CN104710622B - Intumescent halogen-free Si-P-N-based polymer fire retardants - Google Patents
Intumescent halogen-free Si-P-N-based polymer fire retardants Download PDFInfo
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Abstract
The invention provides intumescent halogen-free Si-P-N-based polymer fire retardants, preparation methods thereof, and a system, a combination and a product respectively containing the fire retardants. The intumescent halogen-free Si-P-N-based polymer fire retardants have better fire retardation performance at low content than routine N-P-based fire retardation compositions.
Description
The application is the applying date to be on December 2nd, 2010, and (international application no is PCT/ to Application No. 201080071104.1
CN2010/079398), the application for a patent for invention of entitled " the halogen-free polymer flame retardant based on silicon-phosphorus-nitrogen of intumescence "
Divisional application.
Technical field
The present invention relates to halogen-free silicon-phosphorus-nitrogen (SPN) polymer flame retardant of intumescence, the method for preparing them, and
Wherein introduce combinations thereof thing and product.
Background technology
Because the concern to environment and security against fire increasingly increases, the nothing for making great efforts to be developed for various polymeric systems is needed
Halogen flame (HFFR).Widely use intumescence fire retardant (IFR) system based on phosphorus and nitrogen.But, by the fire-retardant of high-load
During agent (FR) is incorporated into polymeric matrix, the property of polymer composition may be damaged, for example physical property, electrical properties,
Or ageing property.Accordingly, it would be desirable to reduce the property that contents of the HFFR in fire-retardant combination keeps polymeric matrix simultaneously.Have
When, using low-molecular-weight based on phosphorus and the IFR of nitrogen, but the migration of IFR can be faced.
The content of the invention
In one embodiment, the present invention is halogen-free silicon-phosphorus-nitrogen (IHFSPN) polymer of the intumescence of formula (I)
Wherein R1To R6Can be same to each other or different to each other and be selected from：Hydrogen, C1-C5Alkyl, C3-C5Hydroxy alkyl, C3-C4Alkene
Base, C6-C10Aryl, C7-C8Aryl alkyl, or cyclic alkyl structure (for example, cyclohexyl), and " n " is 2 to 100 and usually 5
To 20.
In one embodiment, the present invention is the IHFSPN polymer of formula (II)
Wherein " n " is 2 to 100 and usually 5 to 20.
In one embodiment, the present invention is the fire retardant of the IHFSPN polymer comprising two or more formulas (I)
System.
In one embodiment, the present invention is the IHFSPN polymer comprising one or more formula (I) and base polymer
The compositionss of thing, wherein base polymer are not formula (I) polymer.
In one embodiment, the present invention is the product of the IHFSPN polymer comprising formula (I).In a kind of embodiment
In, the present invention is the product of the IHFSPN polymer comprising formula (II).
In one embodiment, the present invention is the method for the IHFSPN polymer for preparing formula (I), and the method includes following
Step：
I () makes at reaction conditions dihalide halosilanes and diamidogen contact to form silane diyl diamidogen；
(ii) dihalo- substituted phosphate and polyhydric alcohol is made to contact to prepare spiral shell dihalo- substituted phosphate at reaction conditions；With
(iii) the silane diyl diamidogen and the spiral shell dihalo- substituted phosphate is made to contact with formula at reaction conditions
(I) polymer.
In one embodiment, the present invention is the method for the IHFSPN polymer for preparing formula (II), the method include with
Lower step：
Dichloro base silane and ethane -1,2- diamidogen is set to contact in the presence of triethylamine to form N at reaction conditions,
N- (diphenyl silane diyl) bisethane -1,2- diamidogen；
(ii) phosphinylidyne trichlorine and tetramethylolmethane is made to contact to prepare tetramethylolmethane-spiral shell either dichlorophosphate at reaction conditions；
With
(iii) N, N- (diphenyl silane diyl) bisethane -1,2- diamidogen and tetramethylolmethane-spiral shell two are made at reaction conditions
Chlorine phosphate ester contacts to prepare formula (II) polymer.
The IHFSPN polymer of formula (I) be used as various flame-retardant systems and polymer composition (for example for manufacture wire rod and
Those of cable coatings) in fire retardant.
The application is related to implementation below：
Halogen-free silicon-phosphorus-nitrogen (IHFSPN) polymer of the intumescence of the formula of embodiment 1. (I)
Wherein " n " is 2 to 100, R1To R6Can be same to each other or different to each other and be selected from：Hydrogen, C1-C5Alkyl, C3-C5Hydroxyl alkane
Base, C3-C4Alkenyl, C6-C10Aryl, C7-C8Aryl alkyl, or cyclic alkyl structure.
The IHFSPN polymer of the embodiment 1 of embodiment 2., wherein " n " is 5 to 20.
The IHFSPN polymer of the embodiment 1 of embodiment 3., it is the material of formula (II)
Wherein " n " is 2 to 100.
Embodiment 4.IHFSPN flame retardance of polymer systems, it includes the IHFSPN polymer of one or more formula (I).
The IHFSPN flame retardance of polymer systems of the embodiment 4 of embodiment 5., it is further comprising at least one halogen-free
Fire retardant, wherein the halogen-free flame-retardant is not formula (I) polymer.
The IHFSPN flame retardance of polymer systems of the embodiment 5 of embodiment 6., wherein the halogen-free flame-retardant is following
At least one：Ammonium polyphosphate (APP), red phosphorus, silicon dioxide, aluminium oxide, titanium oxide, CNT, Talcum, clay is organic
Modified clay, organosilicon polymer, Firebrake ZB, antimony trioxide, wollastonite, Muscovitum, hindered amine stabilizer, ammonium octamolybdate, eight
Molybdic acid tripolycyanamide, frit, hollow glass micro-ball, intumescent compounds, expansible graphite, Ethylene diamine phosphate, phosphoric acid trimerization
Cyanamide, melamine pyrophosphate, and melamine polyphosphate.
Embodiment 7.IHFSPN polymer compositions, it is included
A) the IHFSPN polymer of embodiment 1；With
B) base polymer.
The compositionss of the embodiment 7 of embodiment 8., wherein the base polymer includes following at least one：Epoxy
Ring, acid groups, and anhydride group.
The compositionss of the embodiment 7 of embodiment 9., wherein making formula (I) polymer be coupled with the base polymer.
The compositionss of the embodiment 7 of embodiment 10., wherein the base polymer includes following at least one：Second
Alkene vinyl acetate copolymer, poly- (ethylene-ethylacrylate) copolymer, thermoplastic polyurethane, polyethylene and polypropylene.
The compositionss of the embodiment 7 of embodiment 11., its include the formula (I) of 10 to 50wt% IHFSPN polymer and
The base polymer of 50 to 90wt%.
The compositionss of the embodiment 11 of embodiment 12., its include the formula (I) of 25 to 30wt% IHFSPN polymer and
Poly- (ethylene-ethylacrylate) of 70 to 75wt%.
The product of IHFSPN polymer of the embodiment 13. comprising embodiment 1.
The product of the embodiment 13 of embodiment 14., its form is cable coatings.
The product of the embodiment 13 of embodiment 15., its form is film.
Embodiment 16. synthesizes the method for IHFSPN polymer, comprises the following steps：
I () makes at reaction conditions dihalide halosilanes and diamidogen contact to form silane diyl diamidogen；
(ii) dihalo- substituted phosphate and polyhydric alcohol is made to contact to prepare spiral shell dihalo- substituted phosphate at reaction conditions；With
(iii) the silane diyl diamidogen and the spiral shell dihalo- substituted phosphate is made to contact with formula at reaction conditions
(I) IHFSPN polymer.
The method of the embodiment 16 of embodiment 17., wherein
The dihalide halosilanes are dichloro base silanes,
The diamidogen is ethane -1,2- diamidogen,
The silane diyl diamidogen is N, N- (diphenyl silane diyl) bisethane -1,2- diamidogen,
The dihalo- substituted phosphate is phosphinylidyne trichlorine,
The polyhydric alcohol is tetramethylolmethane,
The spiral shell dihalo- substituted phosphate is tetramethylolmethane-spiral shell either dichlorophosphate, and
The IHFSPN polymer is the material of formula (II).
The method of the embodiment 17 of embodiment 18., comprises the following steps：
I () makes at reaction conditions 0.025mol dichloros base silane and 0.1mol ethane -1,2- diamidogen in 0.1mol
Contact to form N, N- (diphenyl silane diyl) bisethane -1,2- diamidogen in the presence of triethylamine；
(ii) 0.2mol phosphinylidynes trichlorine and 0.1mol tetramethylolmethanes is made to contact to prepare tetramethylolmethane-spiral shell at reaction conditions
Either dichlorophosphate；With
(iii) 0.1mol N, N- (diphenyl silane diyl) bisethane -1,2- diamidogen and 0.1mol are made at reaction conditions
Tetramethylolmethane-spiral shell either dichlorophosphate contacts to prepare the IHFSPN polymer of formula (II).
Description of the drawings
Fig. 1 is the SEM image of poly- (ethylene-ethylacrylate)/ammonium polyphosphate (EEA/APP) complex.
Fig. 2 is the SEM image of the complex of EEA/ formulas (II) polymer.
Specific embodiment
Silicon-phosphorus-nitrogen (SPN) fire retardant of halogen-free (HF) polymerization of present invention offer intumescence, the method for preparing them,
And wherein introduce their product, system and compositionss.With routinely being compared with fire-retardant (IFR) compositionss of nitrogen based on phosphorus, originally
The halogen-free SPN polymer compositions of the intumescence of invention provide good fire resistance in relatively low content.
Definition
Unless pointed out, from context cues or prior art convention, all parts and percentages are based on weight, Er Qiesuo
Some method of testings are synchronous with the submission date of the application.For purposes of United States patent practice, any patent being related to,
Patent application or disclosure be hereby incorporated by reference (or its US of equal value it is of the same clan be also introduced into as reference), especially
It is the disclosure with regard to the definition (any definition specifically not provided with the application is inconsistent) in this area and general knowledge.
Digital scope in the application is approximation, therefore unless otherwise stated, otherwise it can be included beyond the scope
Value.Numerical range includes all numerical value from lower limit to higher limit increased with 1 unit, and condition is in any lower value
There is the interval of at least 2 units between any high value.For example, if compositional, physics or other properties, such as molecule
Amount is 100 to 1,000, it is meant that clearly list all of single number, such as 100,101,102, and all of son
Scope, such as 100 to 144,155 to 170,197 to 200.For comprising the numerical value less than 1 or comprising the fraction (example more than 1
Such as 1.1, scope 1.5), 1 unit is regarded as 0.0001,0.001,0.01 or 0.1 when appropriate.For comprising less than 10
The scope of the unitss of (such as 1 to 5), generally regards 1 unit as 0.1.These are only showing for concrete intended content
Example, and the numerical value between cited minimum and peak is possible to combine and is considered to clearly be documented in the application
In.Digital scope in the application particularly provides the amount of each component of compositionss, technological parameter etc..
The term such as "comprising", " including ", " having " is not excluded for the presence of any other component, step or process, and not
Whether pipe the application especially disclosed them.To eliminate any query, unless explanation, it is otherwise all this application claims use art
The compositionss of language " including " can include one or more other step, part of appliance or components, and/or material.Conversely, removing
Those unnecessary for operating characteristics, term "consisting essentially of ..." excludes any other component, step or process
Outside what scope described below in office.Term " Consists of " does not include any component, step not specifically described or list
Or process.Unless explanation, otherwise term "or" refers to the separate member or its any combinations for listing.
The terms such as " compositionss ", " preparation " represent the mixture or blend of two or more components.It is being used to manufacture
In the mixture of the material of cable sheathing or other article of manufacture or the context of blend, compositionss include all of mixture
Component, for example, polypropylene, polyethylene and ethylene copolymers, metal hydroxidess and any other additive such as curing catalysts, antioxygen
Agent, fire retardant etc..
" polymer " represents the compound by preparing monomer polymerization, but regardless of whether the monomer is identical or different
Type.Therefore general term polymer (generally refers to what is only prepared by a type of monomer including term homopolymer
Polymer) and by term interpretation defined below.
" interpretation " represents the compound prepared by the polymerization of at least two different types of monomers.The general term
Including copolymer (generally referring to the polymer prepared by two kinds of different type monomers) and by more than two kinds of different monomers preparations
Polymer (for example, terpolymer, quadripolymer etc.).
" thermoplasticity " material list is linear or branched polymer, and it can soften repeatedly, and becomes easily stream when heated
Move and return upon cooling to room temperature hard state.The elastic modelling quantity of its method measured using ASTM D638-72 is generally big
In 10,000psi (68.95MPa).And, when soft state is heated to, thermoplastic can be molded or be extruded into tool
There is the product of any reservation shape.
The terms such as " cable ", " cable " represent protectiveness chuck or at least one electric wire or optical fiber in sheath.Allusion quotation
Type ground, cable is the common protectiveness chuck of typical DIYU or two or more the electric wires tied together or optics in sheath
Fiber.Individual wires or fiber in chuck can be exposed, cladding or insulation.Combination cable can simultaneously comprising electricity
Line and optical fiber.Can be for low voltage application, middle voltage application and high voltage applications design cable etc..Typical cable sets
Meter explanation in USP 5,246,783,6,496,629 and 6,714,707.
Terms such as " halogen-free " represents that the compositionss of the present invention do not have or substantially do not have content of halogen, i.e. this
Bright compositionss are measured comprising the halogen less than 2000mg/kg by chromatography of ions (IC) or similar analysis method.Think little
In the amount content of halogen for many products for example by the present invention compositionss prepare wire rod or cable covering effect
It is unimportant.
Terms such as " intumescence fire retardants " represent be exposed to during flame produce on surface of polymer material formed
The fire retardant of foaming carbide.
IHFSPN flame retardance of polymer systems
IHFSPN polymer of the IHFSPN flame retardance of polymer system of the present invention comprising one or more formula (I).IHFSPN
Flame-retardant system can include other halogen-free flame-retardants of one or more non-formula (I), such as ammonium polyphosphate (APP), red phosphorus, two
Silicon oxide, aluminium oxide, titanium oxide, CNT, Talcum, clay, organically-modified clay, organosilicon polymer, Firebrake ZB, three
Stibium oxide, wollastonite, Muscovitum, hindered amine stabilizer, ammonium octamolybdate, eight molybdic acid tripolycyanamide, frit (frits), hollow glass
Glass microsphere, intumescent compounds, expansible graphite, Ethylene diamine phosphate, melamine phosphate, melamine pyrophosphate, and many phosphorus
Sour tripolycyanamide.IHFSPN flame retardance of polymer system can include filler, antioxidant, pigment, UC stabilizers, processing aid,
Toughener etc..
The mixture of IHFSPN polymer or two or more IHFSPN polymer includes 50wt% or more
IHFSPN flame retardance of polymer systems, usually 60wt% or more, or 70wt% or more, or 80wt% or more, or
90wt% or more.
In one embodiment, IHFSPN polymer of the IHFSPN flame retardance of polymer system comprising formula (II).
IHFSPN polymer compositions
IHFSPN polymer is generally used as fire retardant in polymer composition, but they can also be in such combination
It is used as processing aid, cross-linking agent, or firming agent in thing.For example, the IHFSPN polymer of formula (I) can serve as with acid groups,
The firming agent of the polymer of anhydride group or epoxide group.
The compositionss of the present invention are generally by prepared by IHFSPN polymer and base polymer blending.Base polymer is not
It is formula (I) polymer, representational base polymer includes polyolefin, polyurethane, polyester, polystyrene, Merlon, epoxy
Resin etc..Generally, base polymer can include following at least one：Ethylene vinyl acetate copolymer, poly- (ethylene-the third
Olefin(e) acid ethyl ester) copolymer, thermoplastic polyurethane, polyethylene and polypropylene.IHFSPN polymer compositions can comprising 10 to
Formula (I) polymer and the base polymer of 50 to 90wt% of 50wt%.It is highly preferred that IHFSPN polymer compositions can be wrapped
The base polymer of poly- (ethylene-ethylacrylate) of formula (I) polymer containing 25 to 30wt% and 70 to 75wt%.
The more specific examples of base polymer include polyolefin such as ethene polymerss (for example, Low Density Polyethylene
(LDPE), ULDPE, medium density polyethylene (MDPE), LLDPE, HDPE, uniform branched linear tetrafluoroethylene polymer, substantially linear
Ethene polymerss, the ethene polymerss of graft modification, ethylene-stryene interpretation, ethylene vinyl acetate interpretation, ethylene
Acrylic acid interpolymers, ethylene-ethyl acetate interpretation, ethylene methacrylic acid interpretation, ethylene methacrylic acid ionomer etc.),
Merlon, polystyrene, (for example, polypropylene homopolymer, polypropylene copolymer, random block polypropylene is mutual for conventional polypropylene
Polymers etc.), thermoplastic polyurethane, polyamide, polylactic acid interpretation, (for example, styrene butadiene is common for thermoplastic block polymers
Polymers, styrene butadiene styrene triblock copolymer, styrene ethylene-butene styrene triblock copolymer etc.), polyethers
Block copolymer (for example, PEBAX), copolyester polymer, polyester and polyether block polymer (for example, HYTEL), the oxygen of ethylene one
Change carbon interpretation (for example, ethylene/carbon monoxide (ECO) copolymer, ethylene/acrylic acid/carbon monoxide (EAAVO) ternary polymerization
Thing, ethylene/methacrylic acid/carbon monoxide (EMAACO) terpolymer, ethylene/acetic acid ethyl ester/carbon monoxide (EVACO)
Terpolymer and styrene/carbon monoxide (SCO)), polyethylene terephthalate (PET), chlorinated polyethylene etc. and its
Mixture.In other words, the polyolefin for present invention practice can be two or more polyolefinic blends, or it is a kind of or
The blend of various polyolefin and one or more non-polyolefinic polymer.
IHFSPN polymer compositions can also include conventional additives, the additive can be incorporated into into IHFSPN polymerizations
In compositions or it is introduced directly in IHFSPN flame retardance of polymer systems, the example is antioxidant, coupling agent, ultraviolet is inhaled
Receipts agent, stabilizer, antistatic agent, pigment, dyestuff, nucleator, reinforcer or polymeric additive, slip agent, plasticizer, plus
Work auxiliary agent, lubricant, viscosity-control additive, viscosifier, antiblocking agent, surfactant, extending oil, metal deactivator, voltage is steady
Determine agent, fire-retardant filler, cross-linking agent, accelerator, catalyst, and smog inhibitor.The addition of additive and filler can be little
In about 0.1 to greater than about 50 weight %, the weight based on compositionss.
IHFSPN polymer and base polymer can be crosslinked or be coupled, the base polymer itself is probably what is be crosslinked
Or it is uncrosslinked.IHFSPN polymer can account for 10 to the 50wt% of whole composition weight.More typically, IHFSPN polymer
25 to the 30wt% of whole composition weight can be accounted for.
The example of antioxidant is：Hindered phenol, such as four [methylene (3,5- di-t-butyl -4- hydroxy groups-cinnamic acid
Ester)] methane, two [(β-(3,5- di-tert-butyl-4-hydroxyl benzyl)-methyl carboxy ethyl)] thioethers, 4,4'- thiobiss (2- first
Base -6- tert-butyl phenols), and sulfenyl di ethylene bis (3,5- di-t-butyl -4- hydroxyls) hydrogenated cinnamate；Phosphite ester and
Phosphinate, such as phosphorous acid three (2,4- di-tert-butyl-phenyl) ester and di-tert-butyl-phenyl-phosphinate；Thio-compoundss, such as
Thiodipropionate dilauryl, thio-2 acid myristyl ester and thio-2 acid distearyl base ester；Various silica
Alkane；With various amine, such as polymerization -1,2- dihydro -2,2,4- trimethylquinolines, 4,4 '-two (alpha, alpha-dimethylbenzyl) hexichol
Amine and alkylating diphenylamines.The consumption of antioxidant can be about 0.1 to about 5 weight %, the weight based on compositionss.
Processing aid can be included in IHFSPN polymer compositions for their known purpose.Therefore, although being
The viscosity of homogeneous blend and reduction is obtained it is not always necessary that adding processing aid, but can be to add them to the present invention's
Further enhancing these properties in compositionss.For example, processing aid can including but not limited to, Polyethylene Glycol, metal Hard Fat
Hydrochlorate such as zinc stearate and aluminium stearate, stearate, stearic acid, polysiloxanes, stearmide, ethylene-dioleoyl amine, second
Alkene-distearyl amide, silicon polymer, fluoropolymer, its mixture etc..When the compositionss of the present invention are added to, processing is helped
The consumption of agent is typically about 0.1 to 5 weight %, the gross weight based on IHFSPN polymer compositions.
IHFSPN polymer compositions can comprising coupling agent and/or cross-linking agent with improve fire retardant and base polymer it
Between the compatibility.The example of coupling agent or cross-linking agent include silane, titanate/ester, sircontates, maleic anhydride grafting
Various polymer, the copolymer of maleic anhydride grafting, and its mixture.The amount of the coupling agent that compositionss include can be 0.5 to 5
Weight %, the weight based on compositionss.Organic peroxide is preferably used as free radical generating agent and cross-linking agent.Useful organic mistake
Oxide cross linking agent is included but is not limited to, two (tert-butylperoxyiso-propyl) benzene, dicumyl peroxide, two (tert-butyl group) peroxides
Compound, and 2,5- dimethyl -2,5- bis- (t-butyl peroxy)-hexane.Known auxiliary agent can also be with coupling agent or cross-linking agent group
Conjunction is used.Organic peroxide cross-linking agent is disclosed in United States Patent (USP) 3,296,189.
Product based on IHFSPN
Included but is not limited to by the product of the IHRSPN polymer compositions manufacture of the present invention, wire rod and cable coatings, film,
Foams, molded item, the coating of electrical connector, the plastics of electronic product casing, footwear, furniture, ornament, printed circuit board (PCB),
The coating of air vane (wind mill blades), the thermal insulation of building, timber or steel construction, and binding agent.These
Product can be prepared using known device and known method (for example, extruding, molding, curtain coating etc.).
The method for preparing IHFSPN polymer
The synthesis of IHFSPN polymer is started with preparing silane diyl diamidogen and spiral shell dihalo- substituted phosphate.Silane diyl diamidogen
It is anti-in the presence of 0.1mol triethylamines (TEA) by 0.1 mole of (mol) dichlorosilane and 0.025mol diamidogen according to below scheme
Should synthesize：
Wherein R7To R13Can be same to each other or different to each other, and be selected from：Hydrogen, C1-C5Alkyl, C3-C5Hydroxy alkyl, C3-C4
Alkenyl, C6-C10Aryl, C7-C8Aryl alkyl, or cyclic alkyl structure (for example, cyclohexyl)；X can be any halogen, generally
It is chlorine.
Spiral shell dihalo- substituted phosphate is formed by the reaction of 0.2mol dihalo-s substituted phosphate and 0.1mol polyhydric alcohol.Reactant can
To be selected from：Dihalide halosilanes, diamidogen, silane diyl diamidogen and dihalo- substituted phosphate/phosphate ester/phosphonate ester.Structure is listed below
Scheme：
Wherein R14To R21Can be same to each other or different to each other, and be selected from：Hydrogen, C1-C5Alkyl, C3-C5Hydroxy alkyl, C3-C4
Alkenyl, C6-C10Aryl, C7-C8Aryl alkyl, or cyclic alkyl structure (for example, cyclohexyl)；X can be any halogen, generally
It is chlorine.
IHFSPN polymer is by making 0.1mol silane diyl diamidogen and 0.1mol dihalo-s substituted phosphate in 0.2mol tertiary amines
In the presence of reaction formed.The temperature of reaction can be room temperature to about 200 DEG C, and this has depended on used those skilled in the art
The solvent known.Formula (I) polymer is formed by below scheme：
R wherein in above scheme1To R6Can be same to each other or different to each other, and be selected from：Hydrogen, C1-C5Alkyl, C3-C5Hydroxyl
Base alkyl, C3-C4Alkenyl, C6-C10Aryl, C7-C8Aryl alkyl, or cyclic alkyl structure (for example, cyclohexyl)；X can be appointed
What halogen, typically chlorine.
Embodiment
All of material and solvent are all purchased from Sinopharm Chemical Reagent Co., Ltd.
The synthesis of the IHFSPN polymer of formula (II) is preparing N, N- (diphenyl silane diyl) bisethane -1,2- diamidogen
(DPSEA) start with tetramethylolmethane-spiral shell either dichlorophosphate (PSDCP).0.1mol dichloros base silane and 0.025mol ethane-
Reaction of the 1,2- diamidogen in the presence of 0.1mol triethylamines (TEA) forms DPSEA.0.2mol phosphinylidynes trichlorine and 0.1mol seasons penta 4
The reaction of alcohol forms PSDCP.0.1mol DPSEA and 0.1mol PSDCP react in the presence of 0.2mol TEA, form formula (II)
IHFSPN polymer.
Synthesis DPSEA
20ml dichloromethane 6.18g (0.1mol) EDA and 10.1g (0.1mol) TEA being dissolved in three-neck flask, should
Flask equipped has reflux condenser, overhead mechanical agitator, thermometer and ice-water bath.Then, by 6.33g (0.025mol) DCPS
It is dissolved in 80ml dichloromethane and it is added dropwise under a dry nitrogen atmosphere in flask.Reaction proceeds 5-6 hours.
The mixture for obtaining is washed with water to remove unreacted TEA, EDA and triethylamine hydrochloride, so as to obtain white powder.Pass through
Vacuum drying, with 92% yield product is obtained.
Synthesis PSDCP
By 30.38g (0.2mol) TCP, 13.61g (0.1mol) PER and 0.05g AlCl3It is merged into three neck round bottom
In 250ml MeCN in, the flask equipped has reflux condenser, overhead mechanical agitator and thermometer.Heat the mixture to
80 DEG C and make its reaction 7 hours.After the reaction was completed, solvent evaporation is obtained into white powder.Cold water, ethanol and two are used respectively
Chloromethanes washing powder.By the way that in an oven product is vacuum dried into 5 hours come desciccate at 50 DEG C, 23.67g products are obtained
PSDCP (yield 80%).
The IHFSPN polymer of synthesis formula (II)
The molecular weight of Ubbelohde viscometers estimation embodiment product is 7000, is 13 corresponding to " n " value.
The 100ml METHYLPYRROLIDONEs (NMP) 30.24g (0.1mol) DPSEA being merged in three-neck flask
In, the flask equipped has reflux condenser, overhead mechanical agitator and thermometer.Mixture is stirred under a dry nitrogen atmosphere
Until DPSEA is completely dissolved in room temperature.Then 20.20g (0.2mol) TEA and 29.7g (0.1mol) PSDCP are added to into reaction
In, reaction temperature increases to 90 DEG C.After the reaction of 24 hours, by being filtrated to get light-yellow precipitate thing.Wash with water
The solid for arriving, then by solid in vacuum drying oven in 80 DEG C of dryings 6 hours, obtain formula (II) polymer (yield 94%).
The sign of the IHFSPN polymer of formula (II)
The IHFSPN polymer of formula (II) does not dissolve in usual vehicle.Characterize by elementary analysiss (according to ASTM D7455-
08) carry out.As a result it is listed in table 1.
Table 1
The elementary analysiss result of the IHFSPN polymer of formula (II)
The gas composition analysis that constituent content is produced by burning cpd.Nitrogen and phosphorus content are in close proximity to containing for calculating
Amount.The carbon content for measuring is far below value of calculation, and this is attributed to during combustion testing and forms carbide.And, by FTIR
Triethylamine hydrochloride (byproduct of reaction) is detected with NMR, the polycondensation reaction between reactant is which demonstrated.Therefore, it can push away
Break the structure of the IHFSPN polymer for formula (II).
Table 2 reports the composition and performance data of comparative example 1-3 and embodiment 1 and 2.Poly- (ethylene-ethylacrylate)
(EEA) for example for example it is purchased from Clariant purchased from the EA103 of The Dow Chemical Company, and ammonium polyphosphate (APP)
Exolit AP 442 abridge in table 2.All of sample is mixed by HAKKE Rheocord systems at 160 DEG C and 60rpm
Match somebody with somebody.Then mixed thing is compression molded into into the test print that thickness is 3 millimeters (mm).Vertical combustion experiment (UL94) passes through ZCF-
3UL94 instruments are carried out using 125mm X 13mm X 3mm strips according to ASTM D3801.Five assay strips are for the test.
The test print of compression moulding is prepared in 185 DEG C of molding temperatures, promotes melting using low pressure recycle, then using high pressure so that 3X
200X 200mm test sample sheetmoldings, then make mould be maintained at high pressure (15MPa) and room temperature is cooled in a period of 8min
So that test print solidification.
Table 2
Embodiment preparation and UL94 test results
Composite preparation in the table 2 of comparative example 1-3 and embodiment 1 and 2 is referred to poly- (ethylene-ethylacrylate)
, and ammonium polyphosphate (APP) (EEA).
Table 2 reports the flammable criteria classifications of UL 94 of plastics.Bunsen flame is put on into the bottom of sample.Flame applies
Time is 10 seconds.First burning time t1 be by Bunsen flame from sample remove after on sample flame persistent period.
After one fray-out of flame, apply Bunsen flame 10 seconds again, then remove from sample.Second burning time t2 is to remove Bunsen flame
Afterwards, on the sample during fray-out of flame on sample flame persistent period.For V0 grades each burning time should not be more than
10 seconds, for V1 or V2 grades should not be more than 30 seconds.For total burning time of three samples of V0 grades should not be more than 50
Second, for V1 or V2 grades should not be more than 250 seconds.V0 and V1 grades light the dropping of the cotton balls under sample all without having,
And V2 grades may have dropping.It is nonrated for any test result for being unsatisfactory for V0, V1 or V2 grade.
As shown in table 2, IHFSPN polymer compositions of the invention only reach UL94V0 and (implement in the content of 25 weight %
Example 1).Conversely, the sample with 32%APP contents reaches UL94V1 in EEA, the sample with 40%APP contents in EEA
Reach UL94V0 (comparative example 1-3).And, the sample after-flame with 40%APP/MC contents (2/1), do not meet UL94 etc.
Level.The result proves, with routinely being compared with the preparation of APP/MC based on APP, the IHFSPN polymer comprising formula (II) this
Bright IHFSPN polymer compositions provide preferable fire resistance in lower content.
The SEM image of the EEA/IHFSPN polymer complexes of EEA/APP complex and formula (II) is figures 1 and 2 show that, they
Content all be 32%.From accompanying drawing, APP is big particle.But, the fusing point of the IHFSPN polymer of formula (II) is in polymer
In the range of processing temperature (～160 DEG C), thus formula (II) polymer can become well dispersed in the polymer matrix.Therefore,
The fire-retardant combination of the expected IHFSPN polymer comprising formula (II) has no adverse effect to the engineering propertiess of polymeric matrix.Together
The IHFSPN polymer of sample addition formula (II) can aid in the processability for improving polymeric matrix.
Although by the preceding description of some preferred implementations with certain detailed description the present invention, details master
To be directed to descriptive purpose.Without departing from the spirit and scope of the invention, those skilled in the art can be carried out a lot
Variants and modifications, the spirit and scope of the present invention are by described by claims.
Claims (13)
1.IHFSPN flame retardance of polymer systems, it includes the IHFSPN polymer of one or more formula (II)
Wherein " n " is 2 to 100.
2. IHFSPN flame retardance of polymer systems of claim 1, it is further comprising at least one halogen-free flame-retardant, wherein institute
It is not formula (II) polymer to state halogen-free flame-retardant.
3. IHFSPN flame retardance of polymer systems of claim 2, wherein the halogen-free flame-retardant is following at least one：It is many
Ammonium phosphate (APP), red phosphorus, silicon dioxide, aluminium oxide, titanium oxide, CNT, Talcum, clay, organosilicon polymer, boric acid
Zinc, antimony trioxide, wollastonite, Muscovitum, hindered amine stabilizer, ammonium octamolybdate, eight molybdic acid tripolycyanamide, frit, hollow glass
Microsphere, intumescent compounds, expansible graphite, Ethylene diamine phosphate, melamine phosphate, melamine pyrophosphate, and polyphosphoric acid
Tripolycyanamide.
4. IHFSPN flame retardance of polymer systems of claim 3, wherein the clay is organically-modified clay.
5.IHFSPN polymer compositions, it is included
A) the IHFSPN polymer of formula (II)
Wherein " n " is 2 to 100；With
B) base polymer.
6. compositionss of claim 5, wherein the base polymer includes following at least one：Epoxide ring, acid groups, and
Anhydride group.
7. compositionss of claim 5, wherein making formula (II) polymer be coupled with the base polymer.
8. compositionss of claim 5, wherein the base polymer includes following at least one：Ethane-acetic acid ethyenyl ester
Copolymer, poly- (ethylene-ethylacrylate) copolymer, thermoplastic polyurethane, polyethylene and polypropylene.
9. compositionss of claim 5, it includes the IHFSPN polymer of the formula (II) of 10 to 50wt% and 50 to 90wt%
The base polymer.
10. compositionss of claim 9, it includes the IHFSPN polymer of the formula (II) of 25 to 30wt% and 70 to 75wt%
Poly- (ethylene-ethylacrylate).
The product of the 11. IHFSPN polymer comprising formula (II)
Wherein " n " is 2 to 100.
The product of 12. claim 11, its form is cable coatings.
The product of 13. claim 11, its form is film.
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| CN201080071104.1A CN103328544B (en) | 2010-12-02 | 2010-12-02 | Intumescent, halogen-free, silicon-phosphorus-nitrogen based polymeric flame retardant |
| CN201510052543.2A CN104710622B (en) | 2010-12-02 | 2010-12-02 | Intumescent halogen-free Si-P-N-based polymer fire retardants |
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| US20180334775A1 (en) * | 2015-11-03 | 2018-11-22 | E I Du Pont De Nemours And Company | Cables made of phase change material |
| CN106700920B (en) * | 2017-01-22 | 2019-05-17 | 太原理工大学 | A kind of response type polysiloxanes flame retardant coating and preparation method thereof |
| CN106700081B (en) * | 2017-01-22 | 2020-04-07 | 太原理工大学 | Polysiloxane flame retardant containing nitrogen, phosphorus and silicon and preparation method thereof |
| CN106905688A (en) * | 2017-03-17 | 2017-06-30 | 新疆广巨诚信防腐保温工程有限公司 | A kind of polyurethane industry silicon ash fire retardant |
| CN107459673A (en) * | 2017-07-17 | 2017-12-12 | 兰州大学 | A kind of synthetic method of the fire-retardant carbon forming agent of ethylenediamine phosphorus borate |
| CN110041797A (en) * | 2019-04-02 | 2019-07-23 | 中国人民解放军92228部队 | A kind of aqueous ultra-thin expansion type graphene fireproof coating and preparation method thereof |
| CN112646122A (en) * | 2020-12-21 | 2021-04-13 | 安徽嘉明新材料科技有限公司 | Preparation method and application of reactive flame-retardant TPU (thermoplastic polyurethane) |
| CN115819783B (en) * | 2022-09-26 | 2023-08-22 | 山东天一化学股份有限公司 | Hyperbranched macromolecular flame retardant containing P, N, si and preparation method thereof |
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| JP2003171467A (en) * | 2001-12-05 | 2003-06-20 | Nippon Unicar Co Ltd | Phosphorylated polyorganosiloxane, method for producing the same, flame-retardant and resin composition |
| CN1631942A (en) * | 2004-11-11 | 2005-06-29 | 上海交通大学 | Phosphorus containing siloxane and process for preparing same |
| CN101671568A (en) * | 2009-09-06 | 2010-03-17 | 青岛科技大学 | Phosphorus-contained organic silicon resin fire retardant and preparation method thereof |
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| JP2003171467A (en) * | 2001-12-05 | 2003-06-20 | Nippon Unicar Co Ltd | Phosphorylated polyorganosiloxane, method for producing the same, flame-retardant and resin composition |
| CN1631942A (en) * | 2004-11-11 | 2005-06-29 | 上海交通大学 | Phosphorus containing siloxane and process for preparing same |
| CN101671568A (en) * | 2009-09-06 | 2010-03-17 | 青岛科技大学 | Phosphorus-contained organic silicon resin fire retardant and preparation method thereof |
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