CN107325329A - A kind of halogen-free flame retardants and the high polymer material containing the fire retardant - Google Patents
A kind of halogen-free flame retardants and the high polymer material containing the fire retardant Download PDFInfo
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- C08K5/13—Phenols; Phenolates
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- 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
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- C08K5/00—Use of organic ingredients
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- 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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- C08K5/00—Use of organic ingredients
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- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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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
A kind of high polymer material this application discloses halogen-free flame retardants and containing the fire retardant, 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 at least one of the acid radical anion of hydrogen atom formation and the nonacid metal salt of metal cation formation；The compound C, which is selected from, has at least one of compound of chemical formula as shown in formula (I)；The compound B is selected from the compound of chemical formula shown in formula (II), with least one of compound of chemical formula shown in formula (III).The halogen-free flame retardants overcomes existing alkyl phosphonate as the deficiency of fire retardant, particularly overcome alkyl phosphonate in the prior art cause high polymer material degraded and high polymer material xanthochromia the problem of.
Description
Technical field
The application is related to a kind of halogen-free flame retardants and the high polymer material containing the fire retardant, belongs to flame retarded polymeric material
Preparation field.
Background technology
Flame retarded polymeric material particularly glass-fiber-reinforced polyamide, polyester PBT and high-temperature nylon etc. are widely used in electricity
Receptacle in son and electrical apparatus industry, connector, the manufacture of the miniature electric component such as relay.Traditionally high polymer material
It is fire-retardant realized by bromide fire retardant, but bromide fire retardant can produce strong carcinogenic bioxin when burning, together
When the hydrogen bromide that produces 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 organic phosphorus flame retardant generally has heat endurance low, volatility is big, and the characteristics of poor chemical stability, it is impossible to meet high
The processing of molecular material and use requirement.To improve heat-resisting and chemical-resistant stability, phosphate flame retardants resulting in development.
But phosphate flame retardants are flammable simultaneously in reduction high polymer material, under the physical property for usually causing high polymer material
Drop, causes poor practicability.
For example, United States Patent (USP) US3894986 reports the acid phosphonate of alkali metal, and such phosphonate volatility is low, and heat is steady
Qualitative height, good flame retardation effect, but they contain acid phosphorus oh group, easily cause polyamide-based and makrolon family macromolecule
The degraded of material, while alkali metal phosphonate is soluble in water, is easily separated out in high polymer 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 heat endurance of alkyl phosphonic acid aluminium, it is impossible to meet 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 degraded of the classes such as polyamide.
United States Patent (USP) US8026303 describes alkoxyalkyl phosphonic acids aluminium, but its heat endurance is not high, it is impossible to meet polyamides
The high temperature process requirement of amine engineering plastics, polyamide-based engineering plastics are usually needed in 300 DEG C of even above processing.
United States Patent (USP) US4180495 describes dialkylphosphinic salts, and such salt has good heat endurance, 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 to improve fire-retardant effect with inorganic metal salt
Rate, but inorganic metal salt causes high polymer material with discovery inorganic metal salt in the poor compatibility of high polymer material, and experiment
Degraded.
WO2016014113 reports the acid phosphonate of alkyl 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, easily hydrolysis.
Aminomethylphosphonic acid or its alkali metal salt are widely known by the people as metal-chelator, for example United States Patent (USP) US3234124
Report ATMP and its alkali metal salt is used as iron, copper, the chelating agent of manganese ion is used as water treatment agent.
United States Patent (USP) US3257479 reports alkylamino dimethylene-phosphonic acid alkali metal salt or alkali salt, and it is used as
Surfactant or deflocculant, have no and refer to and being used as fire retardant.
United States Patent (USP) US4054544 report ATMP bromo Arrcostab and its as polyurethane foam
Fire retardant, but the heat endurance of phosphonic acids bromo Arrcostab is poor, and contains bromine atoms, and the feature of environmental protection is low.
The content of the invention
According to the one side of the application there is provided a kind of halogen-free flame retardants, the halogen-free flame retardants overcomes existing alkylphosphines
Hydrochlorate particularly overcomes alkyl phosphonate in the prior art to cause degraded and the high score of high polymer material as the deficiency of fire retardant
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 nonacid metal salt formed with metal cation；
The compound C, which is selected from, has at least one of compound of chemical formula as shown in formula (I)：
In formula (I), R1, R2, R3, R4Independently selected from hydrogen, C1~C8Alkyl and C6~C12Aryl in one kind；x+y+
Z=3；And x=0,1 or 2, y=0,1 or 2, z=1,2 or 3；
The compound B, which is selected from, has the compound of chemical formula shown in formula (II), the change with chemical formula shown in formula (III)
At least one of compound：
In formula (II), R5、R6Independently selected from C1~C8Alkyl, one kind in aryl；
Mm+Metal ion is represented, m is metal M valence state；
In formula (III), A is selected from C1~C10Alkylene, C6~C10Arylene, alkyl substitution arylene, aryl
Replace one kind in alkylene；
R7、R8Independently selected from C1~C8Alkyl, one kind in aryl；
Lp+Metal ion is represented, p is metal L valence state.
Preferably, the mass ratio of the compound A and compound B are 1~30：1~20.
Preferably, the mass ratio of the compound A and compound B are 2~15：3~18.
Preferably, the mass ratio of the compound A and compound B are 1~30：5~20.
Preferably, the mass ratio of the compound A and compound B are 10~30：5~10.
Preferably, the mass ratio of the compound A and compound B are 20~30：1~5.
Preferably, the compound C is selected from the compound of chemical formula shown in formula (I-1), with formula (I-2) shownization
The compound of formula, with the compound of chemical formula shown in formula (I-3), with the compound of chemical formula shown in formula (I-4), have
At least one of 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, the acidity of the 3rd hydroxyl is just very weak, does not interfere with high polymer material.
It is described nonacid to refer to：When with sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and compound C, in gained
And the pH of compound is between 6~7.5, now to replace compound A obtained by sodium ion to be non-according to equivalent with metal cation
Bisalt.Do not contain P-OH in the nonacid structure for not meaning here that compound A, even if but contain P-OH, by
Contain basic amine group in molecule, even if the acidity that compound A shows has, be also very weak, be not enough to cause macromolecule material
The degraded 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 be by compound C first with alkali (in sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide
It is at least one) pH=6~7.5 are neutralized to, add metal cation precipitation and obtain.
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 the compound of chemical formula shown in formula (I-1), with formula (I-2) shownization
At least one of 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
In sour aluminium, Methylethyl phosphinic acids zinc, ethyl-butyl phosphinic acids aluminium, diphenyl phosphonic acid aluminium, methylphenylphosphinic acid aluminium extremely
Few one kind.
As a kind of embodiment, also contain borate in the halogen-free flame retardants.
Those skilled in the art according to actual needs, can select the species and addition of borate.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 Firebrake ZB.
According to the another aspect of the application, there is provided a kind of halogen-free flame-retardant polymer material, the halogen-free flame-retardant polymer material
Contain described halogen-free flame retardants in material.
Preferably, contents of the compound A in halogen-free flame-retardant polymer material is 1~30wt%；Compound B hinders in Halogen
The content fired in high polymer material is 1~20wt%, depending on compound A and high polymer material.
When contents 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；During more than 30%, the physical property reduction of fire proofing.
Preferably, weight percentages 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, contents of the compound A in halogen-free flame-retardant polymer material is 2~15wt%.
It is further preferred that contents of the compound A in halogen-free flame-retardant polymer material is 2wt%, 5wt%, 10wt%
Or 12wt%.
Preferably, the weight percentage upper limits 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, contents of the compound B in halogen-free flame-retardant polymer material is 5~20wt%.
Preferably, contents of the compound B in halogen-free flame-retardant polymer material is 3~18wt%.
It is further preferred that contents of the compound B in halogen-free flame-retardant polymer material is 5wt%, 10wt%, 14wt%
Or 15wt%.
Preferably, the high polymer material in halogen-free flame-retardant polymer material is thermoplastic macromolecule material.
The thermal plastic high polymer refers to there is heating and softening, the plastics of hardening by cooling characteristic.
Macromolecule refers to by numerous atoms or the main molecular weight with Covalent bonding together of atomic group more than 10,000
Compound.It includes polyethylene, polypropylene, polystyrene, high impact polystyrene, acrylonitrile-butadiene-styrene (ABS) copolymerization
Thing, Maranyl, Fypro, polyester plastics, polyester fiber, makrolon etc..
Preferably, the high polymer material in the halogen-free flame-retardant polymer material is at least one of polyamide, polyester.
Polyamide, is the high molecular general name containing-NH-C (O)-amide group in its construction unit, passes through one or more
Dicarboxylic acids and one or more diamines, and/or one or more amino acid, and/or one or more lactams contractings
Close or ring-opening reaction synthesis.
Polyester, is the high molecular general name containing-O-C (O) -ester group in its construction unit, passes through dicarboxylic acids and binary
Alcohol condensation reaction is synthesized.
Preferably, the high polymer material in the halogen-free flame-retardant polymer material is polyamide 6, polyamide 66, gathered to benzene
At least one of dioctyl phthalate second diester, polytrimethylene terephthalate, polybutylene terephthalate.
Preferably, the halogen-free flame-retardant polymer material includes antioxidant, reinforcing agent, anti-dripping agent, stabilizer, face
At least one of material, dyestuff, char forming catalyst, dispersant, nucleator, 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, dispersant, nucleator, inorganic filler) in halogen-free flame-retardant polymer material
In content be 0~40wt%, still more preferably further preferred 10~40wt%, 20~40wt%.
Alternatively, 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) with irgasfos 168 (three [2.4- di-tert-butyl-phenyls] phosphite esters) with 1:1 part by weight is mixed.
Alternatively, the reinforcing agent is glass fibre.
Alternatively, the anti-dripping agent is Teflon Teflon.
Alternatively, 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, contents of the compound A in halogen-free flame-retardant polymer material is 1 in the halogen-free flame-retardant polymer material
~30wt%；Contents 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, dispersant, nucleator, inorganic filler) in nothing
Content in halogen flame retarded polymeric material is 10~40wt%.
Those skilled in the art can according to specific needs, select halogen-free flame-retardant polymer material in high polymer material and
Other additives (reinforcing agent, anti-dripping agent, stabilizer, pigment, dyestuff, char forming catalyst, fire retardant, dispersant, nucleator,
At least one of antioxidant, inorganic filler) consumption.All components percentage by weight sum in halogen-free flame-retardant polymer material
For 100wt%.
Compound A has excellent when compound B fire retardants are used together to glass reinforced polyamide and polyester in the present invention
Different fire resistance, and the xanthochromia of flame retarded polymeric material, the latter can be greatly reduced it is particularly surprising that, because tradition is recognized
It will cause xanthochromia for the presence of amino.In addition, the presence of amino it also avoid the acid phosphonate of known simple alkyl due to acidity
Caused by high polymer material degraded.Alpha-aminoalkyl phosphonate compared to other class alkyl phosphonates these advantages
Have in document and be not realized also, but their fire resistances to raising material, keep good color and physical property
Tool plays a very important role.
In the application, C1~C8、C6~C12Etc. referring both to the carbon number that group is included.
In the application, " alkyl " is that the group that any one hydrogen atom is formed is lost on alkane compound molecule.
In the application, " alkylene " is that the group that any two hydrogen atom is formed is lost on hydrocarbon molecules,
Including alkylidene, arlydene, sub- aralkyl, alkarylene, alkyl-aryl-group subunit etc..
In the application, " aryl " is that the base that a hydrogen atom is formed on aromatic rings is lost on aromatic compounds molecule
Group；As lost the phenyl that any one hydrogen atom is formed on phenyl ring.
In the application, " arylene " is that the base that two hydrogen atoms are formed on aromatic rings is lost on aromatic compound molecule
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 replaces formed group；Wherein, any one hydrogen atom in alkyl, aryl can be taken by other
For base substitution.
The beneficial effect that the application can be produced includes：
1) halogen-free flame retardants provided herein, can avoid fire proofing physics caused by known acid phosphonate
The problem of performance excessive descent and the degraded of the acid phosphonate high polymer material caused by acidity of known simple alkyl.
2) halogen-free flame retardants provided herein, has excellent fire resistance 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 compound A use in halogen-free flame retardants provided herein, with tradition
The compound of nitrogen atom easily causes the understanding of xanthochromia to be opposite.
4) halogen-free flame retardants provided herein, source is wide, and cost is low.
Embodiment
The features described above that the application is mentioned, or the feature that embodiment is mentioned can be in any combination.Disclosed in this case specification
All features can be used in combination with any combinations thing form, each feature disclosed in specification, can by it is any provide it is identical,
The alternative characteristics substitution of impartial or similar purpose.Therefore except there is special instruction, disclosed feature is only impartial or similar spy
The general example levied.
With reference to embodiment, the present invention is expanded on further.It should be understood that these embodiments be merely to illustrate the present invention without
For limiting the scope of the present invention.The experimental method of unreceipted actual conditions in the following example, generally according to normal condition or
According to the 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 is
30wt%.
PBT (also known as polybutylene terephthalate)：Dupont Crastin SK605NC010, content of glass fiber is
30wt%.
ATMP (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 companies.
DePAl-2：Aluminum diethylphosphinate, German Clariant CorporationOP1230。
DePAl-3：Aluminum diethylphosphinate, German Clariant CorporationOP935。
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 companies of the U.S..
Compound antioxidant：Antioxidant 1010 (four [β-(and 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 1:1 part by weight is mixed.
In embodiment and comparative example, the fire resistance (burning according to the method in GB/T 2408-2008 standards to sample
Testing standard) it is measured, the measure of plastic tensile performance is determined according to method in GB/T1040.1-2006, plastics bendability
The measure of energy is determined according to method in GB/T9341-2000.
Embodiment 1
ATMP-Zn preparation
The 50wt%ATMP aqueous solution (173.00g, 0.29 mole) is added in a 500mL beakers, is added dropwise at room temperature
The 25wt%NaOH aqueous solution, 6~7 are adjusted to by pH, and 231.32 grams of the NaOH aqueous solution (1.45 moles of NaOH) is consumed altogether, equivalent to
5 acid in ATMP are neutralized, an acid is also left.At room temperature, under low whipping speed is 300~400 revs/min of stirring, incite somebody to action
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
Finish, stirring at normal temperature 0.5h.Then carry out obtaining white powdery solids after suction filtration, washing and drying successively, common 120.84g,
Yield is 91.50%, is designated as ATMP-Zn.
Embodiment 2
The preparation of ATMP-Zn-Ca salt-mixtures
The 50wt%ATMP aqueous solution (19.38g, 0.0324 mole) is added in a 200mL beakers, is added dropwise at room temperature
The 10wt%NaOH aqueous solution, 7 are adjusted to by pH, and 66.4 grams of (0.166 mole) NaOH aqueous solution are consumed altogether, equivalent to neutralization ATMP
In 5.12 acid.Under low whipping speed is 300~400 revs/min of stirring at room temperature, it is added dropwise to and is 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
In liquid, completion of dropping in 40min, stirring at normal temperature 0.5h.Then carry out suction filtration, washing and drying successively and obtain white powder consolidating
Body, common 13.17g, yield is 90.1%, is designated as ATMP-Zn-Ca.
Embodiment 3
By polyamide PA66-B, DePAl-1, ATMP-Zn and compound antioxidant according to 79.6：15：5：0.4 weight ratio
Example, is mixed in rotating speed is 50 revs/min of banbury, sets temperature to take out cooling after 280 DEG C, 5 minutes, dry.Then
It is filled with mould, is preheated 10 minutes in 280 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Sample is in ash
White, cuts sample, test after it is cooled down.1.6mm samples and 0.8mm fire-retardant rank are V-0.
Embodiment 4
By polyamide PA66-A, DePAl-2, ATMP-Zn and compound antioxidant according to 82.6：5：12：0.4 weight ratio
Example, is mixed in rotating speed is 50 revs/min of banbury, sets temperature to take out cooling after 280 DEG C, 5 minutes, dry.Then
It is filled with mould, is preheated 10 minutes in 280 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Sample is in ash
White, cuts sample, test after it is cooled down.The fire-retardant rank of 1.6mm samples is V-0.
Embodiment 5
By polyamide PA66-B, ATMP-Zn, Firebrake ZB and DePAl-1 and compound antioxidant according to 80.1：5：0.5：
14：0.4 part by weight, is mixed in rotating speed is 50 revs/min of banbury, and it is taking-up after 280 DEG C, 5 minutes to set temperature
Cool down, dry.Then it is filled with mould, is preheated 10 minutes in 280 DEG C of vulcanizing presses, 10MPa pressurizes 5 minutes
Afterwards, it is cold-pressed.Batten is canescence, and sample, test are cut after it is cooled down.1.6mm samples and 0.8mm fire-retardant rank is
UL94V-0。
Embodiment 6
By polyamide PA66-A, ATMP-Zn-Ca and DePAl-3 and compound antioxidant according to 83.6：2：14：0.4 weight
Amount ratio, is mixed in rotating speed is 50 revs/min of banbury, sets temperature to take out cooling after 280 DEG C, 5 minutes, dry.
Then it is filled with mould, is preheated 10 minutes in 280 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Batten
For canescence, sample, test are cut after it is cooled down.The fire-retardant rank of 1.6mm samples is UL94V-0.
Embodiment 7
By polyamide PA6, DePAl-1, ATMP-Zn and compound antioxidant according to 79.6：10：10：0.4 part by weight,
Mixed in rotating speed is 50 revs/min of banbury, set temperature to take out cooling after 260 DEG C, 5 minutes, dry.Then by it
It is filled in mould, is preheated 10 minutes in 260 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Sample is in greyish white
Color, cuts sample, test after it is cooled down.The fire-retardant rank of 1.6mm samples is V-0.
Embodiment 8
By polyester PBT, ATMP-Zn, DePAl-1 and compound antioxidant according to 79.6：10：10：0.4 part by weight,
Rotating speed sets temperature to take out cooling after 260 DEG C, 5 minutes, dry to mix in 50 revs/min of banbury.Then filled out
Fill in mould, preheated 10 minutes in 260 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Batten is white, is treated
It cuts sample, test after cooling down.The fire-retardant rank of 1.6mm samples is UL94V-0.
Embodiment 9
By polyester PBT, ATMP-Zn, DePAl-1 and compound antioxidant according to 82.6：2：15：0.4 part by weight, is turning
Speed sets temperature to take out cooling after 260 DEG C, 5 minutes, dry to mix in 50 revs/min of banbury.Then it is filled with
In mould, preheated 10 minutes in 260 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Batten is white, treats it
Sample, test are cut after cooling.The fire-retardant rank of 1.6mm samples is UL94V-0.
Comparative example 1
By polyamide PA66-B and compound antioxidant according to 99.6：0.4, mixed in rotating speed is 50 revs/min of banbury
Close, set temperature to take out cooling after 280 DEG C, 5 minutes, dry.Then it is filled with mould, in 280 DEG C of flat board sulphur
Change machine is preheated 10 minutes, after 10MPa pressurizes 5 minutes, cold pressing.Sample is brown.The fire-retardant rank of 1.6mm samples is without rank.
Comparative example 2
By polyamide PA66-A, ATMP-Zn and compound antioxidant according to 84.6：15：0.4 part by weight, be in rotating speed
Mixed in 50 revs/min of banbury, set temperature to take out cooling after 280 DEG C, 5 minutes, dry.Then it is filled with mould
In tool, preheated 10 minutes in 280 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Sample is brown.1.6mm sample
Fire-retardant rank be without rank.
Comparative example 3
By polyamide PA66-B, DePAl-1 and compound antioxidant according to 79.6：20：0.4 part by weight, be in rotating speed
Mixed in 50 revs/min of banbury, set temperature to take out cooling after 280 DEG C, 5 minutes, dry.Then it is filled with mould
In tool, preheated 10 minutes in 280 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Sample treats that its is cold in light brown
But sample, test are cut afterwards.The fire-retardant rank of 3.2mm samples is without rank.
Comparative example 4
By polyamide PA6, DePAl-1 and compound antioxidant according to 79.6：20：0.4 part by weight, is 50 in rotating speed
Rev/min banbury in mix, set temperature be 260 DEG C, 5 minutes after take out cooling, dry.Then it is filled with mould
In, preheated 10 minutes in 260 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Sample is brown, after after its cooling
Cut sample, test.The fire-retardant rank of 1.6mm samples is without rank.
Comparative example 5
By polyester PBT, DePAl-1 and compound antioxidant according to 83.6：16：0.4 part by weight, rotating speed be 50 turns/
Mixed in the banbury of minute, set temperature to cool down, dry for taking-up after 260 DEG C, 5 minutes.Then it is filled with mould,
Preheated 10 minutes in 260 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Sample is white, is cut after after its cooling
Sample, test.The fire-retardant rank of 1.6mm samples is V-1 ranks.
Comparative example 6
By polyamide PA66-A, ATMP-Zn and compound antioxidant according to 69.6：30：0.4 part by weight, be in rotating speed
Mixed in 50 revs/min of banbury, set temperature to take out cooling after 280 DEG C, 5 minutes, dry.Then it is filled with mould
In tool, preheated 10 minutes in 280 DEG C of vulcanizing presses, after 10MPa pressurizes 5 minutes, cold pressing.Sample is brown.1.6mm sample
Fire-retardant rank be without 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 is compared with embodiment 7 as can be seen that using provided herein
Halogen-free flameproof immunomodulator compounds A and compound B be used in combination, preventing polyamide discoloration above with outstanding performance, simultaneously
It also provides good fire resistance 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 more preferable flame retardant rating using cheap ATMP-Zn, this is economically to have very much
Profit.
Table 1
NR：Without rank
The tensile property and bending property of gained sample in embodiment 3, comparative example 3, embodiment 7, comparative example 4 are entered respectively
Row is determined, and acquired results as shown in table 2, as a result illustrate that the physical property of embodiment and comparative example is close.
Table 2
It is described above, only it is several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, but and be not used to limit the application, any those skilled in the art are not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical scheme.
Claims (10)
1. a kind of halogen-free flame retardants, it is characterised 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 acid radical anion and gold that hydrogen atom is formed
Belong at least one of nonacid metal salt of cation formation；
The compound C, which is selected from, has at least one of compound of chemical formula as shown in formula (I)：
In formula (I), R1, R2, R3, R4Independently selected from hydrogen, C1~C8Alkyl and C6~C12Aryl in one kind；X=0,1 or
2, y=0,1 or 2, z=1,2 or 3, and x+y+z=3；
The compound B, which is selected from, has the compound of 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 kind in aryl；
Mm+Metal ion is represented, m is metal M valence state；
In formula (III), A is selected from C1~C10Alkylene, C6~C10Arylene, alkyl substitution arylene, aryl substitution
One kind in alkylene；
R7、R8Independently selected from C1~C8Alkyl, one kind in aryl；
Lp+Metal ion is represented, p is metal L valence state.
2. halogen-free flame retardants according to claim 1, it is characterised in that the compound A and compound B quality
Than for 1~30：1~20；
Preferably, the compound A and compound B mass ratio is 2~15：3~18.
3. halogen-free flame retardants according to claim 1 or 2, it is characterised in that the compound C, which is selected from, has formula (I-1)
The compound of shown chemical formula, with the compound of chemical formula shown in formula (I-2), the chemical combination with chemical formula shown in formula (I-3)
Thing, with the compound of chemical formula shown in formula (I-4), with least one of compound of chemical formula shown in formula (I-5)：
4. the halogen-free flame retardants according to any one of claims 1 to 3, it is characterised in that the metal cation is selected from Zn2 +、Al3+、Ca2+、Mg2+、Fe2+、Fe3+、Ti4+At least one of.
5. halogen-free flame retardants according to claim 1 or 2, it is characterised in that the halogen-free flame retardants includes borate.
6. halogen-free flame retardants according to claim 1 or 2, it is characterised in that the compound B is selected from diethyl phosphinic acids
In salt, Methylethyl phosphinates, ethyl-butyl phosphinates, diphenyl phosphonic acid salt, methylphenylphosphinic acid salt at least
It is a kind of；
Preferably, the compound B is selected from aluminum diethylphosphinate, diethyl phosphinic acids zinc, Methylethyl phosphinic acids aluminium, methyl
At least one of ethylphosphinic acid zinc, ethyl-butyl phosphinic acids aluminium, diphenyl phosphonic acid aluminium, methylphenylphosphinic acid aluminium.
7. a kind of halogen-free flame-retardant polymer material, it is characterised in that contain claim 1 in the halogen-free flame-retardant polymer material
To the halogen-free flame retardants described in 6 any one.
8. halogen-free flame-retardant polymer material according to claim 7, it is characterised in that the compound A is in halogen-free flameproof
Content in high polymer material is 1~30wt%；Contents of the compound B in halogen-free flame-retardant polymer material be 1~
20wt%；
Preferably, contents of the compound A in halogen-free flame-retardant polymer material is 2~15wt%；The compound B is in nothing
Content in halogen flame retarded polymeric material is 3~18wt%.
9. halogen-free flame-retardant polymer material according to claim 7, it is characterised in that the halogen-free flame-retardant polymer material
In high polymer material be selected from least one of polyamide, polyester；
Preferably, the high polymer material in the halogen-free flame-retardant polymer material is selected from polyamide 6, and polyamide 66 gathers to benzene two
At least one of formic acid second diester, polytrimethylene terephthalate, polybutylene terephthalate.
10. halogen-free flame-retardant polymer material according to claim 7, it is characterised in that the halogen-free flame-retardant polymer material
Material includes antioxidant, reinforcing agent, anti-dripping agent, stabilizer, pigment, dyestuff, char forming catalyst, dispersant, nucleator, inorganic
At least one of filler.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057201A (en) * | 2019-12-31 | 2020-04-24 | 南京同宁新材料研究院有限公司 | Low-odor amino trimethylene phosphonate-containing metal salt flame-retardant polyurethane foam material, and preparation method and application thereof |
| CN113881178A (en) * | 2021-09-28 | 2022-01-04 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2017
- 2017-06-22 CN CN201710480414.2A patent/CN107325329B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057201A (en) * | 2019-12-31 | 2020-04-24 | 南京同宁新材料研究院有限公司 | Low-odor amino trimethylene phosphonate-containing metal salt flame-retardant polyurethane foam material, and preparation method and application thereof |
| CN113881178A (en) * | 2021-09-28 | 2022-01-04 | 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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