CN108219153A - Siliceous hyperbranched poly phosphamide expansion type flame retardant and its preparation method and application - Google Patents
Siliceous hyperbranched poly phosphamide expansion type flame retardant and its preparation method and application Download PDFInfo
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- CN108219153A CN108219153A CN201711238311.1A CN201711238311A CN108219153A CN 108219153 A CN108219153 A CN 108219153A CN 201711238311 A CN201711238311 A CN 201711238311A CN 108219153 A CN108219153 A CN 108219153A
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- 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
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Abstract
The invention discloses a kind of siliceous hyperbranched poly phosphamide expansion type flame retardants and preparation method thereof, and preparation method is：It is NH through phosphorus oxychloride and general structure2‑R‑NH2Compound and general structure are
Description
Technical field
The invention belongs to technical field of flame retardant, and in particular to a kind of siliceous hyperbranched poly phosphamide expansion type flame retardant and
Preparation method and application.
Background technology
High molecular material has the multifrequency natures such as density is low, elasticity is good, intensity is high, processability is good, in traffic, building, packet
The fields such as dress, daily life are widely used, but there are a critical defects --- and easy firing comes to mankind's property and safety belt
Very big hidden danger.Therefore, it is that high molecular material is promoted to send out at a high speed to research and develop safe and reliable, environment-protecting and non-poisonous, cost effective fire retardant
The safety guarantee of exhibition.
Expansion type flame retardant can form one layer of fine and close foaming layer of charcoal, tool because of P, N synergistic effect in polymer surface
There are good heat-insulated, oxygen barrier, suppression cigarette and anti-molten drop effect, good flame retardation effect, the application increasingly extensive.Current industrialized intumescent
Fire retardant is mainly made of carbon source, acid source and a variety of micromolecular compound compoundings of air source, is existed not water-fastness, easy to migrate, easy
Reunite, the defects of with polymeric matrix poor compatibility, lead to that its flame retarding efficiency is low, and persistence is poor.And three sources are integrated in one
Hyperbranched expandable type fire retardant, not only the fire-retardant synergy of three is good, but also utilizes its unique 3 D stereo reticular structure, low
Viscosity, high activity, easily modified etc. characteristics can also improve the interface compatibility between matrix and play enhancing, toughening effect, should
It is very wide with prospect.
CN 102304222 A, CN 102633999 A, CN 104262680 A, CN 106380595 A be respectively adopted not
Phosphorus-containing compound is grafted to nitrogenous dissaving polymer end with mode, is prepared for different types of end phosphate hyperbranched poly
Phosphate flame retardant.CN 103360605 A, CN 101880393 A AB is respectively adopted2Monomer, A2+B3It is prepared by monomer, one-step method
Hyper branched polyphosphate amine ester containing phosphoric acid ester bond and phosphinylidyne amine key simultaneously has certain biodegradability.CN
103073725 A are first prepared for amino-containing hyperbranched polyorganosiloxane, then are reacted with the dichloropentate of synthesis, form one
Kind while the expansion type flame retardant containing P, N, Si.The expansion type flame retardant end group of these right dissaving structures is mostly highly polar acyl
Amido is phosphate-based, and the interface compatibility between nonpolar substrates is poor, bad dispersibility, and then leads to composite material easy phase point
From flame retarding efficiency reduces, and mechanical property deteriorates.Therefore, how to retain hyperbranched poly phosphamide superior heat-stability and high resistant
Under the premise of fuel efficiency fruit, improve its interface interaction between nonpolar substrates and be of great significance and value.
Invention content
The technical problems to be solved by the invention are to provide a kind of siliceous hyperbranched poly phosphamide expansion type flame retardant, tool
The features such as polarized is adjustable, and thermal stability is good, and ignition-proof element content is high and nonpolar substrates interface compatibility is good.
Another technical problem to be solved by this invention is to provide a kind of above-mentioned siliceous hyperbranched poly phosphamide intumescent
The preparation method of fire retardant.
Third technical problem to be solved by this invention is to provide a kind of above-mentioned siliceous hyperbranched poly phosphamide intumescent
The application of fire retardant.
To solve above-mentioned first technical problem, siliceous hyperbranched poly phosphamide expansion type flame retardant of the invention is nucleocapsid
Structure --- nuclear structure be " rigid hyperbranched poly phosphamide ", shell structure be " long flexible chain siloxanes ", general structure such as (I)
It is shown：
The wherein described R is alkyl, cycloalkyl, and aryl is connected with alkyl, the ring of alkoxy, cycloalkyloxy or aryloxy group
Alkyl or aryl is connected with alkyl, cycloalkyl or the aryl of alkylthio group, cycloalkylthio or arylthio, is connected with alkylamino radical, cycloalkanes
The alkyl of amido or aryl amine, cycloalkyl or aryl, the alkylamino radical, cycloalkanes amido or aryl amine refer to a hydrogen on amino
The group replaced by alkyl, cycloalkyl or aryl.
DescribedFor alkyl or it is the alkyl for being connected with alkoxy, alkylthio group or alkylamino radical.
The R ' and R " is methyl or ethyl, and R ' and R " is differed.
The x, y, m, n are 0,1,2 or 3, and x+y ≠ 0, x+y+m+n=3.
To solve above-mentioned second technical problem, siliceous hyperbranched poly phosphamide expansion type flame retardant of the invention is by trichlorine
Oxygen phosphorus is respectively NH with general structure2-R-NH2Compound, general structure be(x, y, m, n are 0,1,2 or 3, and x+y ≠ 0, x+y+m+n=
3) polycondensation reaction under catalyst action of compound is made, and specific reaction equation is as follows：
Specifically reaction step is:
1) under 0~10 DEG C of temperature condition, NH is added in into the reaction unit with blender2-R-NH2Compound is urged
Agent (and acid binding agent) and solvent, so that NH2-R-NH2A concentration of 0.1~5mol/L of compound, a concentration of the 0.01 of catalyst
~3mol/L；And reaction system is made to be placed in inert atmosphere；
2) phosphorus oxychloride is slowly dropped in step 1) reaction system, control time for adding 0.5~3 hour drips
Bi Hou, maintenance reaction temperature is constant, and the reaction was continued 0.5~4 hour；Then raising reaction temperature is to 50~90 DEG C, and the reaction was continued 6
~24 hours；
3) it then, is added in into reaction systemCompound, control
The reaction was continued 6~24 hours at 50~90 DEG C for temperature processed；
4) stop stirring, be distilled to recover solvent, washing, products therefrom is 12~48 hours dry at 50~100 DEG C, obtains
The siliceous hyperbranched poly phosphamide expansion type flame retardant.
The solvent of the step 1) is aprotic organic solvent, preferably n,N-Dimethylformamide (DMF), N, N- diformazans
Any one of yl acetamide (DMAc), n-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, acetone, acetonitrile.
The general structure of the step 1) is NH2-R-NH2Compound, R is defined as described above, preferably NH2-R-NH2
For 1,6- hexamethylene diamines, 1,4- cyclohexanediamine, isophorone diamine, normal heptane diamines, n-dodecane diamines, n-tetradecane diamines,
P-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-diaminodiphenylmethane, 4,4 '-diamino bibenzyl, 4,4 '-diaminodiphenyl ether, 4,4'-
Diaminobenzophenone, 4,4'- diaminodiphenyl sulfides, 4,4 '-diaminodiphenylsulfone any one or a few.
The catalyst of the step 1) is also acid binding agent, preferably triethylamine, pyridine, 4-dimethylaminopyridine, N, N- bis-
Any one in wopropyl ethyl amine.
Step 2) the NH2-R-NH2Compound is (0.1~3) by the rate of charge of the amount of substance with phosphorus oxychloride：1.
The step 3)Compound, R, R ", x, y, m, n's
It is defined as described above, preferablyFor γ-aminopropyltriethoxy diethoxy
Silane, γ-aminopropyltriethoxy dimethoxy silicon, 3- aminopropyl triethoxysilanes, 3- aminopropyl trimethoxysilanes, N- ammonia second
Base -3- aminopropyl trimethoxysilanes, N- aminoethyl -3- aminopropyl triethoxysilanes, N- (β-aminoethyl)-γ-aminopropyl
One kind in metil-dimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxy-diethoxy silane. It is (0.1~1.5) that the ratio between amount of substance is pressed with phosphorus oxychloride：1.
It is of the invention by above-mentioned siliceous hyperbranched poly phosphamide expansion type flame retardant to solve above-mentioned third technical problem
(Si-HBPA) with ammonium polyphosphate (APP) Application of composite in non-polar polymer matrix to prepare highly effective flame-retardant apolar polymeric
Object composite material, includes the following steps：
By 10wt%~30wt% by siliceous hyperbranched poly phosphamide fire retardant (Si-HBPA) and ammonium polyphosphate (APP)
Compound flame retardant, the 90wt%~70wt% non-polar polymer matrix of composition, antioxidant be (polymer matrix weight
0.1wt%~0.5wt%) it adds in torque rheometer, temperature is controlled between 100~200 DEG C, and speed of agitator is 20~50r/
Min, process time are 10~30min, you can obtain the highly effective flame-retardant non-polar polymer composite material.
The antioxidant is [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol resin.
In the compound flame retardant, the mass ratio of siliceous hyperbranched poly phosphamide expansion type flame retardant and ammonium polyphosphate is
(0.5~3)：1.
The non-polar polymer matrix is preferably one kind in polyethylene (PE), polypropylene (PP), polystyrene (PS).
Siliceous hyperbranched poly phosphamide expansion type flame retardant advantage according to the present invention is：1) " one-step method " work is used
Skill, easy to operate, easy to produce, solvent recoverable, conducive to environmental protection；2) contain fire-retardant member in super branched molecule structure simultaneously
Plain P, N, Si, act synergistically, and foamed char is closely knit, and flame retarding efficiency is high；3) the hyperbranched nucleocapsid of " an iron hand in a velvet glove " makes it
Thermal stability is high, good with nonpolar substrates compatibility, there is toughening effect.
Description of the drawings
Fig. 1 is the infrared spectrum for the siliceous hyperbranched poly phosphamide expansion type flame retardant Si-HBPA1 that embodiment 1 synthesizes.
Fig. 2 is the siliceous hyperbranched poly phosphamide expansion type flame retardant Si-HBPA1's that embodiment 1 synthesizes1H nuclear magnetic spectrograms.
Specific embodiment
The present invention is further described specifically below in conjunction with the drawings and specific embodiments, chemicals Jun Ke cities of institute
It sells.Polyethylene (model in non-polar polymer matrix：LA, 50D012) and polystyrene (model：GPPS-500 in) coming from
Petroleum gas Co., Ltd of state, polypropylene (model：PPH-T03) from Sinopec North Sea refinery Co., Ltd.It needs
It is to be noted that following case study on implementation is served only for, the present invention is described further, it is impossible to be interpreted as to the scope of the present invention
Limitation.Field technology personnel make the present invention according to foregoing invention content some nonessential modifications and adaptations, still belong to
In protection scope of the present invention.
Embodiment 1：By the 4,4 ' of 0.025mol -- diaminodiphenylmethane and 0.05mol triethylamines are dissolved in 100mL second
Nitrile is added in the 500mL three-necked flasks with reflux agitating device；Nitrogen is passed through so that system keeps inert atmosphere, 0~10
Under DEG C reaction temperature, (time for adding totally 1 hour) is added dropwise in system in 0.020mol phosphorus oxychloride, is dispersed with stirring stabilization,
Reaction 30 minutes is kept, 60 DEG C is then heated to and reacts 24 hours；Again by the 3- aminopropyl triethoxysilanes of 0.012mol
(KH550) reaction system is added in, control temperature is reacted 12 hours at 80 DEG C.After the completion of reaction, solvent is distilled to recover, ethyl alcohol is washed
Wash 3 times, in 80 DEG C of vacuum drying ovens dry 12 hours to get to siliceous hyperbranched poly phosphamide expanding fire retardant Si-HBPA1.
As shown in Figure 1 it is found that 3400cm in infrared spectrogram-1And 1619cm-1For secondary amino group (N-H) stretching vibration and flexural vibrations peak,
1388cm-1Locate as P-N stretching vibration peaks, and 1234cm-1Locate the stretching vibration peak for P=O, 1041cm-1Locate as Si-O-Si's
Stretching vibration peak.Shown in Fig. 21It is found that chemical shift in 3.42ppm and 1.17ppm is respectively siloxanes in H nuclear magnetic spectrum figures
The chemical shift peak of methylene and methyl, chemical shift are respectively P-NH-ph- and P-NH-CH in 3.11ppm and 2.08ppm2-
Chemical shift peak.
Embodiment 2：By the 4,4 ' of 0.03mol -- diaminodiphenylsulfone and 0.06mol pyridinium dissolutions are in 120mL dimethyl Asia
Sulfone is added in the 500mL three-necked flasks with reflux agitating device；It is passed through nitrogen and keeps inert atmosphere, in 0~10 DEG C of reaction temperature
Under degree, (time for adding totally 1.5 hours) is added dropwise in system in 0.025mol phosphorus oxychloride, is dispersed with stirring stabilization, keeps anti-
It answers 40 minutes, then heats to 60 DEG C and react 24 hours；The 3- aminopropyl trimethoxysilanes of 0.018mol are added in again and are reacted
System, control temperature are reacted 12 hours at 80 DEG C.After the completion of reaction, solvent is distilled to recover, ethyl alcohol washs 3 times, true at 80 DEG C
In empty baking oven dry 12 hours to get to siliceous hyperbranched poly phosphamide expanding fire retardant Si-HBPA2.
Embodiment 3：1, the 6- hexamethylene diamines of 0.028mol and 0.065mol triethylamines are dissolved in 120mL chloroforms, added
Enter into the 500mL three-necked flasks with reflux agitating device；It is passed through nitrogen and keeps inert atmosphere, under 0~10 DEG C of reaction temperature,
(time for adding totally 1.25 hours) is added dropwise in system in 0.023mol phosphorus oxychloride, is dispersed with stirring stabilization, keeps reaction 30
Minute, it then heats to 60 DEG C and reacts 24 hours；The γ of 0.015mol-aminopropyltriethoxy dimethoxysilane is added in into reaction again
System, control temperature are reacted 12 hours at 80 DEG C.After the completion of reaction, solvent is distilled to recover, ethyl alcohol washs 3 times, true at 80 DEG C
In empty baking oven dry 12 hours to get to siliceous hyperbranched poly phosphamide expanding fire retardant Si-HBPA3.
Embodiment 4：The 4-dimethylaminopyridine of 0.03mol p-phenylenediamine and 0.06mol is dissolved in 150mL acetone, is added
Enter into the 500mL three-necked flasks with reflux agitating device；Nitrogen is passed through so that system keeps inert atmosphere, at 0~10 DEG C instead
At a temperature of answering, (time for adding totally 1.5 hours) is added dropwise in system in 0.025mol phosphorus oxychloride, is dispersed with stirring stabilization, protected
Reaction 50 minutes is held, 60 DEG C is then heated to and reacts 24 hours；Again by the N- of 0.018mol (2- aminoethyls) -3- aminopropyl front threes
Oxysilane adds in reaction system, and control temperature is reacted 12 hours at 80 DEG C.After the completion of reaction, it is distilled to recover solvent, ethyl alcohol
Washing 3 times, in 80 DEG C of vacuum drying ovens dry 12 hours to get to siliceous hyperbranched poly phosphamide expanding fire retardant Si-
HBPA4。
Embodiment 5：By the 1,4- cyclohexanediamine of 0.032mol and 0.062mol pyridinium dissolutions in the N- methyl -2- of 180mL
Pyrrolidones is added in the 500mL three-necked flasks with reflux agitating device；Be passed through nitrogen so that system keep inert atmosphere,
Under 0~10 DEG C of reaction temperature, 0.023mol phosphorus oxychloride is added dropwise in system (time for adding 1.5 hours) totally, is stirred
Stably dispersing keeps reaction 45 minutes, then heats to 60 DEG C and reacts 24 hours；Again by the N- of 0.010mol (2- aminoethyls)-
3- aminopropyl triethoxysilanes add in reaction system, and control temperature is reacted 12 hours at 80 DEG C.After the completion of reaction, distill back
Solvent is received, ethyl alcohol washs 3 times, expands resistance to get to siliceous hyperbranched poly phosphamide within dry 12 hours in 80 DEG C of vacuum drying ovens
Fire agent Si-HBPA5.
Embodiment 6：By the 4,4 ' of 0.04mol-diaminodiphenyl ether and the N of 0.08mol, N- diisopropylethylamine is dissolved in
In the n,N-Dimethylformamide of 200mL, it is added in the 500mL three-necked flasks with reflux agitating device；Be passed through nitrogen so that
System keeps inert atmosphere, and under 0~10 DEG C of reaction temperature, 0.031mol phosphorus oxychloride is added dropwise in system (during dropwise addition
Between totally 2 hours), be dispersed with stirring stabilization, keep reaction 1 hour, then heat to 60 DEG C and react 24 hours；Again by 0.022mol's
γ-aminopropyltriethoxy dimethoxysilane adds in reaction system, and control temperature is reacted 12 hours at 80 DEG C.After the completion of reaction,
Be distilled to recover solvent, ethyl alcohol washs 3 times, in 80 DEG C of vacuum drying ovens dry 12 hours to get to siliceous hyperbranched poly phosphamide
Expanding fire retardant Si-HBPA6.
Embodiment 7：By dried PP 37.5g, antioxidant 1010 0.18g (0.5wt% of PP mass), Si-HBPA1
6.25g, APP 6.25g, it is blended uniformly after, be placed in torque rheometer, controlled at 190 DEG C, rotating speed 35r/min,
Process time is 15min, and obtained blend pressure of 15MPa at 190 DEG C depresses to tablet, according to standard GB/T/T
2406.1-2008 and GB/T 2408-2008 cut sample and test the oxygen index (OI) of PP fire proofings and vertical combustion grade (table respectively
1), its tensile and impact properties (table 2) is tested according to standard GB/T/T 1040.1-2006 and GB/T 1843-2008.
Embodiment 8：By dried PP 35g, antioxidant 1010 0.22g (0.5wt% of PP mass), Si-HBPA2
10g, APP 5g, it is blended uniformly after, be placed in torque rheometer, controlled at 190 DEG C, rotating speed 35r/min, during processing
Between for 15min, obtained blend pressure of 15MPa at 190 DEG C depresses to tablet, according to standard GB/T/T 2406.1-
2008 and GB/T 2408-2008 cut sample and test the oxygen index (OI) of PP fire proofings and vertical combustion grade (table 1) respectively, according to
Standard GB/T/T 1040.1-2006 and GB/T 1843-2008 cuts sample and tests its tensile and impact properties (table 2).
Embodiment 9：By dried PP 40g, antioxidant 1010 0.20g (0.5wt% of PP mass), Si-HBPA3
3.33g, APP 6.67g, it is blended uniformly after, be placed in torque rheometer, controlled at 190 DEG C, rotating speed 35r/min,
Process time is 15min, and obtained blend pressure of 15MPa at 190 DEG C depresses to tablet, according to standard GB/T/T
2406.1-2008 and GB/T 2408-2008 cut sample and test the oxygen index (OI) of PP fire proofings and vertical combustion grade (table respectively
1), sample is cut according to standard GB/T/T 1040.1-2006 and GB/T 1843-2008 test its tensile and impact properties (table 2).
Embodiment 10：By dried PE 37.5g, antioxidant 1010 0.18g (0.5wt% of PE mass), Si-
HBPA4 8.33g, APP 4.17g, it is blended uniformly after, be placed in torque rheometer, controlled at 160 DEG C, rotating speed is
30r/min, process time 20min, obtained blend pressure of 15MPa at 160 DEG C depress to tablet, are marked according to country
Quasi- GB/T 2406.1-2008 and GB/T 2408-2008 cut sample and test the oxygen index (OI) and vertical combustion of PE fire proofings respectively
Grade (table 1) cuts sample according to standard GB/T/T 1040.1-2006 and GB/T 1843-2008 and tests its stretching and impact
Energy (table 2).
Embodiment 11：By dried PE 35g, antioxidant 1010 0.22g (0.5wt% of PE mass), Si-HBPA5
5g, APP 10g, it is blended uniformly after, be placed in torque rheometer, controlled at 160 DEG C, rotating speed 30r/min, during processing
Between for 20min, obtained blend pressure of 15MPa at 160 DEG C depresses to tablet, according to standard GB/T/T 2406.1-
2008 and GB/T 2408-2008 cut sample and test the oxygen index (OI) of PE fire proofings and vertical combustion grade (table 1) respectively, according to
Standard GB/T/T 1040.1-2006 and GB/T 1843-2008 cuts sample and tests its tensile and impact properties (table 2).
Embodiment 12：By dried PS 37.5g, antioxidant 1010 0.18g (0.5wt% of PS mass), Si-
HBPA6 6.25g, APP 6.25g, it is blended uniformly after, be placed in torque rheometer, controlled at 180 DEG C, rotating speed is
40r/min, process time 10min, obtained blend pressure of 15MPa at 180 DEG C depress to tablet, are marked according to country
Quasi- GB/T 2406.1-2008 and GB/T 2408-2008 cut sample and test the oxygen index (OI) and vertical combustion of PS fire proofings respectively
Grade (table 1) cuts sample according to standard GB/T/T 1040.1-2006 and GB/T 1843-2008 and tests its stretching and impact
Energy (table 2).
Comparative example 1：It is blended uniform by dried PP 50g, antioxidant 1010 0.25g (0.5wt% of PS mass)
Afterwards, it is placed in torque rheometer, controlled at 190 DEG C, rotating speed 35r/min, process time 15min, obtained blending
Object pressure of 15MPa at 190 DEG C depresses to tablet, according to standard GB/T/T 2406.1-2008 and GB/T 2408-2008
It cuts sample and tests the oxygen index (OI) of PP fire proofings and vertical combustion grade (table 1) respectively, according to standard GB/T/T 1040.1-
2006 and GB/T 1843-2008 cut sample and test its tensile and impact properties (table 2).
Comparative example 2：By dried PP 37.5g, antioxidant 1010 0.18g (0.5wt% of PP mass), APP
12.5g, it is blended uniformly after, be placed in torque rheometer, controlled at 190 DEG C, rotating speed 35r/min, process time is
15min, obtained blend pressure of 15MPa at 190 DEG C depresses to tablet, according to standard GB/T/T 2406.1-2008
Sample is cut with GB/T 2408-2008 and tests the oxygen index (OI) of PP fire proofings and vertical combustion grade (table 1) respectively, according to country
Standard GB/T 1040.1-2006 and GB/T 1843-2008 cut sample and test its tensile and impact properties (table 2).
Comparative example 3：It is blended uniform by dried PE 50g, antioxidant 1010 0.25g (0.5wt% of PE mass)
Afterwards, it is placed in torque rheometer, controlled at 160 DEG C, rotating speed 30r/min, process time 20min, obtained blending
Object pressure of 15MPa at 160 DEG C depresses to tablet, according to standard GB/T/T 2406.1-2008 and GB/T 2408-2008
It cuts sample and tests the oxygen index (OI) of PE fire proofings and vertical combustion grade (table 1) respectively, according to standard GB/T/T 1040.1-
2006 and GB/T 1843-2008 cut sample and test its tensile and impact properties (table 2).
Comparative example 4：By dried PE 37.5g, antioxidant 1010 0.18g (0.5wt% of PE mass), APP
12.5g, it is blended uniformly after, be placed in torque rheometer, controlled at 160 DEG C, rotating speed 30r/min, process time is
20min, obtained blend pressure of 15MPa at 160 DEG C depresses to tablet, according to standard GB/T/T 2406.1-2008
Sample is cut with GB/T 2408-2008 and tests the oxygen index (OI) of PE fire proofings and vertical combustion grade (table 1) respectively, according to country
Standard GB/T 1040.1-2006 and GB/T 1843-2008 cut sample and test its tensile and impact properties (table 2).
Comparative example 5：It is blended uniform by dried PS 50g, antioxidant 1010 0.25g (0.5wt% of PS mass)
Afterwards, it is placed in torque rheometer, controlled at 180 DEG C, rotating speed 40r/min, process time 10min, obtained blending
Object pressure of 15MPa at 180 DEG C depresses to tablet, according to standard GB/T/T 2406.1-2008 and GB/T 2408-2008
It cuts sample and tests the oxygen index (OI) of PS fire proofings and vertical combustion grade (table 1) respectively, according to standard GB/T/T 1040.1-
2006 and GB/T 1843-2008 cut sample and test its tensile and impact properties (table 2).
Comparative example 6：By dried PS 37.5g, antioxidant 1010 0.3g (0.5wt% of PS mass), APP
12.5g, it is blended uniformly after, be placed in torque rheometer, controlled at 180 DEG C, rotating speed 40r/min, process time is
10min, obtained blend pressure of 15MPa at 180 DEG C depresses to tablet, according to standard GB/T/T 2406.1-2008
Sample is cut with GB/T 2408-2008 and tests the oxygen index (OI) of PS fire proofings and vertical combustion grade (table 1) respectively, according to country
Standard GB/T 1040.1-2006 and GB/T 1843-2008 cut sample and test its tensile and impact properties (table 2).
1 flame retardant property of table
2 mechanical property of table
(include as it can be seen from table 1 APP is used alone and is only capable of improvement non-polar polymer fire proofing as fire retardant
Polyethylene, polypropylene and polystyrene) oxygen index (OI), and its vertical combustion grade is not improved, burning time is long, still
There is drip phenomenon.And after Si-HBPA and APP is used in combination, under equal additive amount, the oxygen of non-polar polymer fire proofing
Index reaches fire retardant rank, can also pass through UL-94V-0 ranks, it was demonstrated that siliceous hyperbranched poly phosphamide intumescent resistance of the invention
Combustion agent Si-HBPA and APP has preferable fire-retardant synergy in non-polar polymer matrix.
From table 2 it can be seen that the tensile strength and impact strength of non-polar polymer/APP composite materials are compared with simple polymerisation
Object material, which is compared, to be declined, it is seen that single APP, which does fire retardant, can deteriorate the mechanical property of polymeric matrix.And nonpolarity is poly-
Close object/Si-HBPA/APP composite materials tensile strength, stretch modulus have clear improvement compared with straight polymer material, especially its
Impact strength improves 50%~100% to some extent, these prove that silicon hyperbranched poly phosphinylidyne amine polymer is poly- to nonpolarity
Closing object material has notable toughening effect.
Claims (8)
1. a kind of siliceous hyperbranched poly phosphamide expansion type flame retardant, which is characterized in that the chemical structure of general formula of the fire retardant is such as
Under：
The wherein described R is alkyl, cycloalkyl, and aryl is connected with alkyl, the cycloalkyl of alkoxy, cycloalkyloxy or aryloxy group
Or aryl, alkyl, cycloalkyl or the aryl of alkylthio group, cycloalkylthio or arylthio are connected with, is connected with alkylamino radical, cycloalkanes amido
Or alkyl, cycloalkyl or the aryl of aryl amine, the alkylamino radical, cycloalkanes amido or aryl amine refer to a hydrogen on amino by alkane
The group that base, cycloalkyl or aryl are replaced；
DescribedFor alkyl or it is the alkyl for being connected with alkoxy, alkylthio group or alkylamino radical；
The R ' and R " is methyl or ethyl, and R ' and R " is differed；
The x, y, m, n are 0,1,2 or 3, and x+y ≠ 0, x+y+m+n=3.
2. the preparation method of siliceous hyperbranched poly phosphamide expansion type flame retardant described in claim 1, it is characterised in that：The resistance
Combustion agent is that phosphorus oxychloride is difference NH with general structure respectively2-R-NH2Compound, general structure beCompound under catalyst action polycondensation reaction be made, wherein
X, y, m, n are 0,1,2 or 3, and x+y ≠ 0, x+y+m+n=3, specific reaction step are：
1) under 0~10 DEG C of temperature condition, NH is added in into the reaction unit with blender2-R-NH2Compound, catalyst
And solvent, so that NH2-R-NH2A concentration of 0.1~5mol/L of compound, a concentration of 0.01~3mol/L of catalyst；And make
Reaction system is placed in inert atmosphere；
2) phosphorus oxychloride is slowly dropped in step 1) reaction system, control time for adding is 0.5~3 hour, is added dropwise
Afterwards, maintenance reaction temperature is constant, and the reaction was continued 0.5~4 hour；Then raising reaction temperature is to 50~90 DEG C, and the reaction was continued 6~
24 hours；
3) it then, is added in into reaction systemTemperature is controlled 50
~90 DEG C, the reaction was continued 6~24 hours；
4) stop stirring, be distilled to recover solvent, washing, products therefrom is 12~48 hours dry at 50~100 DEG C, obtains described
Siliceous hyperbranched poly phosphamide expansion type flame retardant.
3. preparation method according to claim 2, which is characterized in that any one is non-proton organic to be following for the solvent
Solvent：N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-Methyl-2-Pyrrolidone, dimethyl sulfoxide, acetone, acetonitrile
Any one.
4. the preparation method according to Claims 2 or 3, which is characterized in that the general structure is NH2-R-NH2Chemical combination
Object is any one or a few of following compound：The positive hexamethylene diamines of 1,6-, 1,4- cyclohexanediamine, isophorone diamine, normal heptane
Diamines, n-dodecane diamines, n-tetradecane diamines, p-phenylenediamine, m-phenylene diamine (MPD), 4,4 '-diaminodiphenylmethane, 4,4 '-two
Amino bibenzyl, 4,4 '-diaminodiphenyl ether, 4,4'- diaminobenzophenones, 4,4'- diaminodiphenyl sulfides, 4,4 '-diamino
Base diphenyl sulphone (DPS).
5. the preparation method according to Claims 2 or 3, which is characterized in that the catalyst is arbitrary for following compound
It is a kind of：Triethylamine, pyridine, 4-dimethylaminopyridine, N, in N- diisopropylethylamine.
6. the preparation method according to Claims 2 or 3, which is characterized in that the general structure isCompound be following compound any one：γ-aminopropyl
Methyldiethoxysilane, γ-aminopropyltriethoxy dimethoxy silicon, 3- aminopropyl triethoxysilanes, 3- aminopropyl trimethoxies
Base silane, N- aminoethyl -3- aminopropyl trimethoxysilanes, N- aminoethyl -3- aminopropyl triethoxysilanes, N- (β-ammonia second
Base)-γ-aminopropyltriethoxy-dimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxy-diethoxy silane.
7. the preparation method according to Claims 2 or 3, which is characterized in that the NH2-R-NH2Compound and phosphorus oxychloride
The ratio between the amount of substance be (0.1~3)：1；It is describedWith phosphorus oxychloride
The ratio between amount of substance is (0.1~1.5)：1.
8. siliceous hyperbranched poly phosphamide expansion type flame retardant described in claim 1 answering in non-polar polymer matrix
With, which is characterized in that include the following steps：
By the compound flame retardant, the 90wt% that are made of siliceous hyperbranched poly phosphamide and ammonium polyphosphate of 10wt%~30wt%
~70wt% non-polar polymer matrix, antioxidant (0.1wt%~0.5wt% of polymer quality) add in torque rheometer
In, temperature is controlled between 100~200 DEG C, and speed of agitator is 20~50r/min, and process time is 10~30min, you can
To the highly effective flame-retardant non-polar polymer composite material；
The antioxidant is [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol resin；
In the compound flame retardant, the mass ratio of siliceous hyperbranched poly phosphamide and ammonium polyphosphate is (0.5~3)：1；
The non-polar polymer matrix is preferably one kind in polyethylene, polypropylene, polystyrene.
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| CN113461963A (en) * | 2021-07-15 | 2021-10-01 | 山东天一化学股份有限公司 | Functionalized hyperbranched phosphorus-containing intumescent flame retardant, preparation method and flame-retardant polymer coating composition |
| CN113549222A (en) * | 2021-08-04 | 2021-10-26 | 中国科学技术大学 | Hyperbranched flame retardant based on phosphorus-silicon-nitrogen synergistic flame retardance and preparation method and application thereof |
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