CN105061815B - A kind of halogen-free flameproof composite assistant, its preparation method and PP composite material - Google Patents
A kind of halogen-free flameproof composite assistant, its preparation method and PP composite material Download PDFInfo
- Publication number
- CN105061815B CN105061815B CN201510593428.6A CN201510593428A CN105061815B CN 105061815 B CN105061815 B CN 105061815B CN 201510593428 A CN201510593428 A CN 201510593428A CN 105061815 B CN105061815 B CN 105061815B
- Authority
- CN
- China
- Prior art keywords
- halogen
- free flameproof
- composite assistant
- weight
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 CC(C1)C2(C3C*CC2)C13C(C)(C)C Chemical compound CC(C1)C2(C3C*CC2)C13C(C)(C)C 0.000 description 2
Abstract
The invention provides a kind of halogen-free flameproof composite assistant, its preparation method and PP composite material, the fire-retardant composite assistant includes following components：The phosphniline phenolphthalein cyclic oligomer with Formulas I structure of 10~40 parts by weight；The halogen-free inorganic flame retardant of 40~60 parts by weight；The Halogen coupling agent of 1~3 parts by weight.Fire-retardant composite assistant provided by the invention includes phosphniline phenolphthalein cyclic oligomer and halogen-free inorganic flame retardant so that fire-retardant composite assistant is in the application of PP composite material, it is possible to increase the anti-flammability and mechanical property of composite.Test result indicates that：The limited oxygen index (LOI) of the composite is more than 22%, flame retardant rating >=V 2；Tensile strength is 5.3~6.7GPa；Bending strength is 7.2~8.5GPa；Notch impact strength is 9.1~14KJ/m2。
Description
Technical field
The present invention relates to fire proofing technical field, more particularly to a kind of halogen-free flameproof complexing agent, its preparation method and nothing
The PP composite material of the fire-retardant continuous fiber enhancing of halogen.
Background technology
Polypropylene (Polypropylene, abbreviation PP) is a kind of hemicrystalline thermoplastic, has higher impact resistance
Property, engineering properties is tough, antiacid caustic corrosion.It is very sensitive to breach, impact property is poor etc. but polypropylene has that molding shrinkage is big
Shortcoming, limit its use range.
Long glass fiber reinforced polypropylene is answered by the fibre-reinforced thermoplasticity of the different glass of base material of acrylic resin
Condensation material.Long glass fiber reinforced polypropylene can overcome the disadvantages that the deficiency in Properties of Polypropylene, have high impact, high rigidity, low
The advantages that shrinkage factor, polyacrylic application is expanded, steel, polyformaldehyde, nylon etc. can be replaced within the specific limits, passed through
It is widely used in the fields such as automobile, machinery, electrical equipment.Although long glass fiber reinforced polypropylene has obtained extensive at many aspects
Using, but pass through long glass fibres enhancing polypropylene under the higher occasion of some flame-retardancy requirements using nevertheless suffer from limit
System.
In the prior art, in order to improve the polyacrylic anti-flammability of long glass fibres enhancing, fire retardant is added thereto.Mesh
The preceding fire retardant used includes halogen containing flame-retardant and halogen-free flame retardants, can be produced in halogen containing flame-retardant combustion process substantial amounts of poisonous
Pernicious gas, it is impossible to meet the requirement to environmental protection.Halogen-free flame retardants is relatively environmentally friendly, but existing any halogen-free flameproof
Agent can not also take into account mechanical property and the fire resistance of long glass fiber reinforced polypropylene material to meet requirement.
The content of the invention
In view of this, it is an object of the invention to provide a kind of halogen-free flameproof composite assistant, its preparation method and polypropylene
Composite, PP composite material provided by the invention have preferable anti-flammability and mechanical property.
The invention provides a kind of halogen-free flameproof composite assistant, including following components：
The phosphniline phenolphthalein cyclic oligomer with Formulas I structure of 10~40 parts by weight；
The halogen-free inorganic flame retardant of 40~60 parts by weight；
The Halogen coupling agent of 1~3 parts by weight；
In Formulas I, n=2~7.
Preferably, the halogen-free inorganic flame retardant is the inorganic combustion inhibitor that the trade mark is TC-5J.
Preferably, the Halogen coupling agent is silane coupler.
Preferably, the Halogen function additive of 0.5~25 parts by weight is included；
The Halogen function additive includes toughener, activating agent, lubricant, age resistor and antioxidant.
Preferably, the lubricant includes stearic amide；
The age resistor includes 2,2,4- trimethyl -1,2- dihyaroquinoline condensates；
The antioxidant include four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and/or three [2,
4- di-tert-butyl-phenyls] phosphite ester.
Preferably, the mass ratio of the toughener, activating agent, lubricant, age resistor and antioxidant is (3~10):(1~
3):(0.5~2):(0.5~2):(0.5~5).
The invention provides a kind of preparation method of halogen-free flameproof composite assistant, comprise the following steps：
Phosphniline phenolphthalein cyclic oligomer with Formulas I structure, halogen-free inorganic flame retardant and Halogen coupling agent are mixed, obtained
Halogen-free flameproof composite assistant；
In Formulas I, n=2~7.
Preferably, the temperature of the mixing is 50 DEG C~80 DEG C；The time of the mixing is 0.5~3min.
The invention provides a kind of PP composite material, by including acrylic resin, fiber and halogen-free flameproof is compound helps
The raw material of agent is made；
The halogen-free flameproof composite assistant is halogen-free flameproof composite assistant or above-mentioned technical proposal described in above-mentioned technical proposal
Halogen-free flameproof composite assistant prepared by the preparation method.
Preferably, the mass ratio of the acrylic resin and fiber is 0.9~1.1:1；
The quality of the halogen-free flameproof composite assistant accounts for the 10%~40% of PP composite material.
The invention provides halogen-free flameproof composite assistant, including following components：10~40 parts by weight have Formulas I structure
Phosphniline phenolphthalein cyclic oligomer；The halogen-free inorganic flame retardant of 40~60 parts by weight；The Halogen coupling agent of 1~3 parts by weight.The present invention
The halogen-free flameproof composite assistant of offer includes phosphniline phenolphthalein cyclic oligomer and halogen-free inorganic flame retardant so that fire-retardant composite assistant
In the application of PP composite material, it is possible to increase the anti-flammability and mechanical property of PP composite material.Experimental result table
It is bright：The limited oxygen index (LOI) of PP composite material provided by the invention is more than 22%, flame retardant rating >=V-2；Tensile strength
For 5.3~6.7GPa；Bending strength is 7.2~8.5GPa；Notch impact strength is 9.1~14KJ/m2。
Embodiment
The invention provides a kind of halogen-free flameproof composite assistant, including following components：
The phosphniline phenolphthalein cyclic oligomer with Formulas I structure of 10~40 parts by weight；
The halogen-free inorganic flame retardant of 40~60 parts by weight；
The Halogen coupling agent of 1~3 parts by weight；
In Formulas I, n=2~7.
Halogen-free flameproof composite assistant provided by the invention is added in polypropylene matrix, so as to get PP composite material
With preferable anti-flammability and mechanical property.
In the present invention, the halogen-free flameproof composite assistant includes the phosphniline phenol with Formulas I structure of 10~40 parts by weight
Phthalein cyclic oligomer (CPPA), preferably 15~35 parts by weight；The phosphniline phenolphthalein cyclic oligomer has Formulas I structure：
In Formulas I, the n is the degree of polymerization, n=2~7.
The present invention does not have special limitation to the source of the phosphniline phenolphthalein cyclic oligomer with Formulas I structure, uses
Phosphniline phenolphthalein cyclic oligomer well known to those skilled in the art with Formulas I structure, its commercial goods can be such as used,
The technical scheme well known to those skilled in the art for preparing the phosphniline phenolphthalein cyclic oligomer with Formulas I structure can be used voluntarily
Prepare.In the present invention, the phosphniline phenolphthalein cyclic oligomer with Formulas I structure preferably uses Patent No.
It is prepared by the preparation method described in 201510106181.0.In the present invention, the phosphniline phenolphthalein ring with Formulas I structure
The preparation method of shape oligomer preferably includes following steps：
Under the conditions of existing for catalyst, phenylphosphonyl dichloride and phenolphthalein are subjected to polymerisation, obtain that there is Formulas I structure
Phosphniline phenolphthalein cyclic oligomer.
In the present invention, the amount ratio of the material of the phenylphosphonyl dichloride and phenolphthalein is preferably 1：(0.5~2)；In the present invention
Some embodiments in, the amount ratio of the material of the phenylphosphonyl dichloride and phenolphthalein is preferably 1:1.
In the present invention, the catalyst is phase transfer catalyst, preferably cetyl trimethylammonium bromide, the tetrabutyl
Ammonium chloride or adogen, more preferably cetyl trimethylammonium bromide.
In the specific embodiment of the invention, the preparation method of the phosphniline phenolphthalein cyclic oligomer is specially：By phenylphosphorous acid
Two solutions of chlorine are mixed with phenolphthalein solution, and polymerisation is carried out under the conditions of existing for acid binding agent, obtain the phosphniline with Formulas I structure
Phenolphthalein cyclic oligomer.
Phenylphosphonyl dichloride and phenolphthalein are configured to solution by the present invention first, specifically, phenylphosphonyl dichloride is dissolved in into first
In solvent, phenylphosphonyl dichloride solution is obtained, first solvent is organic solvent, preferably dichloromethane or chloroform, the benzene
The concentration of phosphonyl dichloride solution is preferably 0.1mmol/mL~0.2mol/mL；Phenolphthalein is dissolved in the second solvent, obtains phenolphthalein
Solution, second solvent are preferably sodium hydrate aqueous solution or potassium hydroxide aqueous solution, more preferably sodium hydrate aqueous solution,
The mol ratio of sodium hydroxide and phenolphthalein is 1 in the sodium hydrate aqueous solution:(0.5~2), the molar concentration of the phenolphthalein solution
Preferably 0.1mmol/mL~0.2mmol/mL.
It is added dropwise to after phenylphosphonyl dichloride solution is mixed with phenolphthalein solution in reaction vessel, in N2Protection under, side be added dropwise
While it is stirred.The present invention is not specifically limited to the hybrid mode of the phenylphosphonyl dichloride solution and phenolphthalein solution, preferably
Above-mentioned phenylphosphonyl dichloride solution and phenolphthalein solution are added dropwise in reaction vessel simultaneously respectively by peristaltic pump.In the present invention,
It is 5~10mL/h to control the rate of addition of phenylphosphonyl dichloride solution and phenolphthalein solution respectively.The temperature of the dropwise addition be -20 DEG C~
20 DEG C, be preferably -10 DEG C~10 DEG C.
The present invention is not specifically limited to the mode of the stirring, it is preferred to use mechanical agitation.In the reaction vessel
It is contained with the mixture of catalyst, the 3rd solvent and the 4th solvent.In the present invention, the 3rd solvent is organic solvent, excellent
Elect dichloromethane or chloroform as, the 4th solvent is preferably water；The volume and the 4th of the quality of the catalyst, the 3rd solvent
The volume ratio of solvent is preferably 1g:(500~2000) mL:(50~500) mL, it is in some embodiments of the invention, described to urge
The mass volume ratio of agent, the 3rd solvent and the 4th solvent is 1g：1000mL：200mL.
In the present invention, the temperature of the polymerisation is preferably -20 DEG C~20 DEG C, and the time of the polymerisation is preferred
For 5~30h.
After reaction terminates, the organic phase that above-mentioned reaction obtains is washed with deionized water, to remove inorganic salts, is evaporated organic phase
Solvent, obtain the phosphniline phenolphthalein cyclic oligomer with Formulas I structure.
In the present invention, the halogen-free flameproof composite assistant includes the halogen-free inorganic flame retardant of 40~60 parts by weight, preferably
For 45~55 parts by weight.In the present invention, the halogen-free inorganic flame retardant preferably includes the inorganic combustion inhibitor that the trade mark is TC-5J；
The trade mark is that TC-5J inorganic combustion inhibitor is bought and is bestowed by heaven fire proofing Science and Technology Ltd. in Dandong.
In the present invention, the halogen-free inorganic flame retardant is as carrier, and it is layer structure, and granularity is nanoscale, is obtained
Nano load halogen-free flameproof composite assistant；The thermostabilization of halogen-free inorganic flame retardant is good, can significantly improve relatively electric trace index
(CTI) compatibility and cohesive force with plastic resin, are substantially improved；Its loading can be increased, improve the benefit of composite
Epistasis；While continuous fiber reinforced polypropylene compound material anti-flammability is provided, its function vector is realized.
In the present invention, the halogen-free flameproof composite assistant includes the Halogen coupling agent of 1~3 parts by weight, preferably 1.5~
2.5 parts by weight.In the present invention, the Halogen coupling agent completes the above-mentioned phosphniline phenolphthalein ring-type with Formulas I structure with assistance
The function being supported in halogen-free inorganic flame retardant of oligomer；The Halogen coupling agent preferably includes silane coupler；In this hair
In bright specific embodiment, the Halogen coupling agent can be trade mark KH570 silane coupler or trade mark KH560
Silane coupler, can also be trade mark KH550 silane coupler.It is special that the present invention does not have to the source of Halogen coupling agent
Limitation, using Halogen coupling agent well known to those skilled in the art, can such as use its commercial goods.
In the present invention, the halogen-free flameproof composite assistant preferably also includes the Halogen function additive of 0.5~25 parts by weight,
Preferably 1~20 parts by weight.In the present invention, the Halogen function additive preferably includes lubricant, toughener, activating agent, anti-
One or more in old agent and antioxidant.The present invention is to the lubricant, toughener, activating agent, age resistor and antioxidant
Species and source do not have special limitation, using lubricant well known to those skilled in the art, toughener, activating agent, age resistor
With antioxidant, its commercial goods can be such as used.In the present invention, the toughener, activating agent, lubricant, age resistor
Mass ratio with antioxidant is preferably (3~10):(1~3):(0.5~2):(0.5~2):(0.5~5).
In the present invention, the lubricant preferably includes stearic acid amide lubricant.The present invention does not have to the source of lubricant
There is special limitation, using above-mentioned lubricant well known to those skilled in the art, can such as use its commercial goods.At this
In inventive embodiments, the stearic acid amide lubricant is bought in Sichuan sky oil chemistry Co., Ltd.
In the present invention, the toughener is preferably POE-g-MAH toughener；The preparation of the POE-g-MAH toughener
Method comprises the following steps：
POE, cumyl peroxide and maleic anhydride are mixed, mixture will be obtained and melt and be granulated,
Obtain POE-g-MAH toughener.
In the present invention, the POE (POE), cumyl peroxide (DCP), maleic anhydride (MAH)
Mass ratio be preferably (96~97)：(0.25~0.35)：(2~4), more preferably 96.7：0.3：3.The present invention is preferably at this
Mixer known to art personnel carries out the mixing of POE, cumyl peroxide and maleic anhydride；Institute
It is preferably 5500~6500rpm to state the speed stirred during mixing, more preferably 5900~6100rpm.In the present invention, it is described mixed
The time of conjunction is preferably 1~3min, more preferably 2min.The present invention is preferably by POE, cumyl peroxide
Melted with maleic anhydride in well known to a person skilled in the art double screw extruder.In the present invention, the melting
Temperature is preferably 120 DEG C~140 DEG C, and the time of melting is preferably 2~4min.In the present invention, the POE-g-MAH toughener
For elastomer particles.
In the present invention, the activating agent preferably includes diphenyl methane-diisocyanate of caprolactam blocking
(HXF011)；The activating agent can improve the compatibility and effect of impregnation of resin matrix and fiber.In the present invention, it is described oneself
Diphenyl methane-diisocyanate of lactams end-blocking is preferably prepared in accordance with the following methods：
The isocyanide of diphenyl methane-two monomer and caprolactam are subjected to end capping reaction, obtain the hexichol of caprolactam blocking
Methylmethane-diisocyanate.
In the present invention, the mass ratio of the isocyanide of diphenyl methane-two monomer and caprolactam is preferably 85~95:8
~12, more preferably 90:10.In the present invention, the temperature of the end capping reaction is preferably 140 DEG C~160 DEG C；The end-blocking is anti-
The time answered is preferably 60min~90min.
In the present invention, the age resistor preferably includes 2,2,4- trimethyl -1,2- dihyaroquinoline condensates；In this hair
In bright specific embodiment, the age resistor is specially trade mark TMQ age resistor.
In the present invention, the antioxidant preferably included for four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta
Four alcohol esters, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid and three [2.4- di-tert-butyl-phenyls] phosphorous
One or more in acid esters；In the specific embodiment of the invention, the antioxidant can be the antioxidant of the trade mark 1010, also may be used
To be the antioxidant of the trade mark 168, the antioxidant of the trade mark 1076 can also be.
The invention provides a kind of preparation method of halogen-free flameproof composite assistant, comprise the following steps：
Phosphniline phenolphthalein cyclic oligomer with Formulas I structure, halogen-free inorganic flame retardant and Halogen coupling agent are mixed, obtained
Halogen-free flameproof composite assistant；
In Formulas I, n=2~7.
In the present invention, the preparation process of the halogen-free flameproof composite assistant specifically preferably includes：
Halogen-free inorganic flame retardant and Halogen coupling agent are mixed, obtain mixture；
The mixture and the phosphniline phenolphthalein cyclic oligomer with Formulas I structure are mixed, obtain fire-retardant composite assistant.
The present invention mixes halogen-free inorganic flame retardant and Halogen coupling agent, obtains mixture.In order to distinguish following technical sides
Mixture described in case, the mixture that halogen-free inorganic flame retardant and Halogen coupling agent are mixed to get is named as the first mixing
Thing.In the present invention, nothing described in species, source and the dosage and above-mentioned technical proposal of inorganic combustion inhibitor and the Halogen coupling agent
The species of halogen inorganic combustion inhibitor and Halogen coupling agent, source are consistent with dosage, will not be repeated here.In the present invention, the nothing
Halogen inorganic combustion inhibitor and Halogen coupling agent preferably mix in well known to a person skilled in the art ultra-high-speed mixing device；The nothing
Halogen inorganic combustion inhibitor and the temperature of Halogen coupling agent mixing are preferably 50 DEG C~70 DEG C；The halogen-free inorganic flame retardant and Halogen are even
The time for joining agent mixing is preferably 30~60s；The halogen-free inorganic flame retardant and Halogen coupling agent are carried out under conditions of stirring
Mixing, the speed of the stirring are preferably not less than 6000rpm；In embodiments of the present invention, the speed of the stirring is
8000rpm。
After obtaining the first mixture, the present invention is by first mixture and has the phosphniline phenolphthalein ring-type of Formulas I structure neat
Polymers mixes, and obtains halogen-free flameproof composite assistant.In the present invention, the phosphniline phenolphthalein cyclic oligomer with Formulas I structure
It is consistent with having the phosphniline phenolphthalein cyclic oligomer of Formulas I structure described in above-mentioned technical proposal, it will not be repeated here.In the present invention
In, the temperature that first mixture and the phosphniline phenolphthalein cyclic oligomer with Formulas I structure mix is preferably 50 DEG C~70 DEG C；
First mixture and the time that there is the phosphniline phenolphthalein cyclic oligomer of Formulas I structure to mix are preferably 30~60s；Described
One mixture and the phosphniline phenolphthalein cyclic oligomer with Formulas I structure are mixed under conditions of stirring, the speed of the stirring
Rate is preferably not less than 6000rpm；In embodiments of the present invention, the speed of the stirring is 8000rpm.
First mixture and phosphniline phenolphthalein cyclic oligomer with Formulas I structure are preferably mixed to get the by the present invention
Two mixtures and the mixing of Halogen function additive, obtain halogen-free flameproof composite assistant.In the present invention, the Halogen function additive
Species, dosage and source are consistent with the species of Halogen function additive, dosage and source described in above-mentioned technical proposal, no longer superfluous herein
State.In the present invention, the temperature of the second mixture and Halogen the function additive mixing is preferably 60 DEG C~80 DEG C, more preferably
65 DEG C~75 DEG C；The time of second mixture and Halogen the function additive mixing is preferably 30~60s.
In embodiments of the present invention, halogen-free flameproof composite assistant is designated as PMF.
The invention provides a kind of PP composite material, by including acrylic resin, fiber and halogen-free flameproof is compound helps
The raw material of agent is made；
The halogen-free flameproof composite assistant is halogen-free flameproof composite assistant or above-mentioned technical proposal described in above-mentioned technical proposal
Halogen-free flameproof composite assistant prepared by the preparation method.
In the present invention, the mass ratio of the acrylic resin and fiber is preferably 0.9~1.1:1；The halogen-free flameproof
The quality of composite assistant preferably accounts for the 10%~40% of PP composite material.Halogen-free flameproof composite assistant provided by the invention exists
Dosage in matrix resin is smaller, in addition to it can play processing aid effect, while has a variety of modified functions again.It is easy to essence simultaneously
Really metering and control, the mistake of production process is effectively reduced, meet the development trend of processing of high molecular material.
The preparing raw material of PP composite material provided by the invention includes polypropylene (PP) resin.The present invention is to described poly-
Allyl resin does not have special limitation, is used for continuous fiber RPP composite wood using well known to those skilled in the art
Acrylic resin in material.In the present invention, the molecular weight of the acrylic resin be preferably 80000g/mol~
100000g/mol；The melt index of the acrylic resin is preferably 6~10g/10min.
The preparing raw material of PP composite material provided by the invention includes fiber.In the present invention, the fiber is preferred
For continuous fiber, the filament diameter of the fiber is preferably 10~100nm.In embodiments of the present invention, the fiber is specific
For glass fibre or carbon fiber.In the present invention, the present invention does not have special limitation to the source of the fiber, using this area
The fiber being used for known to technical staff in PP composite material, can such as use its commercial goods.Of the invention real
Apply in example, the fiber is bought in Jushi Group Co., Ltd..
It is compound that the preparing raw material of PP composite material provided by the invention includes halogen-free flameproof described in above-mentioned technical proposal
Halogen-free flameproof composite assistant prepared by preparation method described in auxiliary agent or above-mentioned technical proposal.
PP composite material provided by the invention is the polypropylene that halogen-free flameproof composite assistant and continuous fiber strengthen
Composite；In some embodiments of the invention, when the continuous fiber is glass fibre, PP composite material is designated as PP
Resin-glass fibre-PMF alloys.It can simplify PP composite material using halogen-free flameproof composite assistant provided by the invention
Production technology, improve production efficiency.
In the present invention, the preparation method of the PP composite material preferably includes following steps：
By the halogen-free flameproof composite assistant melt blending described in acrylic resin, fiber and above-mentioned technical proposal, gathered
Acrylic composite.
In the present invention, the acrylic resin, the source of fiber and halogen-free flameproof composite assistant, species and dosage with it is upper
It is consistent to state technical scheme, will not be repeated here.
The present invention carries out matrix resin, fiber preferably in low sheraing double screw extruder well known to those skilled in the art
With the melt blending of the halogen-free flameproof composite assistant described in above-mentioned technical proposal.In the present invention, seven sections during the melt blending
The temperature of barrel is respectively preferably 185 DEG C~195 DEG C, 205 DEG C~215 DEG C, 215 DEG C~225 DEG C, 225 DEG C~235 DEG C, 225 DEG C
~235 DEG C, 220 DEG C~230 DEG C and 220 DEG C~230 DEG C.The rotating speed of screw rod is preferably 140~160rpm during melt blending, more excellent
Elect 145~155rpm as.
The present invention carries out the test of anti-flammability and mechanical property to above-mentioned PP composite material.The present invention is according to GB/
T2048-2008《The measure Horizontal Bridgman Method and normal beam technique of Plastics Combustion performance》Specified in method to PP composite material carry out
Vertical burn test；The present invention is according to GB/T2406-83《The measuring method of oxygen index (OI)》Specified in method to polypropylene composite materials
Material carries out limited oxygen index test.The present invention is according to GB/T1040-2006《Plastic tensile method for testing performance》Determine poly- third
The tensile strength of alkene composite.The present invention is according to GB/T9341-2000《Plastics-Oetermination of flexural properties method》Determine polypropylene
The bending strength of composite.The present invention is according to GB/T1843-2008《The measure of plastics cantilever beam impact strength》Determine poly- third
The cantilever beam impact strength (breach) of alkene composite.The present invention is according to GB/T1634-2004《The survey of plastics load deformation temperature
It is fixed》Determine the heat distortion temperature of PP composite material.
Test result indicates that：PP composite material provided by the invention has preferable anti-flammability and mechanical strength.
In order to further illustrate the present invention, helped with reference to embodiment is compound to a kind of halogen-free flameproof provided by the invention
Agent, its preparation method and PP composite material are described in detail, but can not be interpreted as them to protect model to the present invention
The restriction enclosed.
Embodiment 1
The preparation process of phosphniline phenolphthalein cyclic oligomer：
The phenylphosphonyl dichloride for weighing 7mmol is dissolved in 50mL dichloromethane, and the dichloromethane for obtaining phenylphosphonyl dichloride is molten
Liquid, the phenolphthalein monomer for weighing 7mmol are dissolved in 50mL 0.28mol/L sodium hydrate aqueous solution, obtain the hydrogen-oxygen of phenolphthalein monomer
Change sodium water solution；
By above two solution in 10 hours slowly, constant speed be added drop-wise to one equipped with 200mL dichloromethane, 40mL go from
Sub- water and 0.2g cetyl trimethylammonium bromide, in the 500mL four-hole bottles under being stirred vigorously, and it is passed through N2Protection, reaction temperature
Degree control is at -20 DEG C~20 DEG C, after being added dropwise, continues reaction 3 hours.React and get organic phase with separatory funnel after terminating,
It is washed with deionized water 2~3 times, to remove inorganic salts, solvent evaporated obtains white solid product, i.e. phosphniline phenolphthalein ring-type oligomerisation
Thing, the phosphniline phenolphthalein cyclic oligomer have following structures：
N=2~7.
By the Malaysia of the POE of 96.7 parts by weight, the cumyl peroxide of 0.3 parts by weight and 3 parts by weight
Acid anhydrides mixes, and will obtain mixture and melts and be granulated, obtains POE-g-MAH toughener；
The isocyanide of diphenyl methane-two monomer of 90 parts by weight and the caprolactam of 10 parts by weight are sealed at 150 DEG C
End reaction, obtains diphenyl methane-diisocyanate of caprolactam blocking；
The laminar nano inorganic combustion inhibitor and the trade mark of 2 parts by weight that the trade mark by 40 parts by weight is TC-5J are KH570 silane
Coupling agent is added in ultra-high-speed mixing device, under conditions of temperature 60 C, rotating speed 8000r/min, is pre-mixed 45s；Then
The above-mentioned phosphniline phenolphthalein cyclic oligomer (CPPA) of 40 parts by weight is added, continues mixed at high speed 45s, temperature 60 C, rotating speed
8000r/min, complete loading process；Be finally introducing the caprolactam blocking of 2 parts by weight diphenyl methane-diisocyanate,
The POE-g-MAH of 10 parts by weight, the stearic amide of 1 parts by weight, age resistor, the board of 2 parts by weight that the 1 parts by weight trade mark is TMQ
Number for 1010 antioxidant, the 2 parts by weight trades mark be 168 antioxidant, continue mix 45s, temperature 70 C, rotating speed 8000r/min,
Continuous fiber enhancing PP nano load halogen-free flameproof composite assistant is obtained, is designated as PMF-01.
Embodiment 2
The laminar nano inorganic combustion inhibitor that the 55 parts by weight trades mark are TC-5J and the silane that the 2 parts by weight trades mark are KH570 is even
Connection agent is added in ultra-high-speed mixing device, under conditions of temperature 60 C, rotating speed 8000r/min, is pre-mixed 45s；Then plus
Enter the phosphniline phenolphthalein cyclic oligomer (CPPA) of 25 parts by weight of example 1 preparation, continue mixed at high speed 45s, temperature 60 C, rotating speed
8000r/min, complete loading process；It is finally introducing the diphenylmethyl of the caprolactam blocking of the preparation of embodiment 1 of 2 parts by weight
POE-g-MAH, stearic amide, the 1 parts by weight trade mark of 1 parts by weight prepared by alkane-diisocyanate, 10 parts by weight of example 1
The antioxidant that the antioxidant for being 1010 for TMQ age resistor, the 2 parts by weight trades mark, the 2 parts by weight trades mark are 168, continue to mix 45s,
Temperature 70 C, rotating speed 8000r/min, continuous fiber enhancing PP nano load halogen-free flameproof composite assistant is obtained, is designated as
PMF-02。
Embodiment 3
By the laminar nano inorganic combustion inhibitor and the silane coupler KH570 of 2 parts by weight that the trade mark of 70 parts by weight is TC-5J
It is added in ultra-high-speed mixing device, under conditions of temperature 60 C, rotating speed 8000r/min, is pre-mixed 45s；Then 10 are added
Phosphniline phenolphthalein cyclic oligomer (CPPA) prepared by parts by weight of example 1, continue mixed at high speed 45s, temperature 60 C, rotating speed
8000r/min, complete loading process；Then the diphenylmethyl of the caprolactam blocking of the preparation of embodiment 1 of 2 parts by weight is added
POE-g-MAH prepared by alkane-diisocyanate, 10 parts by weight of example 1, the stearic amides of 1 parts by weight, 1 parts by weight it is anti-
The antioxidant that antioxidant that old agent TMQ, the trade mark of 2 parts by weight are 1010, the trade mark of 2 parts by weight are 168, continue to mix 45s, temperature
70 DEG C, rotating speed 8000r/min of degree, continuous fiber enhancing PP nano load halogen-free flameproof composite assistant is obtained, is designated as PMF-
03。
Embodiment 4~12
The halogen-free flameproof composite assistant PMF01~PMF03 that will be prepared in embodiment 1~3, strengthen in continuous long glass fiber
Application verification is carried out in PP composites, the wherein proportioning of PP resins and glass fibre is 50:50, halogen-free flameproof composite assistant
PMF introduction volume is respectively be formulated total mass fraction 10%, 25%, 40%.Formula is added to special low after premixing
Melt blending is carried out in shearing double screw extruder, processing temperature is 190 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 225 DEG C
With 225 DEG C, screw speed 150r/min, obtained sample is PP resins-glass fibre-PMF alloys, and the sample trade mark is designated as
FFRPP01~FFRPP09, raw material proportioning are shown in Table 1.
The raw material proportioning of the PP resins of table 1-glass fibre-PMF alloys
Method of the invention according to GB/T2048 and GB/T2406-83, it is by the trade mark in above-described embodiment 4~12
FFRPP01~FFRPP09 samples are made standard batten and carry out vertical burn test and limited oxygen index test, and and PP- respectively
Glass fiber sample is contrasted, and test result is shown in Table 2：
The fire resistance test result of PP resins-glass fibre-PMF alloys prepared by the embodiment 4~12 of table 2
| The sample trade mark | LOI (%) limited oxygen index | UL-94 fire-protection ratings |
| PP- glasses | 20.1 | It is not fire-retardant |
| FFRPP01 | 22.4 | V-2 |
| FFRPP02 | 27.9 | V-0 |
| FFRPP03 | 31.8 | V-0 |
| FFRPP04 | 21.5 | It is not fire-retardant |
| FFRPP05 | 26.8 | V-0 |
| FFRPP06 | 30.4 | V-0 |
| FFRPP07 | 21.9 | It is not fire-retardant |
| FFRPP08 | 26.3 | V-1 |
| FFRPP09 | 30.1 | V-0 |
According to national standard, be to the trade mark in PP resins-glass fiber alloy and embodiment 4~12 FFRPP01~
FFRPP09 samples carry out the sample preparation and test of mechanical property.Testing standard is：Tensile strength presses GB/T1040-2006, and bending is strong
Spend GB/T9341-2000, cantilever beam impact strength (breach) GB/T1843-2008, heat distortion temperature GB/T1634-2004.Survey
Test result is shown in Table 3, and table 3 is PP resin/glass fiber alloy and PP resins-glass fibre-PMF alloy mechanical properties test knot
Fruit：
The PP resins of table 3-glass fiber alloy and
PP resins-glass fibre-PMF alloy mechanical property test results
From table 3 it can be seen that compared with PP resins-glass fiber alloy, in PP composite material provided by the invention
After adding halogen-free flameproof composite assistant, tensile strength is suitable with its, and bending strength increase, notch impact strength has also increased
By force, heat distortion temperature is substantially unchanged.
Comparative example 1
Phosphniline phenolphthalein cyclic oligomer prepared by embodiment 1 is carried out in continuous long glass fiber strengthens PP composites
Application verification, the wherein proportioning of PP resins and glass fibre are 50:50, phosphniline phenolphthalein cyclic oligomer introduction volume is the total matter of formula
The 10% of fraction is measured, is formulated after premixing to be added in special low sheraing double screw extruder and carries out melt blending, is processed
Temperature is 190 DEG C, 210 DEG C, 220 DEG C, 230 DEG C, 230 DEG C, 225 DEG C and 225 DEG C, screw speed 150r/min, obtained sample
For PP resin-glass fibre-phosphniline phenolphthalein cyclic oligomer alloys.
The present invention closes to comparative example 1 according to above-mentioned method of testing to PP resin-glass fibre-phosphniline phenolphthalein cyclic oligomer
Gold carries out the test of anti-flammability and mechanical property, and its flame retardancy test results is：LOI (%) limited oxygen index is 28.6；UL-94
Fire-protection rating is V-0 levels；Its Mechanical test results is shown in Table 4, and table 4 is PP resin-glass fibre-phosphniline phenolphthalein prepared by comparative example
The mechanical experimental results of cyclic oligomer alloy：
The Mechanics Performance Testing of PP resin-glass fibre-phosphniline phenolphthalein cyclic oligomer alloys prepared by the comparative example of table 4
As a result
As seen from the above embodiment, the invention provides halogen-free flameproof composite assistant, including following components：10~40 weight
The phosphniline phenolphthalein cyclic oligomer with Formulas I structure of part；The halogen-free inorganic flame retardant of 40~60 parts by weight；1~3 parts by weight
Halogen coupling agent.Halogen-free flameproof composite assistant provided by the invention includes phosphniline phenolphthalein cyclic oligomer and halogen-free inorganic is fire-retardant
Agent so that halogen-free flameproof composite assistant is in the application of PP composite material, it is possible to increase PP composite material it is fire-retardant
Property and mechanical property.Test result indicates that：The limited oxygen index (LOI) of PP composite material provided by the invention is more than
22%, flame retardant rating >=V-2；Tensile strength is 5.3~6.7GPa；Bending strength is 7.2~8.5GPa；Notch impact strength is
9.1~14KJ/m2。
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of halogen-free flameproof composite assistant, including following components：
The phosphniline phenolphthalein cyclic oligomer with Formulas I structure of 10~40 parts by weight；
The halogen-free inorganic flame retardant of 40~60 parts by weight；
The Halogen coupling agent of 1~3 parts by weight；
In Formulas I, n=2~7；
The halogen-free inorganic flame retardant is the inorganic combustion inhibitor that the trade mark is TC-5J；
The Halogen coupling agent is silane coupler.
2. halogen-free flameproof composite assistant according to claim 1, it is characterised in that also include the nothing of 0.5~25 parts by weight
Halogen function additive；
The Halogen function additive includes toughener, activating agent, lubricant, age resistor and antioxidant.
3. halogen-free flameproof composite assistant according to claim 2, it is characterised in that the lubricant includes stearic acid acyl
Amine；
The age resistor includes 2,2,4- trimethyl -1,2- dihyaroquinoline condensates；
The antioxidant includes four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and/or three [2,4- bis-
Tert-butyl-phenyl] phosphite ester.
4. halogen-free flameproof composite assistant according to claim 2, it is characterised in that the toughener, activating agent, lubrication
The mass ratio of agent, age resistor and antioxidant is (3~10):(1~3):(0.5~2):(0.5~2):(0.5~5).
5. a kind of preparation method of halogen-free flameproof composite assistant, comprises the following steps：
Phosphniline phenolphthalein cyclic oligomer with Formulas I structure, halogen-free inorganic flame retardant and Halogen coupling agent are mixed, obtain Halogen
Fire-retardant composite assistant；
In Formulas I, n=2~7.
6. preparation method according to claim 4, it is characterised in that the temperature of the mixing is 50 DEG C~80 DEG C；It is described
The time of mixing is 0.5~3min.
7. a kind of PP composite material, it is made by the raw material including acrylic resin, fiber and halogen-free flameproof composite assistant；
The halogen-free flameproof composite assistant is halogen-free flameproof composite assistant described in Claims 1 to 4 any one or right 5~6
Halogen-free flameproof composite assistant prepared by preparation method described in any one.
8. composite according to claim 7, the mass ratio of the acrylic resin and fiber is 0.9~1.1:1；
The quality of the halogen-free flameproof composite assistant accounts for the 10%~40% of PP composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510593428.6A CN105061815B (en) | 2015-09-17 | 2015-09-17 | A kind of halogen-free flameproof composite assistant, its preparation method and PP composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510593428.6A CN105061815B (en) | 2015-09-17 | 2015-09-17 | A kind of halogen-free flameproof composite assistant, its preparation method and PP composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105061815A CN105061815A (en) | 2015-11-18 |
| CN105061815B true CN105061815B (en) | 2018-04-10 |
Family
ID=54491355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510593428.6A Active CN105061815B (en) | 2015-09-17 | 2015-09-17 | A kind of halogen-free flameproof composite assistant, its preparation method and PP composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105061815B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105601996B (en) * | 2016-02-04 | 2018-03-06 | 中国科学院宁波材料技术与工程研究所 | A kind of compound and the high polymer material for applying it |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234413A (en) * | 1998-04-28 | 1999-11-10 | 协和化学工业株式会社 | Fire-retardant resin composition and use thereof |
| CN101423666A (en) * | 2008-10-31 | 2009-05-06 | 广东新会美达锦纶股分有限公司 | Halogen-free flame retardant polyamide 6 composition |
| CN101437888A (en) * | 2006-05-03 | 2009-05-20 | 陶氏环球技术公司 | Halogen-free, flame-retardant wire-and-cable composition and related articles |
| CN101531787A (en) * | 2008-03-14 | 2009-09-16 | 朱正华 | Halogen-free flame-retardant long glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN102492226A (en) * | 2011-12-05 | 2012-06-13 | 大连兴辉化工有限公司 | Special additive SYNOXM4228 for copolymerized polypropylene tube material and application thereof |
| CN104629087A (en) * | 2015-03-11 | 2015-05-20 | 中国科学院长春应用化学研究所 | Cyclic polyphosphoester oligmer, and preparation method and application thereof |
-
2015
- 2015-09-17 CN CN201510593428.6A patent/CN105061815B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234413A (en) * | 1998-04-28 | 1999-11-10 | 协和化学工业株式会社 | Fire-retardant resin composition and use thereof |
| CN101437888A (en) * | 2006-05-03 | 2009-05-20 | 陶氏环球技术公司 | Halogen-free, flame-retardant wire-and-cable composition and related articles |
| CN101531787A (en) * | 2008-03-14 | 2009-09-16 | 朱正华 | Halogen-free flame-retardant long glass fiber reinforced polypropylene composite material and preparation method thereof |
| CN101423666A (en) * | 2008-10-31 | 2009-05-06 | 广东新会美达锦纶股分有限公司 | Halogen-free flame retardant polyamide 6 composition |
| CN102492226A (en) * | 2011-12-05 | 2012-06-13 | 大连兴辉化工有限公司 | Special additive SYNOXM4228 for copolymerized polypropylene tube material and application thereof |
| CN104629087A (en) * | 2015-03-11 | 2015-05-20 | 中国科学院长春应用化学研究所 | Cyclic polyphosphoester oligmer, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105061815A (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104031213B (en) | A kind of low smoke and zero halogen heat-resistant fireproof vinyl ester resin and preparation method thereof | |
| CN102875982A (en) | In-situ modified halogen-free flame retardant thermoplastic resin composition and preparation method thereof | |
| CN106751678A (en) | A kind of low smell, it is low distribute, fire retardation PC/ABS composite material and preparation method thereof | |
| CN103951959A (en) | Intumescent flame-retardant reinforced PC (Polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy and preparation method thereof | |
| EP2581379B1 (en) | Halogen-free material containing phosphorous | |
| Yin et al. | The high efficiency two stage intumescent-contractive flame retardant on ABS | |
| EP1276816A1 (en) | Blends of polyarylether sulphone and polyamide, with improved viscosity and flowability | |
| CN107418201A (en) | A kind of efficient halogen-free anti-inflaming enhancing nylon composite materials and preparation method thereof | |
| CN106497027A (en) | A kind of in-situ polymerization type N P synergistic fire-retardant nylons and preparation method thereof | |
| CN104419180A (en) | Glass fiber-enhanced halogen-free and flame-retardant high-toughness PC composite material | |
| CN109401286A (en) | A kind of formula and preparation method of low water absorption flame-retardant reinforced nylon 56 | |
| CN105061815B (en) | A kind of halogen-free flameproof composite assistant, its preparation method and PP composite material | |
| CN107629450A (en) | A kind of environment friendly non-halogen type fiber glass reinforced polyamide fire retardant | |
| CN109776865A (en) | A kind of toughening flame-proof lactic acid composite material and preparation method thereof | |
| CN103694695B (en) | A kind of fiber glass reinforced halogen-free flame retardant PA6/PS alloy material and preparation method thereof | |
| KR101589324B1 (en) | Polymer composition comprising phenolic resin | |
| CN106398137A (en) | Halogen-free inflaming-retarding long glass fiber reinforced PET (Polyethylene Terephthalate) composite material and preparation method thereof | |
| DE102015209451A1 (en) | Flame-retardant polyamides | |
| US5942584A (en) | Flame-retardant polyamides | |
| WO2012098185A1 (en) | Flame-protected thermoplastic molding compound | |
| CN109575324B (en) | Chemically modified transparent flame-retardant PET master batch and manufacturing method and application thereof | |
| CN105153416A (en) | Bi-phosphorous flame-retardant copolymer nylon and preparation method thereof | |
| CN106633193A (en) | High-quality fire retardant | |
| CN106380788A (en) | Halogen-free flame retardant, halogen-free flame-retarding epoxy resin and preparation method thereof | |
| CN104629320A (en) | Low-smoke nano flame retardant PC/ABS alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |