CN107189427A - A kind of flame retardant compositions - Google Patents
A kind of flame retardant compositions Download PDFInfo
- Publication number
- CN107189427A CN107189427A CN201710489291.9A CN201710489291A CN107189427A CN 107189427 A CN107189427 A CN 107189427A CN 201710489291 A CN201710489291 A CN 201710489291A CN 107189427 A CN107189427 A CN 107189427A
- Authority
- CN
- China
- Prior art keywords
- formula
- salt
- polymer
- fire
- alkyl
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34928—Salts
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- 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
- C08K5/5397—Phosphine oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
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)
- Fireproofing Substances (AREA)
Abstract
The present invention relates to a kind of flame retardant compositions, described composition is included：A) a kind of thermosetting or thermoplastic polymer, b) gross weight based on the flame retardant compositions, by weight from 1% to 60% a kind of fire proofing, the fire proofing is obtained by a kind of method for heating a kind of or more than one compound with formula (I) from 0.01 hour to 25 hours at 220 DEG C or higher of temperature that is included in, and wherein R is C1‑12Alkyl, C6‑10Aryl, C7‑18Alkaryl or C7‑18Aralkyl, wherein the alkyl, aryl, alkaryl or aralkyl are unsubstituted or by halogen, hydroxyl, amino, C1‑4Alkylamino, two C1‑4Alkylamino, C1‑4Alkoxy, carboxyl or C2‑5Alkoxy carbonyl replaces；M is a kind of metal, y be one from 1 to 4 number so that M(+)yA kind of metal cation, wherein (+) y is represented is assigned to the electric charge of the cation in form, and p be one from 1 to 4 number.The present invention relates to a kind of a kind of product containing the flame retardant compositions, especially a kind of electric wire or cable, and it is related to application of the composition in the layer for producing electric wire or cable.
Description
Technical field
1st, the present invention relates to a kind of flame retardant compositions, it is related to a kind of system comprising the flame retardant compositions
Product, especially a kind of electric wire or cable, and it is related to application of the composition in the layer for producing electric wire or cable.
Background technology
2nd, in order to improve the fire resistance of polymer, several method is well known in the art.First, the polymer
The compound for including halide is known.But, these materials release the harmful of such as hydrogen halides after having burning
And the shortcoming of corrosive gas.This is also based on the shortcoming of PVC flame retardant compositions.
In another approach, fire-retardant combination includes relatively great amount of, usually 50-70wt% inorganic filler, example
Such as hydrate and hydroxide, the inorganic filler in combustion in the range of 200-600 DEG C at a temperature of be heated point
Solve and discharge inert gas.Such inorganic filler is for example including Al (OH) 3 and Mg (OH) 2.But, such fire-retardant material
The shortcoming of material is the cost height of inorganic filler and because mass filler causes machinability and degraded in mechanical properties.
The content of the invention
3rd, polymer, such as TPO, polyesters, polycarbonate-based, polyamide-based, polyurethanes, epoxy resin, with
And other thermoplasticity or thermoset polymer resin class, frequently by combining a kind of phosphorous compound wherein, it is halogen
The compound or its mixture of element are made into more fire retardants.For example, United States Patent (USP) 3,689,602 discloses the phosphoric acid of halogenation
Ester is as flame retardant of plastic additive.
4th, these polymer are processed under high temperature (such as 200 DEG C, 220 DEG C, 250 DEG C or higher), and it is many known
Fire retardant due to they it is too volatile, inadequate it is thermally-stabilised, processing had adverse effect etc. be under these conditions
It is unsuitable.Some organophosphorous fire retardant compounds, such as some phosphates, it is also possible to show a kind of plasticization, it may not
The mechanical property of polymer being added in them is influenceed sharply.In addition, if some phosphatic compounds are phases for hydrolysis
To unstable, it may cause the formation of undesirable different phosphate cpds.
5th, phosphorous sour salt is known flame-retardant additive, is specifically used for thermoplastic polymer.United States Patent (USP) 3,
894,986 disclose the flame-retardant thermoplastic polyester of the alkali metal salt comprising phosphonic acids, and the sodium salt or alkane of such as ethane-phosphonic acids-
The sodium salt of the mono-methyl of phosphonic acids.US 4,972,011 discloses the aluminium salt of the monoalkyl ester of alkyl phosphonic acid or alkane-phosphonic acids, i.e.
The salt of compound with formula (Ia), wherein R is such as methyl, ethyl, propyl group or isopropyl etc., unsubstituted or by one
Individual or multiple halogen or oh group substitutions；And R' is hydrogen, methyl, ethyl, propyl group or isopropyl
6th, DE 3833977 disclose from dimethyl methyl phosphinate and metal oxide or hydroxide in water
The metal salt of high pressure and the compound with formula (Ia) prepared from the reaction at a temperature of 120 to 200 DEG C；Illustrate water-soluble
The reaction run at an elevated pressure at a temperature of up to 190 DEG C in an autoclave in liquid.Further disclose these salt
The fire retardant in thermoplastic is used as with the adduct of amine (such as ethylenediamine and melamine), and these adducts
Purposes.
7th, for thermoplastic polymer it is also known that flame-retardant additive be phosphinic acids salt, i.e. the change with formula (II)
Compound, wherein R1 and R2 are alkyl or carbon-based aromatic
8th, wherein M is the nitrogen selected from Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Li, Na, K or protonation
The salt of base is known.For example, US 5,780,534 and 6,013,707 discloses phosphinic acids calcium and time phosphine with formula (II)
Sour aluminium is particularly effective in the polyester, for example, dimethylphosphinic acid, ethylimethyphosphinic acid, diethyl phosphinic acids, n-propyl
Methyl-phosphinic acid, n-propyl ethylphosphinic acid, diη-propyl phosphinic acids, the calcium of diisopropyl phosphinic acids or diphenyl phosphonic acid and
The salt of aluminium.
9 such as with many flame-retardant system identicals, the performance of phosphorous acid derivative can pass through other fire retardants, synergist
Presence with adjuvant strengthens.United States Patent (USP) 6,472,448 discloses flame retarded rigid polyurethane foams, wherein alkoxylate
(oxalkylated) a kind of combination of alkyl phosphonic acid and ammonium polyphosphate exists as fire retardant.
10 United States Patent (USP)s 6,365,071, which disclose one kind, is used for thermoplastic polymer such as engineering plastics, particularly for poly-
The fire-retardant combination of the synergy of esters, the combination includes A) a kind of phosphinates with above formula (II), for example, the secondary phosphine of dimethyl
Sour aluminium, Methylethyl phosphinic acids aluminium and methylpropylphosphinic acid aluminium, and B) a kind of nitrogen compound such as allantoin is (2,5- bis-
Oxygen -4- imidazolidinyls) urea, phenyl guanamines, glycoluril be imidazolidine simultaneously [4,5-d] imidazoles -2,5- diketone, urea cyanurate, three
Poly cyanamid cyanurate and melamine phosphate.
11 United States Patent (USP)s 6,255,371 disclose a kind of flame retardant combination, and the combination includes A) it is a kind of with above formula (II)
Phosphinates, for example, a kind of diethyl phosphinates, wherein M are calcium, magnesium, aluminium and/or zinc, and B) contracting of melamine
Close or reaction product, such as melamine polyphosphate, melam polyphosphate and melem polyphosphate.
12 United States Patent (USP)s 6,547,992 disclose a kind of flame retardant combination for thermoplastic polymer, and the combination is comprising secondary
Phosphonate and a small amount of inorganic and/or mineral compound, it does not include nitrogen.WO 2012/045414 discloses a kind of flame retardant combination
Thing, said composition include A) a kind of phosphinates with above formula (II), wherein M be selected from Mg, Ca, Al, Sb, Sn, Ge,
The nitrogen base of Ti, Zn, Fe, Zr, Ce, Bi, Li, Na, K or a kind of protonation；B a kind of) metal salt of phosphorous acid；And other
The component of choosing.
13 phosphinates cited above, such as United States Patent (USP) 6,365,071 and 6,255,371, it is stated that be it is heat-staple,
And these polymer are neither decomposed during processing and nor affect on the technique for preparing the plastics composite.These phosphinates exist
It is not volatile under the conditions of the preparation of thermoplastic polymer and the common of processing.However, these materials are not necessarily suitable for being used for
In all polymeric systems and can produce the problem of for processing or may lack for some polymer need resistance
Fuel efficiency fruit.For for prepare with highly desirable physical characteristic flame retardant compositions in relatively low addition
The fire retardant with larger effect and improved machinability still suffers from a kind of needs under agent concentration.
14 phosphonates, i.e. according to the salt of the metal salt of the compound of formula (Ia), it is heat-staple to be also reported, but is worked as
So this is a relative word.As disclosed in US 2007/0029532, the decomposition of such phosphonate in the method exists
It is well known at a temperature of running into, in the process of polyester and polyamide, so as to damage these polymer.
16 United States Patent (USP)s 5,053,148 are disclosed by the way that metal phosphinate hydrochlorate or metal phosphinate hydrochlorate precursor to be heated to being more than
The heat resistance foam that 200 DEG C of temperature is obtained, the foam is useful for example as electricity and/or heat insulation material.Also disclose
This reaction expands other substrates or makes other substrates porous purposes.Such substrate includes, for example, thermoplastic polymer
Or plastics such as aromatic polyester, polyethers, polysulfide, polyamide, makrolon, polyimides, polysiloxanes or polyphosphazene, make
It can be introduced into the foaming operation for a kind of mixture with metal phosphinate hydrochlorate and/or its precursor.
17 although United States Patent (USP) 5,053,148 may indicate a kind of porous polyamide can be according to " foaming method "
Produced by the mixture for heating a kind of metal phosphinate hydrochlorate and polyamide, without solution or negative in United States Patent (USP) 5,053,148
US 2007/0029532 disclosure, the at high temperature decomposition of such phosphonate is generated as a kind of engineering thermoplasties'
" disabled frangible composition ".Can be by heating metal phosphinate hydrochlorate and a kind of as poly- except being proposed a kind of porous foam
Beyond the polymer of acid amides is produced, United States Patent (USP) 5,053,148 does not include carrying for the possibility characteristic of such a non-illustration material
And.
18 have been had been acknowledged by experiment the tired of some thermoplastic resins are heat-treated in the presence of alkyl phosphonic acid metal salt
Be difficult to and thus obtained polymer composition poor physical characteristic.But, it has now been found that lead at a temperature of more than 200 DEG C
Cross heat some alkyl phosphonic acid metal salts (such as aluminium salt, calcium salt, zinc salt) acquisition product be at a temperature of more than 400 DEG C
It is heat-staple, and can be bonded to thermojunction on thermoplastic polymer resin, the polymer group obtained without negatively affecting
The produced physical characteristic of compound.It moreover has been found that include the present invention fire retardant polymer composition, for example thermosetting or
Thermoplastic compounds, or individually or combined with other fire retardants, synergist or adjuvant, illustrate excellent anti-flammability.
19 summary of the inventions
Compound with formula (I)
Wherein y be one from 1 to 7 number, such as from 1 to 4, M be one have (+) y formal charge metal sun from
Son, p is one, and from 1 to 7 number, for example from 1 to 4, and R is such as alkyl, aryl, alkaryl or aralkyl, when more than
At a temperature of 200 DEG C, such as at 220 DEG C to 250 DEG C or higher, such as from 200 DEG C, 220 DEG C or 250 DEG C to 400 DEG C of temperature
Experience reaction is to form a kind of different chemical species during lower heating compound, and it is typically for 400 DEG C and higher temperature
Degree is heat-staple and is well suited for use as flame-retardant additive in the polymer.These reaction products have improved resistance
Fire characteristic and be related to the compound with formula (I), and be easier to be processed to fluoropolymer resin, such as polyamide, without
Negatively affect the physical characteristic of the resin.The mechanism now acted on is uncertain, however, when the material and time phosphine of the present invention
Hydrochlorate (that is, the compound with formula (II)), which is combined, obtains excellent and unexpected result when using, and at certain
Plant the possibilities for being indicated in meaning and there may be different and complementary (complimentary) activity two kinds of materials.
20 the invention provides a kind of fire retardant, and the fire retardant is included to be obtained by compound of the heat treatment with formula (I)
Product, it is a kind of to be used to prepare the synergistic blend (example of the fire retardant, the fire retardant and other fire retardants or retardant synergist
Such as, the blend of fire retardant of the invention and phosphinates) and fire retardant comprising the present invention or synergistic blend polymerizeing
The method of compositions.
21 additionally provide a kind of method for preparing flame-retardant polymer, and this method, which is included in, turns compound chemistry
The compound with formula (I) is somebody's turn to do in heating under conditions of being changed into the heat-staple fire proofing of the present invention as described above, and
Then the heat-staple fire retardant prepared in this way is bound in a kind of fluoropolymer resin, for example, led at elevated temperatures
Cross the melt-processed polymer and fire retardant.One specific embodiment is provided a method that, wherein will have by heating
Heat-staple fire retardant prepared by the compound of formula (I) is added to one together with the phosphinates and/or other synergist of formula (II)
Plant in fluoropolymer resin.
22 Brief Description Of Drawings
Fig. 1 shows the heat analysis data of three-[methylphosphonic acid] aluminium salts prepared according to comparison example 1, and it is to be used in fact
The parent material of the fire proofing of example 1.
Fig. 2 shows the heat analysis data of the fire proofing of example 1.
The content of the invention
23 one embodiment of the present of invention are a kind of flame retardant compositions, and said composition includes：
A) a kind of thermosetting or thermoplastic polymer, for example, a kind of thermoplastic polymer,
B) gross weight based on the fire-retardant combination, by weight from 1% to 50% a kind of fire proofing, the fire-retardant material
Material is by by a kind of or more than one phosphonate, i.e. the compound with formula (I)
Wherein R is an alkyl, aryl, alkaryl or aromatic alkyl group, p be one from 1 to 7 number, for example, from 1 to
4, for example, 1,2,3 or 4, M be a kind of metal, y be one from 1 to 7 number, such as from 1 to 4, for example, 1,2,3 or 4, often 2
Or 3 so that M (+) y is a kind of metal cation, wherein (+) y represents the electric charge for being assigned to the cation in form,
24 at 200 DEG C or higher, such as 220 DEG C or higher of temperature, generally at 250 DEG C or higher, for example from 250 DEG C
Heat and obtain at a temperature of to 400 DEG C or from 260 DEG C to 360 DEG C, and
C) fire retardant or retardant synergist optionally added.
25 for example, in formula (I), wherein y is 1 M(+)yRepresent a kind of single cation, such as Li+、Na+Or K+, wherein y is 2
M(+)yRepresent a kind of two cation, such as Mg++, Ca++ or Zn++ and the like, wherein y are that 3 M (+) y represents one kind three
Cation, such as Al+++.Such as common with organometallic species, the formula is preferable and these parent materials may include it
In some valences be shared complex salt or salt, such as one of them single oxygen anion quilt between two metal cations
It is shared.Typically, the salt of the starting is charge balance, i.e. one kind has the compound of formula (I), wherein p=y, for example, working as M
When (+) y is Na+, p is 1, and when M is Al+++, p is 3 etc..
Although 26 need not be bound by theory, spectroscopic data analysis shows the Temperature Treatment model in the present invention with other
The heat treatment that one kind in enclosing has the compound of formula (I) generates a kind of material, and the material includes a kind of compound and it is answered
The dehydration product of conjunction, the compound is considered as universally to be represented by experience formula (IV)：
Wherein R and M be such as defined in formula (I), q be one from 1 to 7 number, such as 1,2 or 3, r are one from 0
To 5 number, such as 0,1 or 2, often 0 or 1, y be one from 1 to 7 number, such as from 1 to 4, and n is 1 or 2, and its condition is
2 (q)+r=n (y).Typically, a kind of material is generated according to the heat treatment of compound of the present invention with formula (I), the material
Including more than one compound and its compound dehydration product, at least one of these compounds is considered as universally to be passed through
Test formula (IV) representative.Such as common with organometallic species, formula (IV) is preferable and the product may include the salt of polymerization, network
Salt, some of which valence are shared salt etc..
27 for example, when M is aluminium, i.e. when the compound that one kind that wherein M is Al has formula (I) is added according to the present invention
When hot, elementary analysis indicates a kind of formation of the product with experience formula (IV), and wherein q is that 1, r is that 1, n is that 1 and y is 3,
That is, it is a kind of with wherein M be Al, q be 1, r be 1 and y be 3 experience formula (IV) product.
The fire proofing ratio obtained according to the present invention has the starting phosphonate of formula (I) more thermally-stabilised and illustrated bigger
Anti-flammability and in multiple polymers resin have improved machinability.
The polymer of the fire-retardant combination of 28 present invention can be any polymer as known in the art, such as, polyene
Hydrocarbon homopolymer and copolymer, rubber, polyester, epoxy resin, polyurethane, polyalkylene terephthalates, polysulfones, polyamides are sub-
Amine, polyphenylene oxide, styrene polymer and copolymer, makrolon, acrylate copolymer, polyamide, polyacetals, epoxy resin with
And biodegradable polymer.The mixture of different polymer can also be used, such as polyphenylene ether/styrene resin fat is blended
The polymer of thing, polyvinyl chloride/ABS or other impact modifications, the ABS such as containing methacrylonitrile and α-methylstyrene, with
And polyester/ABS or makrolon/ABS and the polyester plus some other anti-impact modifiers.Such polymer is commercially available
Or manufacture by means well known in the art.
The fire retardant of 29 present invention is particularly useful in the thermoplastic polymer for being processed and/or using at high temperature
, such as styrene polymerization species, TPO, polyesters, polycarbonate-based, polyamide-based, polyurethanes including HIPS,
Polyphenyl ethers and the like.
For example, the polymer can be a kind of resin of polyester series, it is styrene resin, the resin of polyamide series, poly-
Resin, the resin of polyphenylene oxide series, resin, olefin resin, acrylic resin, the asphalt mixtures modified by epoxy resin of vinyl series of carbonic ester series
Fat or polyurethane.The polymer can be a kind of thermoplasticity or heat cured resin and can be enhanced, for example, glass increases
Strong.There may be more than one fluoropolymer resin.In the particular embodiment, the polymer is a kind of engineering polymers, example
Such as, a kind of thermoplasticity or enhanced thermoplastic polymer, for example, the thermoplastic polymer of glass strengthening, such as a kind of optionally glass
Polyester, epoxy resin or the polyamide of glass filling, for example, a kind of for example a kind of glass-filled of polyester of glass-filled is poly- to benzene two
Formic acid alkylene ester, or a kind of polyamide of glass-filled.
The resin of 30 polyester series includes for example by a kind of dicarboxylic acid component and a kind of polycondensation of diol component, with
And the equal polyester and copolyester that the polycondensation of a kind of hydroxycarboxylic acid or a kind of lactone component is obtained, such as aromatic saturation
Polyester series resin, such as polybutylene terephthalate or PET.
The resin of 31 polyamide series includes being derived from a kind of diamines and a kind of polyamide of dicarboxylic acids；From a kind of aminocarboxylic
The polyamide that sour (if necessary being combined with a kind of diamines and/or a kind of dicarboxylic acids) obtains；And (must derived from a kind of lactams
Will if combined with a kind of diamines and/or a kind of dicarboxylic acids) polyamide.The polyamide also includes a kind of derived from least two
The copolyamide of different types of polyamide constituent component.The example of the resin of polyamide series includes fatty polyamide such as Buddhist nun
Dragon 46, nylon 6, nylon66 fiber, NYLON610, nylon 612, nylon 11 and nylon 12, from a kind of aromatic dicarboxylic acid (for example, right
Phthalic acid and/or M-phthalic acid) and a kind of aliphatic diamine (for example, hexamethylene diamine or nonamethylene diamine) obtain polyamide, with
And from both aromatic series and aliphatic dicarboxylic acid (such as both terephthalic acid (TPA) and adipic acid) and a kind of aliphatic diamine (example
Such as, hexamethylene diamine and other) obtain polyamide.These polyamide can be used alone or in combination.
32 in one embodiment of the invention, and the polymer includes a kind of polyamide, typically in such as 300 DEG C of high temperature
Or higher, 320 DEG C or higher in certain embodiments, such as 340 DEG C or the processing of more relative superiority or inferiority.The example of high temperature polyamide includes heat
Plastic resin, such as nylon 46, nylon 4T, nylon 6T/66 copolymers, nylon 9 T and the like.
33 fire retardants (b) in polymeric system or as unique fire retardant or with other fire retardants, increase
Effect agent or adjuvant, which are combined, illustrates excellent activity.Concentration of the fire retardant of the present invention in the polymer composition takes certainly
Accurate chemical composition certainly in the fire retardant, the polymer found in final polymer composition and other components.Example
Such as, when unique flame retardance element as a kind of polymer formulation, fire retardant of the invention can be with by weight from 1%
Concentration to the gross weight of 50%, such as 1% to 30% final composition is present.Typically, when as unique fire-retardant
During agent, it will the material of the invention for having at least 2% is present, such as 3% or more, 5% or more, 10% or more,
15% or more, 20% or more or 25% or more.In many embodiments, fire retardant of the invention is with up to
45% amount is present, while in other embodiments, the amount of fire retardant of the invention be the polymer composition 40% or more
It is few, such as 35% or less.It is apparent that when to be applied in combination with other fire retardants or retardant synergist, it should need less
Material of the invention.
34 any of mixed technologies can be used for the flame retardant compositions for preparing the present invention, for example, can be with
The fire retardant is introduced in molten polymer by blending, extrusion, into fiber or film forming etc..In some cases, poly-
The fire retardant is introduced in the polymer when compound formation or solidification, such as can be by the resistance of the present invention before crosslinking
Fire agent to be added in a kind of polyurethane prepolymers, or a kind of polyamine or alkane can be added it to before polyamide formation
In based polycarboxylic acid compound, or it is added to before curing in a kind of epoxy mixture.
35 other embodiments of the invention are the fire proofing and the fire proofing and the synergistic blend of other components.This
The fire retardant of invention is by by a kind of or more than one phosphonate, the i.e. compound with formula (I)
36 wherein R are an alkyl, aryl, alkaryl or aromatic alkyl group, p be one from 1 to 7 number, such as 1 to 4,
For example, 1,2,3 or 4, M be a kind of metal, y be one from 1 to 7 number, such as 1 to 4, for example, 1,2,3 or 4 so that M (+) y
A kind of metal cation, wherein (+) y is represented is assigned to the electric charge of the cation in form, 200 DEG C or higher, for example
At 220 DEG C or higher of temperature, generally at 250 DEG C or higher, for example from 250 DEG C to 400 DEG C or from 260 DEG C to 360 DEG C
At a temperature of heat obtain.As described above, by heating the material that the compound with formula (I) is produced at a temperature of listing
Material is considered as a kind of mixture of the compound or one or more compounds generally represented by experience formula (IV)：
37 wherein R and M be such as defined in formula (I), q be one from 1 to 7 number, such as 1,2 or 3, r are one
From 0 to 5 number, such as 0,1 or 2, often 0 or 1, y be one from 1 to 7 number, such as from 1 to 4, for example, 1,2,3 or 4, and
And n is 1 or 2, its condition is 2 (q)+r=n (y).
38 phosphonates with formula (I) are known and describe the not Tongfang for preparing them in the art
Method.For example, US 2006/0138391 discloses the compound with formula (I), wherein R is hydrogen, C1-18 alkyl, C5-6 cycloalkanes
Base, C2-6 alkenyls, C6-10 aryl or C7-11 aralkyl, its alkyl, alkenyl, aryl or aralkyl can be it is unsubstituted or
Person is taken by halogen, hydroxyl, amino, C1-4 alkylaminos, two-C1-4 alkylaminos, C1-4 alkoxies, carboxyl or C2-5 alkoxy carbonyls
Generation；And M can be selected from, for example, IA, IB, IIA, IIB, IIIA, IVA, VA or VII race of the periodic table of elements, such as Li,
K, Na, Mg, Ca, Ba, Zn, Ge, B, Al, Cu, Fe, Sn or Sb etc..It is pointed out that in US 2006/0138391, without one
The compound planted corresponding to above formula (I) is heated more than 200 DEG C or at elevated temperatures by a kind of mixture to polymer tree
In fat.Unique salt of actually illustration is the aluminium salt of methyl methane phosphonic acid in US 2006/0138391, i.e. with above formula
(Ia) salt of compound, wherein R and R' are methyl, i.e.,：
39 are used for the parent material of the fire retardant of the present invention, i.e. the compound with formula (I), can be conveniently selected from
US 2006/0138391 and the salt disclosed in the other places of this area.The compound with formula (I) useful in the present invention
The other R groups not found in US 2006/0138391 are additionally may included in, such as by alkyl-substituted aryl, and are had
The compound with formula (I) that may be included without specifically mentioned metal cation as parent material can be useful
's.
40 in some embodiments of the invention, the salt with formula (I) include wherein R be C1-12 alkyl, C6-10 aryl,
The compound of C7-18 alkaryls or C7-18 aromatic alkyl groups, wherein the group is further substituted, such as in US 2006/
Described in 0138391, but often R is unsubstituted C1-12 alkyl, C6-10 aryl, C7-18 alkaryls or C7-18 virtues
Alkyl.It is typically unsubstituted for example, R is substituted or unsubstituted, C1-6 alkyl, C6 aryl, C7-10 alkaryls or
C7-12 aralkyl, for example, C1-4 alkyl, C6 aryl, C7-19 alkaryls or C7-10 aralkyl.
41 however the present invention most general embodiment in, M (+) y can be substantially any metal cation, and M is usual
Selected from Li, K, Na, Mg, Ca, Ba, Zn, Zr, Ge, B, Al, Si, Ti, Cu, Fe, Sn or Sb, for example, as Li, K, Na, Mg, Ca,
Ba, Zn, Zr, B, Al, Si, Ti, Sn or Sb, in many embodiments M be Li, K, Na, Mg, Ca, Ba, Zn, Zr, B, Al, Sn or
Sb, and M is Al, Zn or Ca in certain embodiments.For example, realizing excellent result when M is Al or Ca.
42 as the R of alkyl be one have specific carbon number straight or branched alkyl group and including, for example,
The alkyl of non-branched such as methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, 12
Alkyl, and non-branched alkyl such as isopropyl, isobutyl group, sec-butyl, the tert-butyl group, ethylhexyl, t-octyl and the like.
For example, R is methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group as alkyl, frequent R be methyl,
Ethyl, propyl group or isopropyl, such as methyl.
Typically, when R is aryl, it is phenyl or naphthyl, for example, phenyl.Include as the example of R alkaryls by one
The phenyl of individual or multiple alkyl groups substitution, be selected from methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl,
The group of the tert-butyl group and the like.As aralkyl R example include for example, benzyl, phenethyl, styryl, cumyl,
Phenylpropyl and the like.
43 in one embodiment, and R is methyl, ethyl, propyl group, isopropyl, phenyl or benzyl, such as methyl or phenyl.
In certain embodiments, for example, the parent material is a kind of compound with formula (I), wherein R is methyl, second
Base, propyl group, isopropyl, benzyl or phenyl, M are Al, Zn or Ca, and p is 2 or 3.In a specific embodiment, R is first
Base, ethyl, propyl group, isopropyl or phenyl, p=3 and M are Al；In another specific embodiment, R be methyl, ethyl,
Propyl group, isopropyl or phenyl, p=2 and M are Zn or Ca, such as Ca.
44 by have formula (I) phosphonate be converted into the present invention fire retardants spend time amounts will depend on it is a variety of because
Element and change, these factors include, for example, the chemical constitution of starting phosphonate, the temperature of reaction, others reaction condition etc..
For example, higher temperature can cause the faster reaction time.It is believed that producing water and a kind of water absorbing agent in the course of reaction
Or the presence of vacuum can also reduce the reaction time.The design of reactor, in heating process presence of other materials etc. also
The time of reaction can be influenceed.
45 by one kind often at for example, at least 200 DEG C, 220 DEG C, 250 DEG C or higher of temperature by having formula (I)
The time that phosphonate is heated 20 hours or less, is typically less than 12 hours obtains good conversion.In some cases, should
Time can be very short, such as using higher temperature, such as 250 DEG C to 400 DEG C or the temperature more than 400 DEG C, one
The reaction time can be greatly reduced to for example, small in the reactor or environment for causing heat efficiently to pass to the parent material by planting
It is possible in 0.2 hour, 0.1 hour or 0.01 hour or less, and with the complete reaction time of second or smaller measurement
's.
46 generally, to the fire retardant of the present invention complete conversion be by a temperature of from 200 DEG C to 400 DEG C by this
The heating of beginning phosphonate is obtained from 0.01 or 0.2 to 20 hour, from 0.1 or 0.2 to 12 hour or from 1 to 8 hour, but such as
The amount of time discussed above for converting completely will depend on the temperature.For example, being heated at from 250 DEG C to 400 DEG C
Phosphonate with formula (I) will need the heating less than 12 (such as from 1 to 8) hours.When the starting phosphonate from 260 DEG C to
Heated 1 to 6 hour at 340 DEG C, such as at 2 to 6 hours, have been obtained for excellent result.
47 for example, by three-[methylphosphonic acid] aluminium salts, i.e. one kind has water-soluble solid compound (the wherein R of formula (III)
Methyl), from heating at a temperature of 250 to 320 DEG C 2 to 6 hours to form a kind of solid material, i.e. compared to starting material
Material, it is insoluble in water and stable at a temperature of more than 400 DEG C.Higher reaction temperature can be used, however, such as at this
Seen in a little examples, heated at 280 DEG C 4 hours and produce excellent result.
Similarly, three-[ethylphosphonic acid] aluminium salts are heated, i.e. the compound wherein R with formula (III) is ethyl, or
Three-[phenyl-phosphonic acid] aluminium salts, i.e. the compound wherein R with formula (III) is phenyl, cause to include class at similar conditions
Like ethyl and the fire proofing of phenyl.
48 generally, the mixture independent heating of selected phosphonic acid metal salt or salt as parent material, i.e. be not present
Other materials.However, people can be such as a kind of inert carrier, another fire retardant or other possible additives
These salt are heated Deng in the presence of, although the presence of water of addition is typically avoided by, as it is believed that during the course of the reaction water from this
It is eliminated in parent material.For example, can be by these parent materials and other fire proofings, poly- before heating is more than 200 DEG C
Polymer stabilizer or the mixing of other known polymeric additive.The thermal transition of these salt can also be in a kind of a small amount of polymerization
Thing occurs as in the presence of inert carrier, however, people must be careful to avoid the conversion of the wherein starting salt by other materials
There is a situation where hindered.For example, a kind of polymer or other materials can at the reaction temperatures melt and coat the salt,
Or even with the reactant salt, so as to produce undesirable result.
50 in many embodiments, and compound of the one kind with formula (I) is heat-treated in the absence of experience under other components.Such as
There are a kind of polymer or other inert carriers in fruit, it exists with the amount of the amount less than phosphonic acid metal salt in the course of reaction,
For example, the combination of phosphonic acid metal salt and polymer by weight is less than 50% or less than 25%, typically it is less than by weight
10%, it is, for example, less than 5% or from 0 to 2%.Due to having the salt of formula (I) to be considered as discharging water in the reaction, it may be desirable to keep away
Exempt to heat the salt in the presence of following material more than 200 DEG C, the material is unstable at high temperature in the presence of water, including can
Undergo the material of the polymer of hydrolysis.
51 according to the present invention, the phosphonic acid metal salt with formula (I) its be incorporated in its protection polymer body it
Before be thermally transformed by the reproducing beam as a kind of different, more thermally stable fire proofings.With salt (it is also referred to as fire retardant) phase with formula (I)
Instead, this fire retardant is stable under the processing temperature more than 200 DEG C and do not suffer from may be for such as polymer (such as polyester
And polyamide) reaction that has adverse effect, these polymer include be easy to react and be broken bonded.
52 for example, poly- phthalic acid alkylene ester, polyamide and a lot of other condensation polymers are processed at high temperature.
At high temperature, the salt experience with formula (I) substantially discharges the reaction of water, and this can cause the hydrolysis in the case where ester or acid amides are bonded
(hydolysis),
53 so as to the loss for causing chain rupture and molecular weight and desired physical characteristic.In comparison example 1, tasted
Try a kind of salt with formula (I) being combined into a kind of polyamide of glass-filled at elevated temperatures, so as to cause polymerization
Thing is degraded.Although whether being responsible for observed degraded being not in the elimination of the heat treatment process reclaimed water of the salt with formula (I)
Know, the fire retardant of the invention from example 1,2 and 3 is successfully bound in the polyamide of identical glass-filled,
Without obvious degraded.
The fire retardant of 54 present invention can be with various other fire retardants, synergist or fire-retardant auxiliary as known in the art
Agent is used together.For example, the fire retardant of the present invention can be prepared with one or more materials selected from following item：
Carbon black, graphite, CNT, silicone；Polyphenylene oxide (PPE), phosphine oxide and polyoxygenated phosphine, such as benzyl phosphine oxide,
Poly- benzyl phosphine oxide and the like；
Melamine, melamine derivative and condensation product, melamine salt, e.g., but are not limited to, melamine cyanogen
Urea hydrochlorate, melamine borate salt, melamine phosphate, melamine metal phosphate, and the like；
Inorganic compound, including clay, metal salt, such as hydroxide, oxide, oxide hydrate, borate, carbonic acid
Salt, sulfate, phosphate, phosphite, hypophosphites, silicate, metal salt of mixing etc., for example, talcum and other silicon
Sour magnesium, calcium silicates, alumino-silicate, alumino-silicate (DRAGONITE), calcium carbonate, magnesium carbonate, barium sulfate, sulphur as hollow pipe
Sour calcium, galapectite or boron phosphate, calcium molybdate, the vermiculite stripped off, zinc stannate, zinc hydroxyl stannate, zinc sulphide and Firebrake ZB, zinc molybdate
(KEMGARD 911A/B), trbasic zinc phosphate (KEMGARD 981), magnesia or magnesium hydroxide, aluminum oxide, oxide hydroxide
(boehmite), aluminum trihydrate, silica, tin oxide, antimony oxide (III and V) and oxide hydrate, titanium oxide and oxygen
Change zinc or oxide hydrate, zirconium oxide and/or zirconium hydroxide and the like.
55 unless otherwise indicated, in the context of this application, term " phosphate ", when with " phosphate " be used as a kind of group
Timesharing, such as with metal phosphate, melamine phosphate, melamine metal phosphate, it must be a kind of phosphate, phosphorus to refer to
Sour hydrogen salt, dihydric phosphate, pyrophosphate, polyphosphate or a kind of anion or polyanion of phosphoric acid condensation product.
Equally, unless otherwise indicated, in the context of this application, term " phosphite " is used as when with " phosphite "
During a kind of component, such as with metal phosphinates, it must be a kind of phosphite or phosphorous acid hydrogen salt to refer to.
The fire retardant of 56 present invention can also be prepared with other fire retardants, such as
Fire retardant, alkyl or aryl phosphine oxide fire retardant, alkyl or aryl phosphate flame retardants, the alkyl or aryl of halogenation
The salt of phosphonate, alkyl or aryl phosphinates and alkyl or aryl phosphinic acids.One specific embodiment provides one kind
The fire retardant of the present invention and a kind of a kind of synergy of the phosphinates (for example, three (dialkyl phosphinic acid) aluminium) with formula (II) are mixed
Compound.
57 therefore, in many embodiments, includes polymer (a), fire-retardant according to the flame retardant compositions of the present invention
Agent (b), and further comprise the additional fire retardant of (c) one or more, and/or one or more synergist or fire-retardant auxiliary
Agent.
58 for example, in certain embodiments, the flame retardant compositions include one or more other fire retardants, example
Such as, the salt of the fire retardant of halogenation, phosphine oxide fire retardant, alkyl or aryl phosphonate or alkyl or aryl phosphinic acids, for example, one
Plant three (dialkyl phosphinic acid) aluminium, such as three (diethyl phosphinic acids) aluminium.
59 in certain embodiments, and the flame retardant compositions include one or more synergist or fire-retardant adjuvant,
For example, melamine, melamine derivative and condensation product, melamine salt, phosphine oxide and polyoxygenated phosphine, metal salt
(such as hydroxide, oxide, oxide hydrate, borate, phosphate, phosphite, silicate and the like), example
Such as, hydrogen phosphite aluminium, melem or a kind of melamine metal phosphate, such as a kind of wherein metal include aluminium, magnesium or zinc
Melamine metal phosphate.In the particular embodiment, the other fire retardant of the one or more, synergist or fire-retardant auxiliary
Auxiliary agent includes the polyarylether of a kind of three (dialkyl phosphinic acid) aluminium, hydrogen phosphite aluminium, methylene-diphenyl phosphine oxide-substituted, benzene
Double (diphenyl phosphine oxide the ylmethyl) -1,1'- biphenyl of dimethyl double (diphenyl phosphine oxides), 4,4'-, ethylenebis -1,2- pairs -
(9,10- dihydro-9-oxy -10- phospho hetero phenanthrene -10- oxides) ethane, melem or double melamine pyrophosphoric zinc.
60 1 specific embodiments are the synergy of a kind of fire retardant comprising the present invention and three (diethyl phosphinic acids) aluminium
Mixture.
For example, the fire retardant of the present invention can be with a kind of other fire retardant, synergist or adjuvant with the resistance of the present invention
Fire agent and the gross weight by weight 100 of other fire retardant, synergist or adjuvant:1 to 1:Combined in the range of 100.Take
Certainly in other fire retardant, synergist or the adjuvant, by weight 10 are used:1 to 1:The fire retardant of 10 scope with addition
Fire retardant, synergist and/or adjuvant can obtain excellent results, such as from 7:1 to 1:7、6:1 to 1:6、4:1 to 1:4、
3:1 to 1:3 and 2:1 to 1:2 weight is used for good interests than scope.The fire retardant of the present invention is typically such a
Key component in combination, for example, by weight 10:1 to 1.2:1 ratio or 7:1 to 2:The fire retardant of the invention of 1 ratio
Material and other fire retardant, synergist and/or adjuvant, but the material of the present invention can also be secondary group of the mixture
Point, for example, 1:10 to 1:1.2 ratio or 1:7 to 1:The fire retardant of 2 ratio and additional fire retardant, synergist and/or auxiliary
Auxiliary agent synergist.
The flame retardant compositions of 61 present invention will also typically comprise the one or more of following item：In the art
Frequently encounter conventional stabilizer or other additives such as phenolic antioxidant, hindered amine as light stabilizer (HALS), UV Absorption
Agent, phosphite, phosphinate, the alkali metal salt of aliphatic acid, hydrotalcite, metal oxide, borate, epoxidised soybean
Oil, azanol, tertiary amino oxides, lactone, the thermal response product of tertiary amino oxides, sulfur synergist class, Basic co-stabilisers (basic
Co-stabilizers) (for example, melamine, melem etc.), polyvinylpyrrolidone, dicyandiamide, cyanuric acid alkatriene third
Ester, urea derivative, hydrazine derivate, amine, polyamide, polyurethane, hydrotalcite, the alkali metal salt and alkaline-earth metal of higher fatty acids
Salt is (for example, calcium stearate, CSL, calcium lactate, zinc stearate, zinc octoate, magnesium stearate, natrium ricinoleicum and palm
Sour potassium, catechol antimony (antimony pyrocatecholate) or catechol zinc (zinc pyrocatecholate)),
Nucleator, fining agent etc..
Other additives can also be present, for example, plasticizer, lubricant, emulsifying agent, pigment, dyestuff, light brightener, its
His fire-proofing chemical, antistatic additive, foaming agent, anti-drip agents (such as PTFE), and the like.
62 optionally, and the polymer may include filler and reinforcing agent, for example, calcium carbonate, silicate, glass fibre, cunning
Stone, kaolin, mica, barium sulfate, metal oxide and hydroxide, carbon black and graphite.Such filler and reinforcing agent are frequent
Can exist under relatively high concentration, including wherein the filler or reinforcing agent are exceeded with the weight based on the final composition
The preparation that 50wt% concentration is present.More typically, filler and reinforcing agent are the weight based on the total polymer composition
From 5 to 50wt%, such as 10 to 40wt% or 15 to 30wt% exist.
63 embodiments
Comparison example 1
Slowly add into a kind of solution of 96.0g methylphosphonic acids (1.00mol) in 210mL deionized waters under a nitrogen
Plus 54.1g ethoxyquins aluminium (0.334mol).Then, the reactant mixture is stirred into 16h at room temperature.Then, by the solution
Concentrate and dry to obtain a kind of clarification, colourless solid in a vacuum at 100 DEG C.As illustrated in fig. 1, heat analysis
Indicate the loss for starting a mole of water at about 250 DEG C.Elementary analysis：29.8%P, 9.0%Al；The 29.8%P of calculating,
8.7%Al.
20 portions of salt and 30 parts of glass are used to the Haake Rheocord equipped with a three-member type Brabender gauge head
90 mixtures are into 50 parts of polyamide 66s.The reduction of moment of torsion is observed during mixture, it can represent the degraded of polymer, produced
A kind of material of the wet newspaper of picture, the material is frangible in cooling and is dust after milling.It cannot be molded
The material of mixture degraded is provided in addition by the analysis of gel permeation chromatography (GPC) and differential scanning calorimetry (DSC)
Evidence.
Fire retardants of the example 1- from methylphosphonic acid aluminium salt, FR-INV1
Delay under a nitrogen in a kind of solution of the cooling to 48.0g methylphosphonic acids (500mmol) in 210ml deionized waters
Slowly add 27.0g ethoxyquins aluminium (167mmol).Then, it is allowed to which the reaction is heated to room temperature and stirs 16h.Then, will
The solution concentrates and dried to obtain a kind of clarification, colourless solid in a vacuum at 100 DEG C.As heat analysis is indicated
Start the loss of a mole of water at 250 DEG C.Colorless solid 4h is heated at 280 DEG C, one kind as shown in Figure 2 is generated
For>400 DEG C of stable pale solids.Elementary analysis：31.5%P,
9.0%Al.
64 comparison examples 2
Added into a kind of solution of stirring of 37.9g ethylphosphonic acids (344mmol) in 150mL deionized waters a kind of
Solution of the 27.7g Aluminum Chloride Hexahydrates (115mmol) in 150mL deionized waters.Then, the solution is concentrated to go in a vacuum
Water removal and HCl.A kind of white powder heat analysis that is dried to obtain at 130 DEG C in a vacuum drying oven is indicated about
Start the loss of a mole of water at 200 DEG C.Elementary analysis：25.0%P, 6.9%Al.
20 portions of salt and 30 parts of glass are used into a mixture of Haake Rheocord 90 into 50 parts of polyamide 66s.Pass through
Mixture is worn it was observed that low moment of torsion, it can represent the degraded of polymer, wherein in the off-test, from bowl dress thing (bowl)
Preparation expand the material for and generating a kind of foaming of the gas due to escape, the material be in cooling it is frangible and
It is dust after grinding.The compound material that cannot be molded provides other degraded by GPC and DSC analysis and demonstrate,proved
According to.
Fire retardants of the example 2- from ethylphosphonic acid aluminium salt, FR-INV2:
Added into a kind of solution of stirring of 149.5g ethylphosphonic acids (1.36mol) in 500mL deionized waters a kind of
Solution of the 109.3g Aluminum Chloride Hexahydrates (453mol) in 250mL deionized waters.Then, by the solution at 130 DEG C in vacuum
It is middle to concentrate and dry to remove water removal and HCl.Heat analysis indicates the loss for starting a mole of water at 180 DEG C.At 225 DEG C
The salt 3h for heating the drying obtains a kind of for about 400 DEG C of stable white powder.Elementary analysis：27.3%P, 7.6%Al.
Fire retardants of the example 3- from ethylphosphonic acid calcium salt, FR-INV3:
Slowly added into a kind of solution of stirring of 52.1g ethylphosphonic acids (473mmol) in 250mL deionized waters
17.5g calcium hydroxides (236mmol).Then, the solution is concentrated and dried in a vacuum at 100 DEG C.Heat analysis shows
Start the loss of a mole of water at 220 DEG C.The salt 3h that the drying is heated at 290 DEG C obtains one kind>400 DEG C stable white
The powder of color.Elementary analysis：25.3%P, 16.3%Ca.
Preparation comprising the fire retardant from example 1,2 and 3 and different synergist is used into a Haake
The mixtures of Rheocord 90 extremely have in the polyamide 66 of glass and using the miniature moulding press (Mini- of a BabyPlast
Molder 1/16 inch of rod) is molded as, the vertical combustion tests of UL 94 of standard are subjected to.Preparation and result are listed in the table below 1
In.
Table 1-FR data
The synergist used in the FR preparations：
SYN1：Three (diethyl phosphinic acids) aluminium, OP 1230
SYN2：The polyarylether of methylene-diphenyl phosphine oxide-substituted
SYN3：Terephthaldehyde's base is double (diphenyl phosphine oxide)
SYN4：Double (diphenyl phosphine oxide the ylmethyl) -1,1'- biphenyl of 4,4'-
SYN5：1,2- pairs-(9,10- dihydro-9-oxy -10- phospho hetero phenanthrene -10- oxides) ethane
SYN6：Melem, NFR HP
SYN7：Hydrogen phosphite aluminium
Al2(HPO3)3
SYN8：Double melamine pyrophosphoric zinc, 400
Claims (5)
1. a kind of flame retardant compositions, comprising：A) a kind of thermosetting or thermoplastic polymer, b) are based on the flame-retardant polymer
The gross weight of composition, by weight from 1% to 60% a kind of fire proofing, the fire proofing is included in 220 by one kind
DEG C or higher temperature under a kind of or more than one compound with formula (I) is heated to method from 0.01 hour to 25 hours
Obtain, wherein R is C1-12Alkyl, C6-10Aryl, C7-18Alkaryl or C7-18Aralkyl, wherein the alkyl, aryl, alkane are fragrant
Base or aralkyl are unsubstituted or by halogen, hydroxyl, amino, C1-4Alkylamino, two-C1-4Alkylamino, C1-4Alkoxy, carboxylic
Base or C2-5Alkoxy carbonyl replaces；M is a kind of metal, y be one from 1 to 4 number so that M(+)yIt is a kind of metal cation,
Wherein (+) y is represented is assigned to the electric charge of the cation in form, and p be one from 1 to 4 number.
2. flame retardant compositions according to claim 1, wherein in formula (I), M be Li, K, Na, Mg, Ca, Ba,
Zn, Zr, B, Al, Si, Ti, Sn or Sb.
It is straight or branched C1-C6- alkane 3. dialkylphosphinic salts wherein R1, R2 with structural formula (1) are identical or different
Base, M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Fe, Zr, Zn, Ce, Bi, Sr, Mn, Li, Na, K and/or be protonated nitrogen base；M is 1
To 4；Wherein telomer content is 0.01 to 6% weight and telomer is ethyl-butyl phosphinates, butyl phosphinates,
Ethylhexyl phosphinates, butyl ethylhexyl hypophosphorous acid salt and/or hexyl ethylhexyl hypophosphorous acid salt.
4. dialkylphosphinic salts as claimed in claim 1, wherein telomer content is 0.5 to 8% weight.
5. such as dialkylphosphinic salts required in claim 1 or 2, wherein telomer content is 0.3 to 5.9% weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710489291.9A CN107189427A (en) | 2017-06-24 | 2017-06-24 | A kind of flame retardant compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710489291.9A CN107189427A (en) | 2017-06-24 | 2017-06-24 | A kind of flame retardant compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107189427A true CN107189427A (en) | 2017-09-22 |
Family
ID=59879536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710489291.9A Pending CN107189427A (en) | 2017-06-24 | 2017-06-24 | A kind of flame retardant compositions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107189427A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107938940A (en) * | 2017-10-20 | 2018-04-20 | 安徽皖江云众创空间管理有限公司 | The fire-retardant partition wall of space lease |
| CN108102353A (en) * | 2017-12-20 | 2018-06-01 | 贵州省材料产业技术研究院 | A kind of fire-retardant semiaromatic high-temperature nylon and preparation method thereof |
| CN109705566A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Fire-retardant Nylon 6 composition and its expanded bead |
| CN113166426A (en) * | 2018-12-20 | 2021-07-23 | 朗盛公司 | Process for the preparation of phosphorus-containing flame retardants and their use in polymer compositions |
| CN115160645A (en) * | 2022-07-13 | 2022-10-11 | 塔里木大学 | Preparation method of vermiculite compound flame retardant material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660857A (en) * | 2003-12-19 | 2005-08-31 | 科莱恩有限公司 | Salts of dialkylphosphinic acids |
| CN104736549A (en) * | 2013-07-24 | 2015-06-24 | 科聚亚公司 | Phosphorus containing flame retardants |
| CN105452264A (en) * | 2014-07-22 | 2016-03-30 | 科聚亚公司 | Phosphorus containing flame retardants |
-
2017
- 2017-06-24 CN CN201710489291.9A patent/CN107189427A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660857A (en) * | 2003-12-19 | 2005-08-31 | 科莱恩有限公司 | Salts of dialkylphosphinic acids |
| CN104736549A (en) * | 2013-07-24 | 2015-06-24 | 科聚亚公司 | Phosphorus containing flame retardants |
| CN105452264A (en) * | 2014-07-22 | 2016-03-30 | 科聚亚公司 | Phosphorus containing flame retardants |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107938940A (en) * | 2017-10-20 | 2018-04-20 | 安徽皖江云众创空间管理有限公司 | The fire-retardant partition wall of space lease |
| CN107938940B (en) * | 2017-10-20 | 2020-04-21 | 安徽皖江云众创空间管理有限公司 | Flame-retardant partition wall for space leasing |
| CN109705566A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Fire-retardant Nylon 6 composition and its expanded bead |
| 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 |
| CN108102353A (en) * | 2017-12-20 | 2018-06-01 | 贵州省材料产业技术研究院 | A kind of fire-retardant semiaromatic high-temperature nylon and preparation method thereof |
| CN113166426A (en) * | 2018-12-20 | 2021-07-23 | 朗盛公司 | Process for the preparation of phosphorus-containing flame retardants and their use in polymer compositions |
| CN113166426B (en) * | 2018-12-20 | 2023-03-10 | 朗盛公司 | Process for the preparation of phosphorus-containing flame retardants and their use in polymer compositions |
| US11993622B2 (en) | 2018-12-20 | 2024-05-28 | Lanxess Corporation | Method of preparing phosphorus-containing flame retardants and their use in polymer compositions |
| CN115160645A (en) * | 2022-07-13 | 2022-10-11 | 塔里木大学 | Preparation method of vermiculite compound flame retardant material |
| CN115160645B (en) * | 2022-07-13 | 2023-10-03 | 塔里木大学 | Preparation method of vermiculite compound flame retardant material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104736549B (en) | Phosphorous fire retardant | |
| CN105452264B (en) | Flame retardants containing phosphorus | |
| KR102350006B1 (en) | Process stabilization of polymer compositions comprising phosphorous containing flame retardants | |
| CN107207779B (en) | The flame retardant compositions of phosphorus compound and melam comprising heat treatment | |
| CN116023410A (en) | Process for the preparation of phosphorus-containing flame retardants and their use in polymer compositions | |
| CN107189427A (en) | A kind of flame retardant compositions | |
| WO2016018484A1 (en) | Salts of pyrophonic acid as flame retardants | |
| US20220081536A1 (en) | Method For Preparing Readily Processable, Thermally-Stable, Phosphorus-Containing Flame Retardant Material | |
| CA2911457C (en) | Phosphorus containing flame retardants | |
| RU2812784C1 (en) | Method for obtaining phosphorus-containing fire-resistant agents and their application in polymer compositions | |
| RU2804662C2 (en) | Method for obtaining easily processed, heat-stable, phosphorus-containing fire-resistant material |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170922 |