CN106243306B - A kind of flame-retardant polyurethane performed polymer and preparation method thereof - Google Patents
A kind of flame-retardant polyurethane performed polymer and preparation method thereof Download PDFInfo
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- CN106243306B CN106243306B CN201610634583.2A CN201610634583A CN106243306B CN 106243306 B CN106243306 B CN 106243306B CN 201610634583 A CN201610634583 A CN 201610634583A CN 106243306 B CN106243306 B CN 106243306B
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/24—Catalysts containing metal compounds of tin
- C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
- C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/55—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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Abstract
The invention discloses a kind of flame-retardant polyurethane performed polymers and preparation method thereof.Preparation method includes the following steps：1) polyether polyol is added in reaction kettle, is vacuumized, temperature control is simultaneously stirred with blender；2) system cools down, and leads to nitrogen protection；3) diisocyanate is added and proper catalyst, temperature control increases mixing speed simultaneously；4) according to NCO content in system, it is slowly added to silane coupling agent to reaction system, continues to stir；5) fire retardant is added in system, continues to stir；6) system vacuumizes removing bubble, you can obtains target product.The base polyurethane prepolymer for use as of gained of the invention is with excellent flame retardant property simultaneously also with good mechanical performance and environment protecting.
Description
Technical field
The present invention relates to a kind of base polyurethane prepolymer for use as, more particularly to a kind of flame-retardant polyurethane performed polymer and its preparation side
Method.
Background technology
Polyurethane is due to good mechanical property, lower temperature resistance, wearability and having good adhesion etc. special base material
Point, it all has a wide range of applications in building trade and transportation.Modernization with urban architecture and transportation
Continuous development, consumption figure of the fluid sealant in house decoration and communications and transportation increase rapidly.But it is not fire retardant treated poly-
The inflammable disadvantage of urethane material significantly limits its application range, also to the economic asset of related field and personal safety structure
At fire threat.Therefore, development flame-retardant polyurethane material sense is great.
Invention content
It is safe and non-toxic the present invention provides a kind of good flame retardation effect, the flame-retardant polyurethane performed polymer of excellent in mechanical performance
And preparation method thereof.
The object of the invention is achieved through the following technical solutions：
A kind of preparation method of flame-retardant polyurethane performed polymer, includes the following steps：
Polyether polyol is added in reaction kettle by the first step, is vacuumized, and control temperature is at 100 DEG C~120 DEG C, stirring
2-3 hours；
Second step makes system cool to 40 DEG C~50 DEG C, and system leads to nitrogen protection；
Third walks, and two different hydrogen acid ether (hydrogen acid ester)s are added in reaction kettle, dibutyl tin laurate is added, while increasing stirring speed
Degree, control temperature are reacted 3-5 hours at 60 DEG C~80 DEG C；
4th step is slowly added to silane coupling agent into reaction system according to dissociateive NCO content in system, continues to stir
Mix reaction 2-5 hours；
5th step, fire retardant is added into system, continues stirring 1-3 hours；The fire retardant is organic boron nitrogen combustion inhibitor
And magnesium hydroxide；
6th step, reaction terminate, and system vacuumizes removing bubble, obtain flame-retardant polyurethane performed polymer.
To further realize the object of the invention, it is preferable that in terms of mass fraction, the dosage of raw material is：Polyether polyol
100-150 parts, 30~50 parts of two different hydrogen acid ether (hydrogen acid ester), 0.1~1 part of dibutyl tin laurate, 0.1-1 parts of silane coupling agent and 5~
50 parts of fire retardants.
To further realize the object of the invention, it is preferable that the polyether polyol is polyether Glycols and/or polyethers ternary
Alcohol.
To further realize the object of the invention, it is preferable that the polyether Glycols be PPG-1000, PPG-1500,
PPG-2000, PPG-4000, PPG-6000 or PPG-8000；The polyether-tribasic alcohol include PPG-3000, PPG-5000 or
PPG-7000。
To further realize the object of the invention, it is preferable that the diisocyanate is toluene di-isocyanate(TDI) (TDI), two
The different hydrogen acid ether (hydrogen acid ester) of phenylmethane -4,4 '-two (MDI), two different hydrogen acid ether (hydrogen acid ester) (IPDI) of isophorone and hexamethylene diisocyanate
(HDI) one or more in.
To further realize the object of the invention, it is preferable that the silane coupling agent is KH-550, KH-170 and Y-9669
In it is one or more.
To further realize the object of the invention, it is preferable that in terms of mass fraction, the organic boron nitrogen combustion inhibitor is 5-20
Part, the magnesium hydroxide is 5-20 parts.
To further realize the object of the invention, it is preferable that the organic boron nitrogen combustion inhibitor is the chemical combination having following structure
It is one or more in object：
A kind of flame-retardant polyurethane performed polymer, is made by above-mentioned preparation method.
The present invention is had the following advantages that compared with existing polyurethane and advantageous effect：
The flame-retardant polyurethane is unique in that, borate group and triazine ring, boron are contained in flame retardant molecule structure
Acid esters group is dehydrated in combustion, is promoted into charcoal, and triazine ring releases a large amount of fire retardant gases in combustion so that charcoal
Layer expansion.The collective effect of borate group and triazine ring promotes base polyurethane prepolymer for use as to form the layer of charcoal for stablizing expansion, is covered in
Base material shows to serve as thermal insulation layer, and the propagation of isolation heat and oxygen prevents the burning of combustible.In addition boron flame retardant is a kind of
The fire retardant of non-toxic efficient can be effectively promoted epoxy resin into charcoal, inhibit burning.Therefore, prepared polyurethane prepolymer
The flame retardant property that body has not only had is expected to become excellent Environment-friendlypolyurethane polyurethane prepolymer.
Specific implementation mode
To more fully understand the present invention, with reference to embodiment, the present invention is described further, but the reality of the present invention
It is unlimited so to apply mode.
Embodiment 1
The first step, in terms of mass fraction, 65 parts of polyether Glycols (PPG-1000) for being 1000 by relative molecular weight, relatively
Molecular weight be 3000 23 parts of polyether-tribasic alcohol (PPG-3000), be added in reaction kettle, vacuumize, control temperature at 120 DEG C,
Stirring 2 hours；
Second step makes system cool to 40 DEG C, and system leads to nitrogen protection；
Third walks, and in terms of mass fraction, by two 32 parts of addition reaction kettles of different hydrogen acid ether (hydrogen acid ester) (MDI) of diphenyl methane, is added
0.1 part of dibutyl tin laurate increases mixing speed to 300rpm/min, and control temperature is reacted 3 hours at 80 DEG C；
4th step is slowly added to 0.13 part of silane coupling agent (KH-550) into reaction system in terms of mass fraction, continues
Stirring is reacted 2 hours；
10 parts of organic boron nitrogen combustion inhibitor 3BT and 15 parts of magnesium hydroxides are added into system in terms of mass fraction for 5th step,
Continue stirring 1 hour；
6th step, reaction terminate, and system vacuumizes removing bubble, pours out while hot, you can obtains target product.
The structural formula of 3BT is：Entitled 2,4,6- tri--([1,3,2] dioxy boron
Penta ring -2- oxos) -1,3,5-triazines, abbreviation 3BT is made by the steps：
1) 7ml ethylene glycol and 80ml toluene are added in three-necked flask, stir and is gradually heating to 45 DEG C, addition 7.56g
Boric acid, is continuously heating to 84 DEG C, and stirring 50 minutes to boric acid is completely dissolved；Wait for that moisture is not further added by water knockout drum, the reaction was continued
2h；
2) reaction solution of the first step is evaporated under reduced pressure and removes toluene, be dried in vacuo at 70 DEG C, obtain water white transparency thick liquid
Intermediate product 1；8.18g intermediate products 1 are dissolved in 60ml tetrahydrofuran solutions；
3) 5.78g Cyanuric Chlorides under nitrogen protection, are weighed to be dissolved in 40ml tetrahydrofuran solutions, 3.97g is then added
Sodium hydroxide.At 23 DEG C, the half of the tetrahydrofuran solution volume dissolved with intermediate product 1 is added, reacts 2h, then heats to
40 DEG C, continues that the remaining tetrahydrofuran solution dissolved with intermediate product 1 is added dropwise, reacts 2h, after being added dropwise, be warming up to 90 DEG C,
Sustained response 4h；
4) reaction mixture of third step gained is filtered, liquid phase is spin-dried for Rotary Evaporators, obtains crude product；With tetrahydrochysene
Mixed liquor (the volume ratio 1 of furans and dichloromethane:10) it is used as flushing liquor, is detached with chromatographic column, obtains white solid
3BT。
Obtained product is characterized using mass spectrum and nuclear magnetic resonance spectroscopy, structural characterization data are as follows：
MS:m/z 339.08(M+)
1H NMR(600MHz,DMSO-d6,ppm):δ4.07(t,12H)。
Wherein δ=4.07ppm is alkyl chain peak；2,4,6- tri--(penta ring -2- oxos of [1,3,2] dioxy boron) -1,3,5- three
The theoretical molecular weight of piperazine (3BT) is 339.08, and in conjunction with mass spectrum, we obtain, which is 3BT.
Embodiment 2
The first step, in terms of mass fraction, 60 parts of polyether Glycols (PPG-4000) for being 4000 by relative molecular weight, relatively
Molecular weight be 5000 30 parts of polyether-tribasic alcohol (PPG-5000) be added in reaction kettle, vacuumize, control temperature at 120 DEG C,
Stirring 2.5 hours；
Second step makes system cool to 42 DEG C, and system leads to nitrogen protection；
Third walks, and in terms of mass fraction, by two 30 parts of addition reaction kettles of different hydrogen acid ether (hydrogen acid ester) (MDI) of diphenyl methane, is added
0.1 part of dibutyl tin laurate increases mixing speed to 300rpm/min, and control temperature is reacted 3 hours at 80 DEG C；
4th step is slowly added to 0.15 part of silane coupling agent (KH-170) into reaction system in terms of mass fraction, continues
Stirring is reacted 2.5 hours；
23 parts of organic boron nitrogen combustion inhibitor 3BeT and 10 parts of magnesium hydroxides are added into system in terms of mass fraction for 5th step,
Continue stirring 2 hours；
6th step, reaction terminate, and system vacuumizes removing bubble, pours out while hot, you can obtains target product.
In the present embodiment, 3BeT is star-like pyrrolotriazine derivatives, entitled 2,4,6- tri--{ 2- (penta rings of [1,3,2] dioxy boron-
2- oxos)-ethyoxyl } -1,3,5-triazines, abbreviation 3BeT is used as expansion type flame retardant, with following molecular structure：
The 3BeT of the present embodiment is made by the steps：
1) 13.5ml ethylene glycol and 140ml toluene are added in three-necked flask, stir and is gradually heating to 48 DEG C, addition
7.35g boric acid, is continuously heating to 73 DEG C, and stirring 50 minutes to boric acid is completely dissolved；It waits for that moisture is not further added by water knockout drum, continues
React 1h；
2) reaction solution of the first step is evaporated under reduced pressure and removes toluene, be dried in vacuo at 70 DEG C, obtain water white transparency thick liquid
Intermediate product；12.29g intermediate products are dissolved in 60ml tetrahydrofuran solutions；
3) 5.67g Cyanuric Chlorides under nitrogen protection, are weighed to be dissolved in 40ml tetrahydrofuran solutions, 4.11g is then added
The half of the tetrahydrofuran solution volume dissolved with intermediate product is added at 26 DEG C in sodium hydroxide, reacts 3h, then heats to
44 DEG C, continue to be added dropwise, reacts 2.5h, after being added dropwise, be warming up to 91 DEG C, sustained response 3h；
4) reaction mixture of third step gained is filtered, liquid phase is spin-dried for Rotary Evaporators, obtains crude product；With tetrahydrochysene
Mixed liquor (the volume ratio 1 of furans and dichloromethane:12) it is used as flushing liquor, isolated white solid base is carried out with chromatographic column
In the expansion type flame retardant (3BeT) of star-like pyrrolotriazine derivatives.
MS:m/z 471.17(M+)
1H NMR(600MHz,DMSO-d6,ppm):δ4.07(t,12H),4.26(t,6H),4.15(t,6H)
Wherein δ=4.07ppm is boron oxygen naphthenic base chain peak, and δ=4.26 and 4.15ppm are linear alkyl chain peak；2,4,6-
The theoretical molecular weight of three-(penta ring -2- oxos of [1,3,2] dioxy boron) -1,3,5-triazines (3BT) is 471.17, is obtained in conjunction with mass spectrum
Go out, which is the expansion type flame retardant (3BeT) based on star-like pyrrolotriazine derivatives.
Embodiment 3
The first step, in terms of mass fraction, 60 parts of polyether Glycols (PPG-2000) for being 2000 by relative molecular weight, relatively
Molecular weight be 3000 32 parts of polyether-tribasic alcohol (PPG-3000) be added in reaction kettle, vacuumize, control temperature at 120 DEG C,
Stirring 2 hours；
Second step makes system cool to 45 DEG C, and system leads to nitrogen protection；
Third walks, and in terms of mass fraction, by two 38 parts of addition reaction kettles of different hydrogen acid ether (hydrogen acid ester) (IPDI) of isophorone, is added two
0.2 part of dibutyl tin laurate increases mixing speed to 300rpm/min, and control temperature is reacted 3 hours at 75 DEG C；
4th step is slowly added to 0.32 part of silane coupling agent (Y-9669) into reaction system in terms of mass fraction, continues
Stirring is reacted 3 hours；
18 parts of organic boron nitrogen combustion inhibitor 6BTP and 12 parts of magnesium hydroxides are added into system in terms of mass fraction for 5th step,
Continue stirring 1.5 hours；
6th step, reaction terminate, and system vacuumizes removing bubble, pours out while hot, you can obtains target product.
In the present embodiment, organic boron nitrogen combustion inhibitor 6BTP be star-like boric ester derivative, entitled 1,3,5- tri--{ 4,6-
Two-(penta ring -2- oxos of [1,3,2] dioxy boron) -1,3,5-triazines -2- oxos } benzene, abbreviation 6BTP, be used as expansion type flame retardant,
With following molecular structure：
Organic boron nitrogen combustion inhibitor 6BTP is made by the steps：
1) by 2.58g phloroglucins and 9.11gN, N- diisopropylethylamine is dissolved in 40ml tetrahydrofuran solutions (mixing
Liquid 1), 16.79g Cyanuric Chlorides are dissolved in 80ml tetrahydrofuran solutions, and 31min (mixing is sufficiently stirred in ice-water bath
Liquid 2), mixed liquor 1 is added dropwise in mixed liquor 2,3h, filtering are stirred at 5 DEG C；
2) tetrahydrofuran in second step filtrate is removed with Rotary Evaporators, white solid is obtained, with petroleum ether and acetone
Mixed liquor (volume ratio 3:1) it is used as flushing liquor, is detached with chromatographic column, obtains intermediate product 1；
3) 7.5ml ethylene glycol and 20ml toluene (as water entrainer) solution are added in three-necked flask, stir and gradually rises
Temperature is added 7.34g boric acid, is continuously heating to 88 DEG C to 42 DEG C, and stirring 47 minutes to boric acid is completely dissolved；Wait for moisture in water knockout drum
It is not further added by, the reaction was continued 2.5h；Vacuum distillation removes toluene, is dried in vacuo at 70 DEG C, obtains the centre of colourless viscous liquid
Product 2；
4) 9.32g intermediate products 2 under nitrogen protection, are weighed to be dissolved in 100ml tetrahydrofuran solutions, are then added
4.68g sodium hydroxide；8.29g intermediate products 1 are dissolved in 80ml tetrahydrofuran solutions, at 50 DEG C, being added should be dissolved with centre
The half of the tetrahydrofuran solution volume of product 1 reacts 4h, continues that remaining tetrahydrofuran solution is added dropwise, then heat to 100
DEG C, sustained response 6h；
5) reaction mixture obtained by the 4th step is filtered, liquid phase is spin-dried for Rotary Evaporators, obtains crude product；With dichloro
Mixed liquor (the volume ratio 4 of methane and ethyl acetate:1) it is used as flushing liquor, isolated white solid is carried out with chromatographic column
6BTP。
Obtained product is characterized using mass spectrum and nuclear magnetic resonance spectroscopy, structural characterization data are as follows：
MS:m/z 879.20(M+)
1H NMR(600MHz,DMSO-d6,ppm):δ4.07(t,24H),5.76(s,3H)
Wherein δ=4.07ppm is alkyl chain peak, and δ=5.76ppm is the peak on phenyl ring.1,3,5- tri- -4,6- bis--([1,
3,2] penta ring -2- oxos of dioxy boron) -1,3,5-triazines -2- oxos benzene (6BTP) theoretical molecular weight be 879.20, connexus
Spectrum show that the product is 6BTP.
Embodiment 4
The first step, in terms of mass fraction, 60 parts of polyether Glycols (PPG-6000) for being 6000 by relative molecular weight, relatively
Molecular weight be 3000 30 parts of polyether-tribasic alcohol (PPG-3000) be added in reaction kettle, vacuumize, control temperature at 120 DEG C,
Stirring 3 hours；
Second step makes system cool to 48 DEG C, and system leads to nitrogen protection；
Third walks, and in terms of mass fraction, by two 40 parts of addition reaction kettles of different hydrogen acid ether (hydrogen acid ester) (IPDI) of isophorone, is added two
0.6 part of dibutyl tin laurate increases mixing speed to 300rpm/min, and control temperature is reacted 3.5 hours at 70 DEG C；
4th step is slowly added to 0.35 part of silane coupling agent (KH-550) into reaction system in terms of mass fraction, continues
Stirring is reacted 3.5 hours；
20 parts of organic fire-retardant 6BeTP and 12 parts of magnesium hydroxides are added into system in terms of mass fraction for 5th step, after
Continuous stirring 4 hours；6th step, reaction terminate, and system vacuumizes removing bubble, pours out while hot, you can obtains target product.
Entitled tri--{ 4,6- bis--[(penta ring -2- oxos of [1,3,2] dioxy boron)-second of 1,3,5- of 6BeTP in the present embodiment
Oxygroup] -1,3,5-triazines -2- oxos } benzene, referred to as 6BeTP, it is used as expansion type flame retardant, is a kind of boric ester derivative, tool
There is following molecular structure：
The 6BeTP is made by the steps：
1) by 2.58g phloroglucins and 9.11gN, N- diisopropylethylamine is dissolved in 40ml tetrahydrofuran solutions (mixing
Liquid 1), 16.79g Cyanuric Chlorides are dissolved in 80ml tetrahydrofuran solutions, and 31min (mixing is sufficiently stirred in ice-water bath
Liquid 2), mixed liquor 1 is added dropwise in mixed liquor 2,3h, filtering are stirred at 5 DEG C；
2) tetrahydrofuran in second step filtrate is removed with Rotary Evaporators, white solid is obtained, with petroleum ether and acetone
Mixed liquor (volume ratio 3:1) it is used as flushing liquor, is detached with chromatographic column, obtains intermediate product 1；
3) 13.5ml ethylene glycol and 30ml toluene solutions are added in three-necked flask, stir and is gradually heating to 42 DEG C, adds
Enter 7.34g boric acid, be continuously heating to 88 DEG C, stirring 47 minutes to boric acid is completely dissolved；Wait for that moisture is not further added by water knockout drum, after
Continuous reaction 2.5h；Vacuum distillation removes toluene, is dried in vacuo at 70 DEG C, obtains the intermediate product 2 of colourless viscous liquid；
4) 13.8g intermediate products 2 under nitrogen protection, are weighed to be dissolved in 100ml tetrahydrofuran solutions, are then added
5.28g sodium hydroxide；8.59g intermediate products 1 are dissolved in 80ml tetrahydrofuran solutions, at 50 DEG C, being added should be dissolved with centre
The half of the tetrahydrofuran solution volume of product 1 reacts 4h, continues the remaining tetrahydrofuran dissolved with intermediate product 1 is added dropwise molten
Liquid then heats to 100 DEG C, sustained response 6h；
5) reaction mixture obtained by the 4th step is filtered, liquid phase is spin-dried for Rotary Evaporators, obtains crude product；With dichloro
Mixed liquor (the volume ratio 5 of methane and ethyl acetate:1) it is used as flushing liquor, isolated white solid is carried out with chromatographic column
6BeTP。
Obtained product is characterized using mass spectrum and nuclear magnetic resonance spectroscopy, structural characterization data are as follows：
MS:m/z 1143.40(M+)
1HNMR(600MHz,DMSO-d6,ppm):δ4.03(t,24H),4.28(t,12H),4.15(t,12H),5.76
(s,3H)
Wherein δ=4.03ppm is the peak of alkyl chain on boron oxygen ring, and δ=4.15 and 4.28ppm are linear alkyl chain peak.1,
3,5- tri--{ 4,6- bis--[(penta ring -2- oxos of [1,3,2] dioxy boron)-ethyoxyl] -1,3,5- triazine -2- oxos } benzene
The theoretical molecular weight of (6BeTP) is 1143.40, can show that the product is 6BeTP in conjunction with mass spectrum.
Embodiment 5
The first step, in terms of mass fraction, 68 parts of polyether Glycols (PPG-6000) for being 6000 by relative molecular weight, relatively
Molecular weight be 5000 30 parts of polyether-tribasic alcohol (PPG-5000) be added in reaction kettle, vacuumize, control temperature at 120 DEG C,
Stirring 3.5 hours；
Second step makes system cool to 48 DEG C, and system leads to nitrogen protection；
Third walks, and in terms of mass fraction, by 42 parts of addition reaction kettles of toluene di-isocyanate(TDI) (TDI), catalyst is added
0.8 part of dibutyl tin laurate increases mixing speed to 300rpm/min, and control temperature is reacted 4 hours at 65 DEG C；
4th step is slowly added to 0.22 part of silane coupling agent (KH-550) into reaction system in terms of mass fraction, continues
Stirring is reacted 4 hours；
The mixed of 15 parts of boron nitrogen combustion inhibitor PTBO and 15 parts of magnesium hydroxides is added into system in terms of mass fraction for 5th step
Object is closed, stirring 2 hours is continued；
5th step, reaction terminate, and system vacuumizes removing bubble, pours out while hot, you can obtains target product.
In the present embodiment, entitled 3,9-, bis--(4,6- bis--phenoxy groups-[1,3, the 5] triazine -2- oxos) -2,4,8 of PTBO,
Tetra- bis- boron of oxa- -3,9- of 10--spiral shell [5.5] hendecane, abbreviation PTBO are used as expansion type flame retardant, are a kind of pentaerythrite derivatives
Object has following molecular structure：
The PTBO is made by the steps：
1) 3.2g boric acid and 6.8g pentaerythrites are added in three-necked flask, addition 40ml toluene is as water entrainer, stirring
It is back to moisture in water knockout drum not to be further added by, keeps temperature after the reaction was continued 2 hours, be evaporated water entrainer, obtain band white solid；
2) the white solid acetone recrystallization that obtains the first step, filtering, drying, obtain intermediate product 1；
3) 7.5g intermediate products 1 are weighed and 2.4g sodium hydroxides are dissolved in distilled water, is flowed back 1 hour, is cooled to room temperature, presses
The acetone soln (Cyanuric Chloride 15.5g, acetone 30ml) of Cyanuric Chloride is added portionwise in ratio, is specifically added in three times, every
15min adds one third；Reaction 4 hours, filters crude product；With volume ratio for 4:1 petroleum ether and dichloromethane
Mixed liquor is detached as flushing liquor with chromatographic column, and intermediate product 2 is obtained；
4) under nitrogen protection, 2.8g phenol and 5ml n,N-diisopropylethylamine are dissolved in 30ml toluene, slowly added
Enter into the toluene solution of intermediate product 2, stirs 1 hour；80 DEG C are gradually heating to, is stirred to react 4 hours, is filtered；
Obtained product is characterized using mass spectrum, nuclear magnetic resonance, structural characterization data are as follows：
MS:m/z 714.22(M+)
1HNMR(600MHz,DMSO-d6,ppm):δ=3.78 (s, 8H), 6.73 (d, 8H), 7.09 (t, 8H), 6.82 (t,
4H)。
Wherein δ=3.78ppm is alkyl chain peak, and δ=6.73ppm and δ=7.09 are phenyl ring ortho position and meta position peak, δ=
6.82 be contraposition peak.Four oxa- -3,9- two of 3,9- bis--(bis--phenoxy groups of 4,6--[1,3,5] triazine -2- oxos) -2,4,8,10-
The theoretical molecular weight of boron-spiral shell [5.5] hendecane (PTBO) is 714.22, can be obtained in conjunction with mass spectrum, which is PTBO.
Embodiment 6
The first step, in terms of mass fraction, 70 parts of polyether Glycols (PPG-1500) for being 1500 by relative molecular weight, relatively
Molecular weight be 7000 35 parts of polyether-tribasic alcohol (PPG-7000) be added in reaction kettle, vacuumize, control temperature at 120 DEG C,
Stirring 3 hours；
Second step makes system cool to 50 DEG C, and system leads to nitrogen protection；
Third walks, and in terms of mass fraction, by two 45 parts of addition reaction kettles of different hydrogen acid ether (hydrogen acid ester) (HDI) of hexa-methylene, is added two
0.8 part of dibutyl tin laurate increases mixing speed to 300rpm/min, and control temperature is reacted 5 hours at 65 DEG C；
4th step is slowly added to 0.38 part of silane coupling agent (KH-550) into reaction system in terms of mass fraction, continues
Stirring is reacted 3.8 hours；
10 parts of 3BT fire retardants, 12 parts of 6BeTP and 8 part of magnesium hydroxides are added into system in terms of mass fraction for 5th step
Mixture, continue stirring 2 hours；3BT fire retardants are shown in embodiment 1；6BeTP is shown in embodiment 4.
6th step, reaction terminate, and system vacuumizes removing bubble, pours out while hot, you can obtains target product.
Embodiment 7
The first step, in terms of mass fraction, 65 parts of polyether Glycols (PPG-8000) for being 8000 by relative molecular weight, relatively
Molecular weight be 3000 35 parts of polyether-tribasic alcohol (PPG-3000) be added in reaction kettle, vacuumize, control temperature at 120 DEG C,
Stirring 4.5 hours；
Second step makes system cool to 50 DEG C, and system leads to nitrogen protection；
Third walks, in terms of mass fraction, by two different hydrogen acid ether (hydrogen acid ester) (HDI) 50 of toluene di-isocyanate(TDI) (TDI) and hexa-methylene
In part addition reaction kettle, 1 part of dibutyl tin laurate is added, increases mixing speed to 300rpm/min, control temperature is 60
DEG C reaction 5 hours；
4th step is slowly added to 0.43 part of silane coupling agent (KH-550) into reaction system in terms of mass fraction, continues
Stirring is reacted 3.6 hours；
15 parts of BPTO boron nitrogen combustion inhibitors, 12 parts of 6BTP and 13 part of hydrogen-oxygens are added into system in terms of mass fraction for 5th step
Change magnesium, continues stirring 3 hours；BPTO boron nitrogen combustion inhibitors are shown in embodiment 5；6BTP is shown in embodiment 3.
6th step, reaction terminate, and system vacuumizes removing bubble, pours out while hot, you can obtains target product.
Thermogravimetric analysis, limit oxygen index test, vertical combustion are carried out to the base polyurethane prepolymer for use as that above-described embodiment 1-7 is obtained
It burns, Mechanics Performance Testing.
Thermogravimetric analysis：Under nitrogen atmosphere, with the heating rate of 10 DEG C/min from room temperature to 800 DEG C, thermogravimetric is carried out
Analysis.
Limit oxygen index：It according to GB/T 2406-1993, is measured using JF-3 type oxygen index measurers, sample size is
100mmx6mmx3mm；
Vertical combustion：It is measured according to FMVSS302, sample size 100mmx12.7mmx4mm.
Tensile property：It according to GB/T 1042-1992, is measured using universal tensile testing machine, rate of extension 50mm/
min.Blank testing program：
The first step, in terms of mass fraction, 60 parts of polyether Glycols (PPG-8000) for being 8000 by relative molecular weight, relatively
Molecular weight be 5000 30 parts of polyether-tribasic alcohol (PPG-5000), be added in reaction kettle, vacuumize, control temperature at 120 DEG C,
Stirring 2 hours；
Second step makes system cool to 40 DEG C, and system leads to nitrogen protection；
Third walks, and in terms of mass fraction, by two 30 parts of addition reaction kettles of different hydrogen acid ether (hydrogen acid ester) (MDI) of diphenyl methane, is added
0.1 part of dibutyl tin laurate, increases mixing speed, and control temperature is reacted 3 hours at 80 DEG C；
4th step is slowly added to 0.13 part of silane coupling agent into reaction system, is continued to stir, instead in terms of mass fraction
It answers 2 hours；
0 part of fire retardant is added into system for 5th step, continues stirring 3 hours；
6th step, reaction terminate, and system vacuumizes removing bubble, pours out while hot, you can obtains target product.
The base polyurethane prepolymer for use as of experiment synthesis does thermogravimetric analysis, limit oxygen index test, vertical combustion, measures addition resistance
The flame retardant property of combustion agent and the polyurethane samples that fire retardant is not added.
The experimental results showed that the polyurethane that synergistic fire retardant is added has good flame retardant property.
Test result is shown in Table 1：
Table 1
Claims (7)
1. a kind of preparation method of flame-retardant polyurethane performed polymer, it is characterised in that include the following steps：
Polyether polyol is added in reaction kettle by the first step, is vacuumized, and for control temperature at 100 DEG C~120 DEG C, stirring 2-3 is small
When；
Second step makes system cool to 40 DEG C~50 DEG C, and system leads to nitrogen protection；
Third walks, and diisocyanate is added in reaction kettle, dibutyl tin laurate is added, while increasing mixing speed, controls
Temperature processed is reacted 3-5 hours at 60 DEG C~80 DEG C；
4th step is slowly added to silane coupling agent into reaction system according to dissociateive NCO content in system, and it is anti-to continue stirring
It answers 2-5 hours；
5th step, fire retardant is added into system, continues stirring 1-3 hours；The fire retardant is organic boron nitrogen combustion inhibitor and hydrogen
Magnesia；
6th step, reaction terminate, and system vacuumizes removing bubble, obtain flame-retardant polyurethane performed polymer；
The organic boron nitrogen combustion inhibitor is one or more in the compound having following structure：
2. preparation method according to claim 1, it is characterised in that：In terms of mass fraction, the dosage of raw material is：Polyethers is more
First alcohol 100-150 parts, 30~50 parts of diisocyanate, 0.1~1 part of dibutyl tin laurate, 0.1-1 parts of silane coupling agent and
5~50 parts of fire retardants.
3. preparation method according to claim 1, it is characterised in that：The polyether polyol be polyether Glycols and/or
Polyether-tribasic alcohol.
4. preparation method according to claim 1, it is characterised in that：The diisocyanate be toluene di-isocyanate(TDI),
One kind or more in diphenyl methane -4,4 '-diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate
Kind.
5. preparation method according to claim 1, it is characterised in that：The silane coupling agent is KH-550, KH-170
With it is one or more in Y-9669.
6. preparation method according to claim 1, it is characterised in that：In terms of mass fraction, the organic boron nitrogen is fire-retardant
Agent is 5-20 parts, and the magnesium hydroxide is 5-20 parts.
7. a kind of flame-retardant polyurethane performed polymer, it is characterised in that：It is by any one of the claim 1-6 preparation method systems
?.
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| CN103374025A (en) * | 2013-07-02 | 2013-10-30 | 华南理工大学 | Triazine boric acid derivatives and preparation methods thereof |
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| CN103374025A (en) * | 2013-07-02 | 2013-10-30 | 华南理工大学 | Triazine boric acid derivatives and preparation methods thereof |
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| 硅烷化聚氨酯预聚体的合成及其固化物的性能;马文石等;《石油化工》;20071231;第36卷(第5期);第497页-第501页 * |
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