property neutralized with amino, third hydroxyl it is acid just very weak, will not influence high molecular material.
It is described nonacid to refer to: when in sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and compound C, in gained
And the pH of compound is between 6~7.5, it is non-for replacing the resulting compound A of sodium ion according to equivalent with metal cation at this time
Bisalt.P-OH is not contained in the nonacid structure for not meaning here that compound A, but even if containing P-OH, by
Contain basic amine group in molecule, even if the acidity that compound A shows has, and very weak, is not enough to cause macromolecule material
The degradation of material.
The compound A can by compound C with and metal oxide, metal hydroxides or metal carbonate etc. in
With obtain to pH=6~7.5；Can also by compound C first with alkali (sodium carbonate, potassium carbonate, sodium hydroxide, in potassium hydroxide
It is at least one) pH=6~7.5 are neutralized to, it adds metal cation precipitating and obtains.
Preferably, the metal cation in compound A is selected from Zn2+、Al3+、Ca2+、Mg2+、Fe2+、Fe3+、Ti4+In at least
It is a kind of.
Preferably, the compound C is selected from compound with chemical formula shown in formula (I-1), with formula (I-2) shownization
At least one of the compound of formula.
It is further preferred that the compound C is the compound with chemical formula shown in formula (I-2).
Preferably, in formula (II), Mm+Selected from least one of divalent metal, trivalent metal cation.
Preferably, in formula (III), Lp+Selected from least one of divalent metal, trivalent metal cation.
Preferably, Mm+、Lp+Independently selected from Mg2+、Ca2+、Ba2+、Fe2+、Fe3+、Al3+、Zn2+At least one of.
The compound B is selected from diethyl phosphinates, Methylethyl phosphinates, ethyl-butyl phosphinates, hexichol
At least one of base phosphinates, methylphenylphosphinic acid salt.
It is further preferred that the compound B is aluminum diethylphosphinate, diethyl phosphinic acids zinc, Methylethyl time phosphine
Sour aluminium, Methylethyl phosphinic acids zinc, ethyl-butyl phosphinic acids aluminium, diphenyl phosphonic acid aluminium, in methylphenylphosphinic acid aluminium extremely
Few one kind.
As an implementation, also contain borate in the halogen-free flame retardants.
Those skilled in the art can select the type and additional amount of borate according to actual needs.Selectively, the boron
Content range lower limit of the hydrochlorate in halogen-free flame retardants be selected from 0wt%, 0.5wt%, 1wt%, the upper limit be selected from 5wt%, 4wt%,
3wt%, 2.6wt%, 2.5wt%, 2.0wt%, 1.5wt%.
Preferably, the borate is zinc borate.
According to the another aspect of the application, a kind of halogen-free flame-retardant polymer material, the halogen-free flame-retardant polymer material are provided
Contain the halogen-free flame retardants in material.
Preferably, content of the compound A in halogen-free flame-retardant polymer material is 1~30wt%；Compound B is hindered in Halogen
Firing the content in high molecular material is 1~20wt%, depends on compound A and high molecular material.
When content of the compound A in halogen-free flame-retardant polymer material is less than 1%, flame retardant effect is bad, yellowing-resistant
Ability is low；When greater than 30%, the physical property of fire proofing is reduced.
Preferably, weight percentage of the compound A in the halogen-free flame retardants in halogen-free flame-retardant polymer material
The upper limit be selected from 30wt%, 28wt%, 26wt%, 24wt%, 22wt%, 20wt%, 18wt%, lower limit be selected from 15wt%,
13wt%, 11wt%, 9wt%, 7wt%, 5wt%, 3wt%, 1wt%.
Preferably, content of the compound A in halogen-free flame-retardant polymer material is 2~15wt%.
It is further preferred that content of the compound A in halogen-free flame-retardant polymer material is 2wt%, 5wt%, 10wt%
Or 12wt%.
Preferably, the weight percentage upper limit of the compound B in halogen-free flame-retardant polymer material be selected from 20wt%,
18wt%, 16wt%, 14wt%, 12wt%, 10wt%, lower limit are selected from 9wt%, 7wt%, 5wt%, 3wt%, 1wt%.
Preferably, content of the compound B in halogen-free flame-retardant polymer material is 5~20wt%.
Preferably, content of the compound B in halogen-free flame-retardant polymer material is 3~18wt%.
It is further preferred that content of the compound B in halogen-free flame-retardant polymer material is 5wt%, 10wt%, 14wt%
Or 15wt%.
Preferably, the high molecular material in halogen-free flame-retardant polymer material is thermoplastic macromolecule material.
The thermal plastic high polymer refers to the plastics with heating and softening, hardening by cooling characteristic.
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 is at least one of polyamide, polyester.
Polyamide is the high molecular general name for containing-NH-C (O)-amide group in its structural unit, by one or more
Dicarboxylic acids and the contracting of one or more diamines and/or one or more amino acid and/or one or more lactams
It closes or ring-opening reaction synthesizes.
Polyester is the high molecular general name for containing-O-C (O) -ester group in its structural unit, passes through dicarboxylic acids and binary
Alcohol condensation reaction synthesis.
Preferably, the high molecular material in the halogen-free flame-retardant polymer material is polyamide 6, polyamide 66, gathers to benzene
At least one of dioctyl phthalate second diester, polytrimethylene terephthalate, polybutylene terephthalate.
It preferably, include antioxidant, reinforcing agent, anti-dripping agent, stabilizer, face in the halogen-free flame-retardant polymer material
At least one of material, dyestuff, char forming catalyst, dispersing agent, nucleating agent, inorganic filler.
Preferably, additive in the halogen-free flame-retardant polymer material (antioxidant, reinforcing agent, anti-dripping agent, stabilizer,
At least one of pigment, dyestuff, char forming catalyst, dispersing agent, nucleating agent, inorganic filler) in halogen-free flame-retardant polymer material
In content be 0~40wt%, further preferred 10~40wt%, still more preferably 20~40wt%.
Optionally, the antioxidant is compound antioxidant.
Preferably, compound antioxidant is antioxidant 1010 (four [β-(3,5- di-tert-butyl-hydroxy phenyl propionic acid] seasons penta
Four alcohol esters) it is mixed with irgasfos 168 (three [2.4- di-tert-butyl-phenyl] phosphite esters) with 1:1 weight ratio.
Optionally, the reinforcing agent is glass fibre.
Optionally, the anti-dripping agent is Teflon Teflon.
Optionally, the inorganic filler is at least one of micarex, calcium carbonate, calcium oxide, silica.
Preferably, the halogen-free flame-retardant polymer material includes glass fibre.
Preferably, content of the compound A in halogen-free flame-retardant polymer material is 1 in the halogen-free flame-retardant polymer material
~30wt%；Content of the compound B in halogen-free flame-retardant polymer material be 5~20wt%, additive (antioxidant, reinforcing agent,
Anti-dripping agent, stabilizer, pigment, at least one of dyestuff, char forming catalyst, dispersing agent, nucleating agent, inorganic filler) in nothing
Content in halogen flame retarded polymeric material is 10~40wt%.
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%.
Have when compound A is used together with compound B fire retardant in the present invention to glass reinforced polyamide and polyester excellent
Different flame retardant property, and the xanthochromia of flame retarded polymeric material can be greatly reduced, the latter it is particularly surprising that, because tradition is recognized
It will cause xanthochromia for the presence of amino.In addition, the presence of amino also avoids known simple alkyl acidity phosphonate due to acidity
Caused by high molecular material degradation.Alpha-aminoalkyl phosphonate compared to other class alkyl phosphonates these advantages
Have in document there are no being realized, but they keep good color and physical property to the flame retardant properties for improving material
Tool plays a very important role.
In the application, C1~C8、C6~C12Etc. 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.
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, " 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, " arylene " is to lose two hydrogen atoms on aromatic rings on aromatic compound molecule to be formed by base
Group, such as:Deng.
In the application, " amino " refers to-NH2Or-NH2In at least one hydrogen atom by alkyl, aryl or other take
At least one of Dai Ji substitution is formed by group；Wherein, alkyl, any one hydrogen atom in aryl can be taken by other
Replace for base.
The beneficial effect that the application can generate includes:
1) halogen-free flame retardants provided herein can be avoided fire proofing physics caused by known acid phosphonate
The degradation of the problem of performance excessive descent and known simple alkyl acidity phosphonate high molecular material due to caused by acidity.
2) halogen-free flame retardants provided herein has excellent flame retardant property to glass reinforced polyamide and polyester,
And the xanthochromia of flame retarded polymeric material can be greatly reduced.
3) xanthochromia of material is greatly lowered in the use of compound A in halogen-free flame retardants provided herein, with tradition
The understanding that the compound of nitrogen atom easily causes xanthochromia is opposite.
4) halogen-free flame retardants provided herein, source is wide, at low cost.
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, content of glass fiber
For 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
30wt%.
Aminotrimethylenephosphonic acid (ATMP): the calm and peaceful water process Science and Technology Co., Ltd. in Shandong.
DePAl-1: aluminum diethylphosphinate, Zhejiang development of evil in febrile disease Hua Yang limited liability company.
DePAl-2: aluminum diethylphosphinate, German Clariant Corporation OP1230。
DePAl-3: aluminum diethylphosphinate, German Clariant Corporation OP935。
Antioxidant 1010: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, Sa grace chemical technology
(Shanghai) Co., Ltd..
Irgasfos 168: three [2,4- di-tert-butyl-phenyl] phosphite esters, Strem chemical company of the U.S..
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.
Flame retardant property (burning in embodiment and comparative example, according to the method in GB/T 2408-2008 standard to sample
Testing standard) it is measured, the measurement of plastic tensile performance is measured according to method in GB/T1040.1-2006, plastics bendability
The measurement of energy is measured according to method in GB/T9341-2000.
Embodiment 1
The preparation of ATMP-Zn
50wt%ATMP aqueous solution (173.00g, 0.29 mole) is added in a 500mL beaker, is added dropwise at room temperature
PH is adjusted to 6~7 by 25wt%NaOH aqueous solution, is consumed 231.32 grams of NaOH aqueous solution (1.45 moles of NaOH) altogether, is equivalent to
5 acid in ATMP are neutralized, also there are an acid.It at room temperature, will under the stirring that low whipping speed is 300~400 revs/min
It is added dropwise to 1000mL equipped with 30wt%ZnSO4·7H2In the beaker of O (207.50g, 0.72 mole) aqueous solution, it is added dropwise in 1.5h
It finishes, stirring at normal temperature 0.5h.Then white powdery solids are obtained after successively being filtered, washed and being dried, total 120.84g,
Yield is 91.50%, is denoted as ATMP-Zn.
Embodiment 2
The preparation of ATMP-Zn-Ca salt-mixture
50wt%ATMP aqueous solution (19.38g, 0.0324 mole) is added in a 200mL beaker, is added dropwise at room temperature
PH is adjusted to 7 by 10wt%NaOH aqueous solution, consumes 66.4 grams of (0.166 mole) NaOH aqueous solutions altogether, is equivalent to and is neutralized ATMP
In 5.12 acid.Under the stirring that low whipping speed is 300~400 revs/min at room temperature, it is added dropwise to dissolved with CaCl2
(1.86g, 0.0168 mole) and ZnCl2The mixing of (9.09g, 0.0668 mole) (wherein the ratio between Zn/Ca moles=4/1) is water-soluble
It in liquid, is added dropwise in 40min, stirring at normal temperature 0.5h.Then successively filtered, wash and drying to obtain white powder solid
Body, total 13.17g, yield 90.1% are denoted as ATMP-Zn-Ca.
Embodiment 3
By polyamide PA66-B, DePAl-1, ATMP-Zn and compound antioxidant according to the weight ratio of 79.6:15:5:0.4
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.Sample is in ash
White cuts sample, test after its cooling.The fire-retardant rank of 1.6mm sample and 0.8mm are V-0.
Embodiment 4
By polyamide PA66-A, DePAl-2, ATMP-Zn and compound antioxidant according to the weight ratio of 82.6:5:12:0.4
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.Sample is in ash
White cuts sample, test after its cooling.The fire-retardant rank of 1.6mm sample is V-0.
Embodiment 5
By polyamide PA66-B, ATMP-Zn, zinc borate and DePAl-1 and compound antioxidant according to 80.1:5:0.5:
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.Batten is canescence, and sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample and 0.8mm is
UL94V-0。
Embodiment 6
By polyamide PA66-A, ATMP-Zn-Ca and DePAl-3 and compound antioxidant according to the weight of 83.6:2:14:0.4
Amount ratio 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.Batten
For canescence, sample, test are cut after its cooling.The fire-retardant rank of 1.6mm sample is UL94V-0.
Embodiment 7
By polyamide PA6, DePAl-1, ATMP-Zn and compound antioxidant according to the weight ratio of 79.6:10:10:0.4,
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.Sample is in greyish white
Color cuts sample, test after its cooling.The fire-retardant rank of 1.6mm sample is V-0.
Embodiment 8
By polyester PBT, ATMP-Zn, DePAl-1 and compound antioxidant according to the weight ratio of 79.6:10:10:0.4,
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 it is filled out
It fills in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.Batten is white, to
It cuts sample, test after cooling down.The fire-retardant rank of 1.6mm sample is UL94V-0.
Embodiment 9
By polyester PBT, ATMP-Zn, DePAl-1 and compound antioxidant according to the weight ratio of 82.6:2:15:0.4, turning
For speed to mix in 50 revs/min of mixer, setting temperature is 260 DEG C, is taken out after five minutes cooling, dry.Then it is filled with
It in mold, is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.Batten is white, to it
Sample, test are cut after cooling.The fire-retardant rank of 1.6mm sample is UL94V-0.
Comparative example 1
By polyamide PA66-B and compound antioxidant according to 99.6:0.4, mixed in the mixer that revolving speed is 50 revs/min
It closes, setting temperature is 280 DEG C, is taken out after five minutes cooling, dry.Then it is filled in mold, in 280 DEG C of plate sulphur
Change machine preheats 10 minutes, and 10MPa pressure maintaining after five minutes, is cold-pressed.Sample is brown.The fire-retardant rank of 1.6mm sample is no rank.
Comparative example 2
By polyamide PA66-A, ATMP-Zn and compound antioxidant according to the weight ratio of 84.6:15:0.4, it is in revolving speed
It is mixed in 50 revs/min of mixer, setting temperature is 280 DEG C, is taken out after five minutes cooling, dry.Then it is filled in mould
It in tool, is preheated 10 minutes in 280 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.Sample is brown.1.6mm sample
Fire-retardant rank be no rank.
Comparative example 3
By polyamide PA66-B, DePAl-1 and compound antioxidant according to the weight ratio of 79.6:20:0.4, it is in revolving speed
It is mixed in 50 revs/min of mixer, setting temperature is 280 DEG C, is taken out after five minutes cooling, dry.Then it is filled in mould
It in tool, is preheated 10 minutes in 280 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.Sample is cold to its in light brown
But sample, test are cut afterwards.The fire-retardant rank of 3.2mm sample is no rank.
Comparative example 4
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 is brown, after its cooling
Cut sample, test.The fire-retardant rank of 1.6mm sample is no rank.
Comparative example 5
By polyester PBT, DePAl-1 and compound antioxidant according to the weight ratio of 83.6:16:0.4, revolving speed be 50 turns/
It is mixed in the mixer of minute, setting temperature is 260 DEG C, takes out cooling, drying after five minutes.Then it is filled in mold,
It is preheated 10 minutes in 260 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.Sample is white, cuts after its cooling
Sample, test.The fire-retardant rank of 1.6mm sample is V-1 rank.
Comparative example 6
By polyamide PA66-A, ATMP-Zn and compound antioxidant according to the weight ratio of 69.6:30:0.4, it is in revolving speed
It is mixed in 50 revs/min of mixer, setting temperature is 280 DEG C, is taken out after five minutes cooling, dry.Then it is filled in mould
It in tool, is preheated 10 minutes in 280 DEG C of vulcanizing presses, 10MPa pressure maintaining after five minutes, is cold-pressed.Sample is brown.1.6mm sample
Fire-retardant rank be 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.
Compare from comparative example 3 and embodiment 3,4,5 and comparative example 4 can be seen that compared with embodiment 7 using provided herein
Halogen-free flameproof immunomodulator compounds A and compound B be used in combination, prevent polyamide discoloration above with outstanding performance, simultaneously
It also provides good flame retardant property for polyamide.From comparative example 5 and embodiment 8 as can be seen that reducing more expensive
DePAl, but still polyester PBT can be made to reach better flame retardant rating using cheap ATMP-Zn, this is economically to have very much
Benefit.
Table 1
NR: without rank
Respectively in embodiment 3, comparative example 3, embodiment 7, comparative example 4 gained sample tensile property and bending property into
Row measurement, acquired results are as shown in table 2, as a result illustrate that the physical property of embodiment and comparative example is close.
Table 2
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (14)
1. a kind of halogen-free flame retardants, which is characterized in that the halogen-free flame retardants includes compound A and compound B；
Wherein, the compound A selects at least one hydroxyl in free compound C to lose the acid radical anion and metal sun that hydrogen is formed
At least one of the nonacid metal salt that ion is formed；
The compound C is selected from least one of the compound with the chemical formula as shown in formula (I):
In formula (I), R1, R2, R3, R4Independently selected from hydrogen, C1~C8Alkyl and C6~C12One of aryl；X=0,1 or
2, y=0,1 or 2, z=1,2 or 3, and x+y+z=3；
The compound B is selected from the compound with chemical formula shown in formula (II), the compound with chemical formula shown in formula (III)
At least one of:
In formula (II), R5、R6Independently selected from C1~C8Alkyl, one of aryl；
Mm+Metal ion is represented, m is the valence state of metal M；
In formula (III), A is selected from C1~C10Alkylene, C6~C10Arylene, alkyl replace arylene, aryl replace
One of alkylene；
R7、R8Independently selected from C1~C8Alkyl, one of aryl；
Lp+Metal ion is represented, p is the valence state of metal L.
2. halogen-free flame retardants according to claim 1, which is characterized in that the quality of the compound A and the compound B
Than for 1~30:1~20.
3. halogen-free flame retardants according to claim 2, which is characterized in that the mass ratio of the compound A and compound B is
2~15:3~18.
4. halogen-free flame retardants according to any one of claims 1 to 3, which is characterized in that the compound C, which is selected from, has formula
(I-1) compound of chemical formula shown in, has chemical formula shown in formula (I-3) at the compound with chemical formula shown in formula (I-2)
Compound, the compound with chemical formula shown in formula (I-4), at least one in the compound with chemical formula shown in formula (I-5)
Kind:
5. halogen-free flame retardants according to any one of claims 1 to 3, which is characterized in that the metal cation is selected from Zn2 +、Al3+、Ca2+、Mg2+、Fe2+、Fe3+、Ti4+At least one of.
6. halogen-free flame retardants according to any one of claims 1 to 3, which is characterized in that include in the halogen-free flame retardants
Borate.
7. halogen-free flame retardants according to any one of claims 1 to 3, which is characterized in that the compound B is selected from diethyl
Phosphinates, Methylethyl phosphinates, ethyl-butyl phosphinates, diphenyl phosphonic acid salt, in methylphenylphosphinic acid salt
At least one.
8. halogen-free flame retardants according to claim 7, which is characterized in that the compound B be selected from aluminum diethylphosphinate,
Diethyl phosphinic acids zinc, Methylethyl phosphinic acids aluminium, Methylethyl phosphinic acids zinc, ethyl-butyl phosphinic acids aluminium, diphenyl time phosphine
At least one of sour aluminium, methylphenylphosphinic acid aluminium.
9. a kind of halogen-free flame-retardant polymer material, which is characterized in that contain claim 1 in the halogen-free flame-retardant polymer material
To 8 described in any item halogen-free flame retardants.
10. halogen-free flame-retardant polymer material according to claim 9, which is characterized in that the compound A is in halogen-free flameproof
Content in high molecular material is 1~30wt%；Content of the compound B in halogen-free flame-retardant polymer material be 1~
20wt%.
11. halogen-free flame-retardant polymer material according to claim 10, which is characterized in that the compound A is hindered in Halogen
Firing the content in high molecular material is 2~15wt%；Content of the compound B in halogen-free flame-retardant polymer material be 3~
18wt%.
12. halogen-free flame-retardant polymer material according to claim 9, which is characterized in that the halogen-free flame-retardant polymer material
High molecular material in material is selected from least one of polyamide, polyester.
13. halogen-free flame-retardant polymer material according to claim 12, which is characterized in that the halogen-free flame-retardant polymer material
High molecular material in material is selected from polyamide 6, polyamide 66, polyethylene terephthalate, and polytrimethylene terephthalate gathers
At least one of butylene terephthalate.
14. halogen-free flame-retardant polymer material according to claim 9, which is characterized in that the halogen-free flame-retardant polymer material
It include antioxidant in material, reinforcing agent, anti-dripping agent, stabilizer, pigment, dyestuff, char forming catalyst, dispersing agent, nucleating agent, inorganic
At least one of filler.
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| CN113881178B (en) * | 2021-09-28 | 2023-05-09 | 江苏金发科技新材料有限公司 | Weather-resistant flame-retardant polymethyl methacrylate composite material and preparation method and application thereof |
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| RU2010122376A (en) * | 2010-06-01 | 2011-12-10 | Открытое акционерное общество "Научно-исследовательский институт по нефтепромысловой химии" (ОАО "НИИнефтепромхим") (RU) | METHOD FOR TREATING A BOREHOLE BOTTOM ZONE |
| CN104497041A (en) * | 2014-12-09 | 2015-04-08 | 东华大学 | Melamine aminotrimethylene phosphonate and preparation method thereof |
| CN105038275A (en) * | 2015-07-28 | 2015-11-11 | 蚌埠南自仪表有限公司 | Lightweight bituminous waterproof sheet material |
| CN105255067A (en) * | 2015-11-23 | 2016-01-20 | 宁波尚高新材料有限公司 | Energy-saving rigid plastic and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2010122376A (en) * | 2010-06-01 | 2011-12-10 | Открытое акционерное общество "Научно-исследовательский институт по нефтепромысловой химии" (ОАО "НИИнефтепромхим") (RU) | METHOD FOR TREATING A BOREHOLE BOTTOM ZONE |
| CN104497041A (en) * | 2014-12-09 | 2015-04-08 | 东华大学 | Melamine aminotrimethylene phosphonate and preparation method thereof |
| CN105038275A (en) * | 2015-07-28 | 2015-11-11 | 蚌埠南自仪表有限公司 | Lightweight bituminous waterproof sheet material |
| CN105255067A (en) * | 2015-11-23 | 2016-01-20 | 宁波尚高新材料有限公司 | Energy-saving rigid plastic and preparation method thereof |
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