CN106832963A - A kind of phosphorous network structure fire retardant - Google Patents
A kind of phosphorous network structure fire retardant Download PDFInfo
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- CN106832963A CN106832963A CN201611257564.9A CN201611257564A CN106832963A CN 106832963 A CN106832963 A CN 106832963A CN 201611257564 A CN201611257564 A CN 201611257564A CN 106832963 A CN106832963 A CN 106832963A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
- C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
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- C08L101/00—Compositions of unspecified macromolecular compounds
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The present invention relates to a kind of network structure fire retardant.For existing small molecule fire retardant it is volatile, easily move out, the limited shortcoming of polymer flame retardant less varieties, application field develops a kind of phosphorous macromolecular network structure fire retardant.Linear performed polymer is prepared first, by changing reaction condition, obtains the linear performed polymer of different polymerization degree；The linked of trifunctional is subsequently adding, the macromolecular fire retardant of heterogeneous networks structure is obtained；Blocked finally by functional group, obtain final product.The product not only improves the problem of the volatilization of small molecule fire retardant and migration, and can adjust the thermal decomposition behavior of fire retardant by changing structure and the extent of reaction such that it is able to obtain the product suitable for different polymeric matrixs.The raw materials used wide material sources of the present invention, cheap, polymerization process condition is gentle, easily production, the structure-controllable of fire retardant.Expansion type flame retardant can be used alone as or as carbon forming agent and other fire retardant compound uses.
Description
Technical field
The present invention relates to a kind of network structure fire retardant, and in particular to a kind of network structure fire retardant of phosphorus element-containing.
Background technology
Macromolecular material is all inflammable due to this body structure, a lot, when it is in building, traffic, automobile, object for appreciation
When many fields such as tool, electrical equipment are applied, very big potential safety hazard is brought due to touching the thermals source such as light, electricity, fire.Therefore,
The fire-retardant safe handling safely to it of macromolecular material has great importance, and is also the current safety measure in the whole world.Currently have
The fire retardant kind of many commodity, is applied in different polymer.Wherein phosphorus flame retardant is the Halogen resistance of current most main flow
Combustion agent, including various phosphates, phosphate etc..With raising in the world to environmental requirement, not only expect what fire retardant had had
Flame retardant effect, and wish to be preferably macromolecular type.Because the fire retardant one side flame retardant effect of macromolecular type is excellent, another
Aspect good stability, can improve the shortcoming that small molecule phosphate ester flame retardants are volatile, easily move out, thus more advantage.
In order to obtain polymer-type phosphorus flame retardant, people have attempted many methods, have been developed a series of on line
The fire retardant of property macromolecular class.In recent years, except the fire retardant of linear polymer type, people also begin to pay close attention to the resistance of branched structure
Combustion agent, such as Deng (European Polymer Journal40,2004,1137-1143) POCl3 and resorcinol
Reaction, obtains dissaving structure polymer, improves the anti-flammability of epoxy resin.(the Journal of Polymer such as Chen
Research, 2011,2229-2237) develop a kind of dissaving structure fire retardant using bisphenol-A, methyl alcohol and POCl3.
But every kind of fire retardant has its shortcoming, it is impossible to meet requirement of the growing new technology to fire proofing.Therefore, the present invention
The advantage of conjugated polymer linear structure and dissaving structure, constructs novel phosphorus-containing network structure fire retardant, by changing line
Property performed polymer reaction time, obtain the linearity range of different extent of polymerizations, be subsequently adding crosslinked group, form network structure, most
After introduce silane coupler, surface property is adjusted, so as to obtain phosphorous network structure fire retardant.The fire retardant belongs to polymer-type
Fire retardant, fire retardant decomposition temperature is regulated and controled by network structure, is blocked by surface and is adjusted its compatibility with polymer, so that
Applicability of the regulation fire retardant in different polymeric matrixs.
The content of the invention
The purpose of the present invention is to synthesize a kind of phosphorous network structure fire retardant by one kettle way (three steps).First, using containing
Phosphorus compound A (binary phosphoryl chloride phosphorus oxychloride, either dichlorophosphate or phosphatization chlorine) and compound B (diamine, dihydroxylic alcohols or dihydric phenol) reacts
The linear performed polymer AB with certain degree of polymerization is prepared, the degree of polymerization is controlled by adjusting reaction condition；Then by trifunctional
POCl3、PCl3Or Cyanuric Chloride etc. forms the macromolecular fire retardant with network structure as crosslinked group；Being finally introducing has
The silane coupler of specific function group is blocked, and adjusts its surface property.With small molecule or linear polymer type fire retardant
Compare, phosphorous network structure fire retardant can regulate and control the decomposition behavior and the compatibility with polymer of fire retardant, so as to be applied to
Different polymeric matrixs；And the phosphorous raw materials used wide material sources of network structure fire retardant, preparation technology are gentle controllable, easy
Realize production.
The phosphorous network structure fire retardant concrete structure of the present invention is as follows：
The first step：
Take compound B and solvent L1 is dissolved under the conditions of 0-200 DEG C, while adding acid binding agent F (B in molar ratio:Acid binding agent=
1:2-1:6), stirred in there-necked flask, lead to N2Protection, and connect device for absorbing tail gas.A (B are taken in molar ratio：A=
1.01:1-1.6:1) solvent L2 is dissolved in, is placed in constant pressure funnel, be added dropwise in B solution with the speed of 1-2 drops/s, instead
Answer 0.5-10h.
Second step：
Take the linked (POCl of trifunctional3、PCl3Or Cyanuric Chloride)
It is dissolved in solvent L2, and above-mentioned solution is instilled with the speed of 1~2 drop/s, maintains the temperature at 30~200 DEG C of 0.5~10h of reaction；
3rd step：
Add coupling agent C (mole C=0.01 (B-A)~0.2 (B-A)) to block fire retardant, continue to react 0.5
~5h, suction filtration is washed 3~5 times with alcohol (ethanol, methyl alcohol), is placed in after being dried in 50~100 DEG C of convection ovens and is obtained product.
The formula of diamine is NH in the B2-R1-NH2Or NH-R1-NH, preferably p-phenylenediamine, m-phenylene diamine (MPD), second two
Amine, 1,6- hexamethylene diamines, Putriscine, 4,4- diaminodiphenyl ethers, 4,4- DADPSs, 4,4- diaminourea hexichol first
One or more in alkane, piperazine；
Dihydroxylic alcohols, the formula of phenol are HO-R1-OH, preferably ethylene glycol, 1,3-PD, BDO, three in the B
Glycol, 1,5- pentanediols, 1,6-HD, 1,4- cyclohexanediols, 1,3- cyclohexanediols, hydroquinones, resorcinol, adjacent benzene two
Phenol, bisphenol-A, 2,7 dihydroxy naphthalene, methylnaphthohydroquinone, 4,4 '-dihydroxy diphenyl ether or 4,4 '-dihydroxydiphenylsulisomer.
The formula of the A is R2-POCl2、R2-OPOCl2Phosphonyl dichloride or R1-PCl2A substitution phosphorus dichloride, it is excellent
Select phenyl phosphonyl chloride, dichloro-phenyl phosphate, phenyl dichloro phosphorus, hexamethylene dichloro phosphine, methylphosphine phthalein dichloro, 4- anisyl phosphines
One or more mixtures of acyl dichloro, cyclohexyl phosphonyl dichloride.
Described R1, R2 are to contain the alkane with phenyl ring on 1~30 straight chained alkyl of carbon atom, cycloalkyl, aryl, straight chain
Aryl with alkyl, cycloalkylaryl or cycloalkyl aryl between base, multiple phenyl ring, or be to contain S, O, N, Si or P atom
Straight chained alkyl, cycloalkyl, aryl, the aryl with alkyl, cycloalkyl virtue between the alkyl with phenyl ring, multiple phenyl ring on straight chain
Base or cycloalkyl aryl.R1, R2 can be with identical, it is also possible to different.
The C is 3- aminopropyl trimethoxysilanes (KH-540), 3- aminopropyl triethoxysilanes (KH-550), 3- mercaptos
Propyl-triethoxysilicane (KH-580), 3- mercaptopropyl trimethoxysilanes (KH-590), anilinomethyl triethoxysilane
(ND-42)。
The L1 is：1,4- dioxane, toluene, paraxylene, tetrahydrofuran, acetone, dichloromethane, chloroform, ether,
1-METHYLPYRROLIDONE (NMP)；
The L2 is：Acetonitrile, Isosorbide-5-Nitrae-dioxane, toluene, tetrahydrofuran, acetone, dichloromethane, normal heptane, n-hexane,
Hexamethylene, NMP；
The F is N, the one kind or several in N- diisopropylethylamine, triethylamine, pyridine, N- methylimidazoles, N- butyl imidazoles
Plant mixture.
Beneficial effects of the present invention：Using a kind of phosphorous network structure fire retardant of one pot process, by adjust structure and
Technique can both be used separately as fire retardant, again can be with other fire retardant compounding uses.And fire retardant will not when decomposing
The toxic gases such as hydrogen halides are produced, is a kind of fire retardant of environmental protection.Fire retardant is in network structure, it is easier into charcoal, in addition
Multielement synergy can also be played, flame retarding efficiency is improved；The degree of polymerization of linear adjustment section can be made with the size of regulating networks
Fire retardant have can modulation structure and performance, expand fire retardant the scope of application；Being blocked by coupling agent can improve fire-retardant
Agent and the compatibility of polymer, obtain the fire proofing of excellent combination property.
Product of the present invention not only improves the problem of the volatilization of small molecule fire retardant and migration, and can be by changing structure
With the thermal decomposition behavior that the extent of reaction adjusts fire retardant such that it is able to obtain the product suitable for different polymeric matrixs.This hair
Bright raw materials used wide material sources, cheap, polymerization process condition is gentle, easily production, and the structure-controllable of fire retardant can be independent
As expansion type flame retardant or as carbon forming agent and other fire retardant compound uses.
Brief description of the drawings
Fig. 1 is product in different proportion, the infared spectrum under the differential responses time；
Fig. 2 be nitrogen atmosphere under product in different proportion, the thermogravimetric curve under the differential responses time.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
As shown in Figure 1,3427cm-1It is the stretching vibration of N-H, 2973cm-1It is the C-H stretching vibrations in-CH2,1631cm-1It is the stretching vibration of C=C in phenyl ring, 1492cm-1It is the skeletal vibration characteristic peak of phenyl ring, 1030cm-1It is the absorption of P-N-C
Peak, with the extension in reaction time, 1030cm-1、2973cm-1The absworption peak enhancing at place, piperazine content increases in illustrating product.
Embodiment 1
Take piperazine 2.58g (0.03mol) and 20ml CH are dissolved under the conditions of 30 DEG C2Cl2, while adding acid binding agent triethylamine
6.07g (0.06mol), is stirred until homogeneous with the rotating speed of 200r/min in there-necked flask, and system leads to N2Protection, and connect tail gas suction
Receiving apparatus.Take phenyl phosphonyl chloride 4.87g (0.025mol) and be dissolved in 20ml dichloromethane and be placed in constant pressure funnel, with 1-
2 drop/s drop speed are added dropwise reacts 1h in piperazine solution, has white precipitate to produce.Then POCl is taken30.51g (0.0033mol) is molten
It is placed in constant pressure funnel in 20ml dichloromethane and instills above-mentioned solution, temperature control continues to react 1h at 40 DEG C, finally adds
Enter coupling agent KH550 0.11g (0.0005mol) to continue to react 2h, suction filtration is simultaneously fully washed with ethanol and obtains sticky mass,
Product is placed in 60 DEG C of convection ovens after drying 1h and is transferred to 60 DEG C of drying 2h of vacuum drying oven, obtain faint yellow after dry, grinding
Powder.
This product is named as P1, and as shown in a curves in Fig. 1, thermogravimetric curve is as shown in a curves in Fig. 2 for infared spectrum.
Embodiment 2
Reaction time first stage of embodiment 1 is changed to 2h, remaining condition is constant, can obtain product P2, infared spectrum
As shown in b curves in Fig. 1, thermogravimetric curve is as shown in b curves in Fig. 2.
Embodiment 3
Take piperazine 3.27g (0.038mol) and 25ml CH are dissolved under the conditions of 30 DEG C2Cl2, while adding acid binding agent N, N- bis-
Wopropyl ethyl amine 10.34g (0.08mol), is stirred until homogeneous with the rotating speed of 300r/min in there-necked flask, and system leads to N2Protection,
And connect device for absorbing tail gas.Take phenyl phosphonyl chloride 4.87g (0.024mol) and be dissolved in 20ml dichloromethane and be placed in constant pressure addition
In funnel, it is added dropwise and 1h is reacted in piperazine solution with 1-2 drops/s drop speed, has white precipitate to produce.Then POCl is taken3 1.42g
(0.0093mol) is dissolved in 20ml dichloromethane and is placed in constant pressure funnel and instill above-mentioned solution, and temperature control is in 30 DEG C of continuation
Reaction 1h, adds coupling agent KH550 0.09g (0.0004mol) to continue to react 3h, and suction filtration and fully being washed with methyl alcohol is glued
Thick liquid matter, product is placed in 70 DEG C of convection ovens after drying 2h and is transferred to 70 DEG C of drying 3h of vacuum drying oven, after dry, grinding
To pale yellow powder.
This product is named as P3, and as shown in c curves in Fig. 1, thermogravimetric curve is as shown in c curves in Fig. 2 for infared spectrum.
Embodiment 4
Reaction time first stage of embodiment 3 is changed to 2h, remaining condition is constant, can obtain product P4, infared spectrum
As shown in d curves in Fig. 1, thermogravimetric curve is as shown in d curves in Fig. 2.
Embodiment 5
Take p-phenylenediamine 3.27g (0.03mol) and 50ml NMP are dissolved under the conditions of 30 DEG C, while adding acid binding agent triethylamine
6.49g (0.06mol), is stirred until homogeneous with the rotating speed of 200r/min in there-necked flask, and system leads to N2Protection, and connect tail gas suction
Receiving apparatus.Take dichloro-phenyl phosphate 5.27g (0.025mol) and be dissolved in 40ml NMP and be placed in constant pressure funnel, with 1-2 drops/s
Drop speed is added dropwise reacts 1h in p-phenylenediamine solution.Then PCl is taken30.48g (0.0035mol) is dissolved in 20ml NMP and is placed in
Above-mentioned solution is instilled in constant pressure funnel, temperature control continues to react 3h at 50 DEG C, adds coupling agent KH580 0.12g
(0.0005mol) continues to react 3h, and suction filtration is simultaneously fully washed with methyl alcohol, product is placed in 70 DEG C of convection ovens after drying 2h and turned
Enter 70 DEG C of drying 3h of vacuum drying oven, product is obtained after dry, grinding.
Embodiment 6
Take ethylenediamine 3.00g (0.05mol) and 40ml chloroforms are dissolved under the conditions of 30 DEG C, while adding acid binding agent pyridine 7.9g
(0.10mol), is stirred until homogeneous with the rotating speed of 200r/min in there-necked flask, and system leads to N2Protection, connects device for absorbing tail gas.Take
Dichloro-phenyl phosphate 9.49g (0.045mol) is dissolved in 50ml dichloromethane and is placed in constant pressure funnel, with 1-2 drops/s drops speed drop
It is added in piperazine solution and reacts 0.5h.Then POCl is taken30.53g (0.0035mol) is dissolved in 20ml dichloromethane and is placed in constant pressure drop
Above-mentioned solution is instilled in liquid funnel, temperature control continues to react 3h at 40 DEG C, adds coupling agent KH590 0.08g
(0.0004mol) continues to react 5h, and suction filtration is simultaneously fully washed with ethanol, product is placed in 70 DEG C of convection ovens after drying 1h and turned
Enter 70 DEG C of drying 4h of vacuum drying oven, product is obtained after dry, grinding.
Embodiment 7
Take piperazine 3.44g (0.04mol) and 30ml CH are dissolved under the conditions of 30 DEG C2Cl2, while adding acid binding agent triethylamine
8.09g (0.08mol), is stirred until homogeneous with the rotating speed of 300r/min in there-necked flask, and system leads to N2Protection, and connect tail gas suction
Receiving apparatus.Take phenyl dichloro phosphorus 5.73g (0.032mol) and be dissolved in 60ml dichloromethane and be placed in constant pressure funnel, with 1-
2 drop/s drop speed are added dropwise reacts 1h in piperazine solution, has white precipitate to produce.Then POCl is taken30.86g (0.0056mol) is molten
Above-mentioned solution is instilled in 20ml dichloromethane is placed in constant pressure funnel, temperature control continues to react 1h at 40 DEG C, adds
Coupling agent ND-42 0.1g (0.0005mol) continues to react 5h, and suction filtration is simultaneously fully washed with ethanol, and product is placed in into 60 DEG C of air blast
60 DEG C of drying 4h of vacuum drying oven are transferred to after 1h is dried in baking oven, product is obtained after dry, grinding.
Embodiment 8
P-phenylenediamine in embodiment 5 is replaced by m-phenylene diamine (MPD), remaining condition is constant to obtain product.
Embodiment 9
Take 1,6- hexamethylene diamines 3.44g (0.035mol) and 40ml NMP are dissolved under the conditions of 70 DEG C, while adding acid binding agent three
Ethamine 8.09g (0.08mol), is stirred until homogeneous with the rotating speed of 300r/min in there-necked flask, and system leads to N2Protection, and connect tail
Aspiration receiving apparatus.Take phenyl phosphonyl chloride 5.85g (0.03mol) and be dissolved in 60ml NMP and be placed in constant pressure funnel, with 1-2
Drop/s drop speed is added dropwise reacts 1h in 1,6- hexamethylene diamine solution, then takes POCl30.54g (0.0035mol) is dissolved in 20ml NMP
It is placed in instilling above-mentioned solution in constant pressure funnel, temperature control continues to react 3h at 80 DEG C, adds coupling agent KH540
0.18g (0.001mol) continues to react 2h, and suction filtration is simultaneously fully washed with ethanol, product is placed in 60 DEG C of convection ovens and dries 1h
After be transferred to 60 DEG C of vacuum drying oven drying 4h, dry, obtain product after grinding.
Embodiment 10
1,6- hexamethylene diamines in embodiment 9 are replaced by Putriscine, remaining condition is constant to obtain product.
Embodiment 11
Take 4,4- diaminodiphenyl ethers 4.00g (0.02mol) and 60ml NMP are dissolved under the conditions of 70 DEG C, while acid is tied up in addition
Agent pyridine 3.16g (0.04mol), is stirred until homogeneous with the rotating speed of 200r/min in there-necked flask, and system leads to N2Protection, and connect
Device for absorbing tail gas.Take phenyl phosphonyl chloride 2.92g (0.015mol) and be dissolved in 30ml NMP and be placed in constant pressure funnel, with 1-
2 drop/s drop speed are added dropwise reacts 1h in 4,4- diaminodiphenyl ether solution, then takes PCl30.48g (0.0035mol) is dissolved in
20ml NMP are placed in instilling above-mentioned solution in constant pressure funnel, and temperature control continues to react 3h at 80 DEG C, adds coupling agent
KH580 0.07g (0.0003mol) continue to react 2h, and suction filtration is simultaneously fully washed with ethanol, and product is placed in into 60 DEG C of convection ovens
60 DEG C of drying 4h of vacuum drying oven are transferred to after middle drying 1h, product is obtained after dry, grinding.
Embodiment 12
4,4- diaminodiphenyl ethers in embodiment 11 are replaced by 4,4- DADPSs, acid binding agent is changed to triethylamine,
Remaining condition is constant to obtain product.
Embodiment 13
4,4- diaminodiphenyl ethers in embodiment 11 are replaced by 4,4- MDAs, remaining condition is constant to be obtained
Product.
Embodiment 14
Take piperazine 2.58g (0.03mol) and 20ml dioxane is dissolved under the conditions of 30 DEG C, while adding acid binding agent triethylamine
6.07g (0.06mol), is stirred until homogeneous with the rotating speed of 200r/min in there-necked flask, and system leads to N2Protection, and connect tail gas suction
Receiving apparatus.Take phenyl phosphonyl chloride 4.87g (0.025mol) and be dissolved in 20ml dioxane and be placed in constant pressure funnel, with 1-2
Drop/s drop speed is added dropwise reacts 1h in piperazine solution, has white precipitate to produce.Then temperature control takes Cyanuric Chloride at 95 DEG C
0.64g (0.0035mol) is dissolved in 20ml dioxane and is placed in constant pressure funnel and instills above-mentioned solution, continues to react 1h, most
Coupling agent KH580 0.09g (0.0004mol) is added to continue to react 2h afterwards, suction filtration is simultaneously fully washed with ethanol, product is placed in
60 DEG C of drying 2h of vacuum drying oven are transferred to after 1h is dried in 60 DEG C of convection ovens, product is obtained after dry, grinding.
Embodiment 15
Take ethylene glycol 3.10g (0.05mol) and 40ml chloroforms are dissolved under the conditions of 30 DEG C, while adding acid binding agent N- methyl miaows
Azoles 12.31g (0.15mol), is stirred until homogeneous with the rotating speed of 200r/min in there-necked flask, and system leads to N2Protection, connects tail gas suction
Receiving apparatus.Take cyclohexyl phosphonyl dichloride 9.04g (0.045mol) and be dissolved in 40ml dichloromethane and be placed in constant pressure funnel, with 1-
2 drop/s drop speed are added dropwise reacts 1h in ethylene glycol solution.Then PCl is taken30.48g (0.0035mol) is dissolved in 20ml dichloromethane
It is placed in constant pressure funnel and instills above-mentioned solution, temperature control continues to react 1h at 60 DEG C, adds coupling agent KH590 0.06g
(0.0003mol) continues to react 4h, and suction filtration is simultaneously fully washed with ethanol, product is placed in 60 DEG C of convection ovens after drying 1h and turned
Enter 60 DEG C of drying 3h of vacuum drying oven, product is obtained after dry, grinding.
Embodiment 16
Take hydroquinones 3.03g (0.03mol) and 50ml NMP are dissolved under the conditions of 90 DEG C, while adding acid binding agent N- butyl
Imidazoles 8.69g (0.07mol), is stirred until homogeneous with the rotating speed of 300r/min in there-necked flask, and system leads to N2Protection, and connect tail
Aspiration receiving apparatus.Take hexamethylene dichloro phosphine 4.62g (0.025mol) and be dissolved in 40ml NMP and be placed in constant pressure funnel, with 1-2 drops/
S drop speed is added dropwise reacts 1h in quinol solution, then takes PCl30.46g (0.0034mol) is dissolved in 20ml NMP and is placed in
Above-mentioned solution is instilled in constant pressure funnel, temperature control continues to react 2h at 90 DEG C, adds coupling agent KH550 0.09g
(0.0004mol) continues to react 2h, and suction filtration is simultaneously fully washed with ethanol, product is placed in 60 DEG C of convection ovens after drying 2h and turned
Enter 60 DEG C of drying 5h of vacuum drying oven, product is obtained after dry, grinding.
Embodiment 17
Take Isosorbide-5-Nitrae-cyclohexanediol 4.65g (0.04mol) and 60ml NMP are dissolved under the conditions of 90 DEG C, while adding acid binding agent pyrrole
Pyridine 7.12g (0.09mol), is stirred until homogeneous with the rotating speed of 300r/min in there-necked flask, and system leads to N2Protection, and connect tail gas
Absorption plant.Take methylphosphine phthalein dichloro 3.99g (0.03mol) and be dissolved in 30ml dioxane and be placed in constant pressure funnel, with 1-2
Drop/s drop speed is added dropwise reacts 0.5h in Isosorbide-5-Nitrae-cyclohexanediol solution, then takes PCl30.96g (0.007mol) is dissolved in 40ml bis-
The ring of oxygen six is placed in instilling above-mentioned solution in constant pressure funnel, and temperature control continues to react 2h at 95 DEG C, adds coupling agent
KH590 0.1g (0.0005mol) continue to react 4h, and suction filtration is simultaneously fully washed with ethanol, product is placed in 70 DEG C of convection ovens
60 DEG C of drying 6h of vacuum drying oven are transferred to after drying 2h, product is obtained after dry, grinding.
Embodiment 18
Take BDO 4.51g (0.05mol) and 50ml NMP are dissolved under the conditions of 0 DEG C, while adding acid binding agent pyridine
23.8g (0.3mol), is stirred until homogeneous with the rotating speed of 200r/min in there-necked flask, and system leads to N2Protection, and connect tail gas suction
Receiving apparatus.Take phenyl phosphonyl chloride 8.58g (0.044mol) and be dissolved in 50mlNMP and be placed in constant pressure funnel, with 1-2 drops/s drops
Speed is added dropwise reacts 0.5h in BDO solution, then takes PCl30.55g (0.004mol) is dissolved in 30mlNMP and is placed in
Above-mentioned solution is instilled in constant pressure funnel, temperature control continues to react 2h at 200 DEG C, adds coupling agent KH590 0.012g
(0.00006mol) continues to react 4h, and suction filtration is simultaneously fully washed with ethanol, product is placed in after drying 2h in 70 DEG C of convection ovens
70 DEG C of drying 5h of vacuum drying oven are transferred to, product is obtained after dry, grinding.
Embodiment 19
Take bisphenol-A 6.85g (0.03mol) and 80ml NMP are dissolved under the conditions of 30 DEG C, while adding acid binding agent pyridine
6.33g (0.08mol), is stirred until homogeneous with the rotating speed of 250r/min in there-necked flask, and system leads to N2Protection, and connect tail gas suction
Receiving apparatus.Take phenyl phosphonyl chloride 4.87g (0.025mol) and be dissolved in 40ml dioxane and be placed in constant pressure funnel, with 1-2
Drop/s drop speed is added dropwise reacts 0.5h in bisphenol-A solution, then takes PCl30.48g (0.0035mol) is dissolved in 20ml dioxane
It is placed in instilling above-mentioned solution in constant pressure funnel, temperature control continues to react 2h at 90 DEG C, adds coupling agent KH550
0.13g (0.0006mol) continues to react 5h, and suction filtration is simultaneously fully washed with ethanol, product is placed in 60 DEG C of convection ovens and is dried
60 DEG C of drying 4h of vacuum drying oven are transferred to after 2h, product is obtained after dry, grinding.
Embodiment 20
Remaining dihydroxy compounds is reacted with embodiment 16,17.
Above-described embodiment is not that, for limitation of the invention, the present invention is not limited only to above-described embodiment, as long as meeting
Application claims, belong to protection scope of the present invention.
Claims (10)
1. a kind of phosphorous network structure fire retardant, it is characterised in that be prepared from using following methods：
The linear performed polymer AB with certain degree of polymerization is prepared using phosphorus-containing compound A and compound B reactions, it is anti-by regulation
Condition is answered to control the degree of polymerization；Then using the linked of trifunctional as crosslinked group, the macromolecular with network structure is formed
Fire retardant；It is finally introducing the silane coupler with specific function group to be blocked, adjusts its surface property；
Described phosphorus-containing compound A is binary phosphoryl chloride phosphorus oxychloride, either dichlorophosphate or phosphatization chlorine；
Described compound B is diamine, dihydroxylic alcohols or dihydric phenol；
The linked of described trifunctional is POCl3、PCl3Or Cyanuric Chloride.
2. a kind of phosphorous network structure fire retardant as claimed in claim 1, it is characterised in that prepared using method in detail below
Form：
Step (1), compound B is placed in solvent L1 is dissolved at 0~200 DEG C, be subsequently adding acid binding agent F, stirred in there-necked flask
Uniformly, B solution is obtained, leads to N2Protection, and connect device for absorbing tail gas；Phosphorus-containing compound A is dissolved in solvent L2, constant pressure is placed in
In dropping funel, it is added dropwise in B solution with the speed of 1~2 drop/s, reacts 0.5~10h, obtains linear performed polymer AB；
The mol ratio of described compound B and acid binding agent F is 1:2~1:6；
The mol ratio of described compound B and phosphorus-containing compound A is 1.01:1~1.6:1；
Described phosphorus-containing compound A is binary phosphoryl chloride phosphorus oxychloride, either dichlorophosphate or phosphatization chlorine；
Described compound B is diamine, dihydroxylic alcohols or dihydric phenol；
Step (2), the linked for taking trifunctional are dissolved in solvent L2, and instill above-mentioned linear performed polymer with the speed of 1~2 drop/s
In AB solution, 30~200 DEG C of 0.5~10h of reaction are maintained the temperature at, obtain the macromolecular fire retardant with network structure；
The mole of the linked of described trifunctional is
The linked of described trifunctional is POCl3、PCl3Or Cyanuric Chloride；
Step (3), addition coupling agent C are blocked to above-mentioned macromolecular fire retardant, continue to react 0.5~5h, and suction filtration is washed with alcohol
Repeatedly, product is obtained after drying；
The mole of described coupling agent C is 0.01 (B-A)~0.2 (B-A).
3. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that binary in the compound B
The formula of amine is NH2-R1-NH2Or NH-R1-NH, dihydroxylic alcohols, the formula of dihydric phenol are HO-R1-OH；Wherein R1 is to contain 1~30
Aryl with alkyl between the alkyl with phenyl ring, multiple phenyl ring on the straight chained alkyl of individual carbon atom, cycloalkyl, aryl, straight chain,
Cycloalkylaryl or cycloalkyl aryl, or be the straight chained alkyl containing S, O, N, Si or P atom, cycloalkyl, aryl, straight chain
Aryl with alkyl, cycloalkylaryl or cycloalkyl aryl between the upper alkyl with phenyl ring, multiple phenyl ring.
4. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that binary in the compound B
Amine is p-phenylenediamine, m-phenylene diamine (MPD), ethylenediamine, 1,6- hexamethylene diamines, Putriscine, 4,4- diaminodiphenyl ethers, 4,4- diaminos
One or more in base diphenyl sulphone (DPS), 4,4- MDAs, piperazine.
5. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that binary in the compound B
Alcohol, dihydric phenol are ethylene glycol, 1,3- propane diols, 1,4- butanediols, triethylene glycol, 1,5- pentanediols, 1,6-HD, 1,4- hexamethylenes
Glycol, 1,3- cyclohexanediols, hydroquinones, resorcinol, catechol, bisphenol-A, 2,7 dihydroxy naphthalene, methylnaphthohydroquinone, 4,
4 '-dihydroxy diphenyl ether or 4,4 '-dihydroxydiphenylsulisomer.
6. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that the phosphorus-containing compound A's
Formula is R2-POCl2、R2-OPOCl2Phosphonyl dichloride or R1-PCl2A substitution phosphorus dichloride；Wherein R1, R2 are each independent
It is containing being carried between the alkyl with phenyl ring, multiple phenyl ring on 1~30 straight chained alkyl of carbon atom, cycloalkyl, aryl, straight chain
The aryl of alkyl, cycloalkylaryl or cycloalkyl aryl, or be the straight chained alkyl containing S, O, N, Si or P atom, cycloalkanes
Aryl, cycloalkylaryl or the aryl cycloalkanes of alkyl are carried on base, aryl, straight chain between the alkyl with phenyl ring, multiple phenyl ring
Base.
7. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that the phosphorus-containing compound A is
Phenyl phosphonyl chloride, dichloro-phenyl phosphate, phenyl dichloro phosphorus, hexamethylene dichloro phosphine, methylphosphine phthalein dichloro, 4- anisyl phosphonos
One or more mixtures of dichloro, cyclohexyl phosphonyl dichloride.
8. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that the coupling agent C is 3- ammonia
Propyl trimethoxy silicane (KH-540), 3- aminopropyl triethoxysilanes (KH-550), 3- mercaptopropyltriethoxysilanes
(KH-580), 3- mercaptopropyl trimethoxysilanes (KH-590) or anilinomethyl triethoxysilane (ND-42).
9. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, it is characterised in that the solvent L1 is Isosorbide-5-Nitrae-two
The ring of oxygen six, toluene, paraxylene, tetrahydrofuran, acetone, dichloromethane, chloroform, ether, 1-METHYLPYRROLIDONE (NMP)；
The solvent L2 be acetonitrile, Isosorbide-5-Nitrae-dioxane, toluene, tetrahydrofuran, acetone, dichloromethane, normal heptane, n-hexane,
Hexamethylene, NMP；
The acid binding agent F is N, one kind in N- diisopropylethylamine, triethylamine, pyridine, N- methylimidazoles, N- butyl imidazoles or
Several mixtures.
10. a kind of phosphorous network structure fire retardant as claimed in claim 1 or 2, can be used alone as expansion type flame retardant or work
It is carbon forming agent and other fire retardant compound uses.
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