CN104211900A - Polyurethane containing DOPO groups and preparation method thereof - Google Patents

Polyurethane containing DOPO groups and preparation method thereof Download PDF

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Publication number
CN104211900A
CN104211900A CN201410444119.8A CN201410444119A CN104211900A CN 104211900 A CN104211900 A CN 104211900A CN 201410444119 A CN201410444119 A CN 201410444119A CN 104211900 A CN104211900 A CN 104211900A
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preparation
urethane
dopo
liquid
diisocyanate
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CN104211900B (en
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何吉宇
唐启恒
杨荣杰
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Beijing Institute of Technology BIT
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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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/388—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to carbon and/or to hydrogen
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to polyurethane containing DOPO groups and a preparation method thereof and belongs to the technical field of high-temperature resistant materials and flame-retardant materials. The preparation method comprises the following steps: mixing liquid polyether diol with liquid diisocyanate, heating to perform addition reaction, subsequently adding a solution of a DOPO derivative, heating to perform condensation polymerization, and drying the solvent, thereby obtaining DOPO polyurethane. The polyurethane has the characteristics of gentle and stable reaction condition, good repeatability, high yield, short period and the like, and is applicable to large-scale production.

Description

A kind of urethane containing DOPO group and preparation method thereof
Technical field
The present invention relates to a kind of urethane containing DOPO group and preparation method thereof, belong to fire retardant material technical field.
Background technology
Polyurethane Thermoplastic Elastomer (TPU) is containing the carbamate segment repeated on its main chain a kind of, macromolecular main chain is lower than the soft segment of room temperature and the second-order transition temperature rigid chain segment block higher than room temperature by second-order transition temperature, it had both had the high strength of plastics, there is again the snappiness of rubber, high elongation rate, can be made into a series of products such as porous plastics, tackiness agent, fiber, water-proof material, be therefore widely used in the fields such as automobile, medical treatment and space flight.But it, as a kind of organic polymer material, very easily burns in atmosphere, during burning, flame very violent and with black smoke, have serious molten drop phenomenon simultaneously, and its limiting oxygen index(LOI) (LOI) is only between 18-20, has serious disaster hidden-trouble.Therefore be a very urgent problem to TPU heat-resisting and flame-retardant modified.
At present, to the heat-resisting and fire-retardant modification of TPU mainly by the mode of physical blending and synthesis inherent flame retardant polymer materials.Additive flame retardant is scattered in polymeric substrate by physical blending mode exactly, and give base material flame retardant properties, complete processing is simple, application is general, but need to improve the interface compatibility between the component such as fire retardant and base material, improve the mechanical property of flame-proofed polymer material, avoid fire retardant to move out.In order to effectively address these problems, research concentrates on the mode of synthesis inherent flame retardant polymer materials more and more.
Phosphoric is a kind of generally acknowledged ignition-proof element.Phosphorus flame retardant is the very effective fire retardant of a class when flame resistance polyurethane elastomer, this is because phosphorus flame retardant can play fire retardation at condensed phase and gas phase simultaneously.In condensed phase, phosphonium flame retardant burning can make the carbonization of oxygen-bearing organic matter rapid dehydration, the carbide generated has three-dimensional dense structure and nonflammable, very thickness, be covered in by combustion thing surface, form the film like material that one deck is good, hinder oxygen to spread to reaction zone, play isolated effect.In the gas phase, phosphonium flame retardant can decomposite difficult combustion gas body, and the concentration of inflammable gas is reduced, and, the free radical such as P and PO of releasing during phosphonium flame retardant burning can the high reactivity H that produces of cancellation Polymer-pyrolysis and HO free radical, thus makes the chain reaction of burning interrupt and reach fire retardation.9,10 1 dihydro 1 oxa-s 1 phospho hetero phenanthrene 1 monoxide (DOPO) are that a kind of cyclic phosphate is cruel, itself has higher thermostability and oxidation-resistance, and the derivative of it and it has had in the polymeric material to be applied widely, as in ethoxyline resin antiflaming.Pass through molecular designing, using the glycol containing DOPO as chainextender, react with PTMG (PTMG) and 4,4-diphenylmethanediisocyanate (MDI), prepare the novel urethane (PU) containing DOPO group.
Summary of the invention
The object of the invention is to prepare a kind of urethane containing DOPO group, and propose its preparation method.This polyurethane material is simultaneously containing DOPO group, and polyethers, isocyanic ester, has good fire retardation in polymer composites.
The object of the invention is to be achieved through the following technical solutions.
A kind of urethane containing DOPO group of the present invention, its structural formula is:
Wherein Ar is or or in any one; N is the polymerization degree of B,
B is-CH 2cH 2cH 2cH 2o-, n=10-45;
Or B is-CH 2cH 2o-, n=20-500;
Or B is n=10-70;
D is or or in any one.
X is the polymerization degree, and x=1-10, y are the polymerization degree, and y=2-15, a are the polymerization degree, and a=20-90, b are the polymerization degree, b=35-150.
The preparation method of a kind of urethane containing DOPO group of the present invention, step is:
1) mixed with liquid diisocyanate by liquid anhydrous polyether glycol, protection of inert gas, stir, addition reaction is carried out in heating, and Heating temperature is 70-90 DEG C, and heat-up time is 1-15h; The mol ratio of liquid anhydrous polyether glycol and liquid diisocyanate is 0.1-1:1
2) corresponding DOPO derivative and solvent are added step 1) product that obtains, stir, polycondensation is carried out in heating, and Heating temperature is 60-100 DEG C, and heat-up time is 2-24h; DOPO derivative and step 1) in the mol ratio of liquid anhydrous polyether glycol be 0.1-1:1; The quality summation of liquid anhydrous polyether glycol, liquid diisocyanate, pyromellitic dianhydride and the mass ratio of solvent are not more than 1;
3) by step 2) solvent of product that obtains after terminating of reaction removes the urethane urethane obtained containing DOPO group.
Step 1) in liquid anhydrous polyether glycol be one in PTMG, polyoxyethylene glycol or polyethylene oxide-tetrahydrofuran (THF) ether glycol.The number-average molecular weight of PTMG is 1000 ± 50,1400 ± 50,1800 ± 50,2000 ± 50 or 3000 ± 100.The number-average molecular weight of polyoxyethylene glycol is 1000 ± 50,1400 ± 50,2000 ± 200,4000 ± 400 and 6000 ± 500; 8000 ± 500,10000 ± 1500 or 20000 ± 1500.The number-average molecular weight of polyethylene oxide-tetrahydrofuran (THF) ether glycol is 1800-6200.
Step 1) in liquid diisocyanate be: 4,4 '-diphenylmethanediisocyanate, Toluene-2,4-diisocyanate, 4-vulcabond or Toluene-2,4-diisocyanate, the one in 6-vulcabond.
Step 1) middle liquid 4, the preparation method of 4 '-diphenylmethanediisocyanate is: by solid 4, and 4 '-diphenylmethanediisocyanate joins in reaction vessel, and heating makes it melt; Heating temperature is 40-80 DEG C.
Step 1) in the preparation method of liquid anhydrous polyether glycol be: by polyether glycol in the vacuum drying oven of high temperature, under vacuum condition, remove moisture; The temperature of vacuum drying oven is 100-120 DEG C, and dewater time 0.5-20h; Vacuum tightness is less than-0.02MPa.
Step 2) in solvent be one in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF).
Beneficial effect
Reaction conditions gentleness of the present invention is stable, reproducible, and the features such as productive rate is high, the cycle is short are applicable to expansion property and produce; Learn that DOPO modification improves the value of the limiting oxygen index(LOI) of urethane through test, and improve the grade of urethane at UL-94 vertical combustion, in addition, DOPO modification also reduces total Heat liberation unit and the heat release rate peak value of urethane.
Accompanying drawing explanation
Infrared spectra adopts NICOLET 6700 IR type determination of infrared spectroscopy; Thermal weight loss (TG) adopts NETZSCH 209 F1 thermogravimetric analyzer to measure, nitrogen atmosphere, temperature rise rate 10 DEG C/min; Limiting oxygen index(LOI) (Liu Bian science company limited) is tested according to GB/T 2406.2-2009; UL-94 testing vertical flammability carries out according to UL94-09, standard model size 125 × 12.5 × 3.2mm 3; Test result as shown in Table 1 and Table 2.
Fig. 1 is the FT-IR spectrogram of the urethane containing DOPO group prepared by embodiment 2;
Fig. 2 is thermogravimetric curve figure and the differential curve figure thereof of the urethane containing DOPO group prepared by embodiment 1,2,3; Figure above in Fig. 2 is thermogravimetric curve figure, and ordinate zou is mass loss per-cent, and figure is below differential curve figure, and its ordinate zou is mass loss rate unit is %/min;
Fig. 3 is the heat release rate curve figure of the urethane containing DOPO group prepared by embodiment 1,2,3, and its ordinate zou represents heat release rate, and unit is kW/m 2;
Total Thermal release graphic representation of the urethane containing DOPO group prepared by Fig. 4 embodiment 1,2,3, its ordinate zou represents total Heat liberation unit, and unit is MJ/m 2.
Table 1 is containing the UL-94 vertical combustion of urethane of DOPO group, limiting oxygen index(LOI) and mechanical strength.
Embodiment
Below by embodiment, the invention will be further described, but embodiment does not limit the scope of the invention.
Embodiment 1
The molar ratio of preparation MDI:PTMG:DOPO-NQ is the urethane containing DOPO group of 3:2:1, is called PU321; The number-average molecular weight of PTMG is 2000; DOPO-NQ molecular formula is:
Raw material is: MDI is 75.0g, PTMG be 400.0g, DOPO-NQ is 37.4g, and DMF solvent is 500mL;
1) by 400.0g PTMG in the vacuum drying oven of 120 DEG C of high temperature, remove moisture 3h under vacuum condition;
2) 75.0g solid MDI is joined in reaction vessel, under 50 DEG C of conditions, make it melt;
3) by step 1) add step 2 in the liquid PTMG of the 400.0g that obtains) in the liquid MDI of 75.0g that obtains, stir under vacuum condition, under 80 DEG C of conditions, carry out addition reaction, 1h, remove vacuum;
4) the DMF solution containing 37.4g DOPO-NQ is joined step 3) in the product that obtains, stir, under 70 DEG C of conditions, carry out chain extending reaction 24h, obtain the polyurethane PU 321 containing DOPO group.
Above-mentioned steps 3) and 4) reaction scheme as follows:
x＝10，y＝5。
Embodiment 2
The molar ratio of preparation MDI:PTMG:DOPO-NQ is the urethane containing DOPO group of 2:1:1, is called PU211;
Raw material is: MDI is 50.0g, PTMG be 200.0g, DOPO-NQ is 37.4g, and DMF solvent is 500mL;
Preparation method, with embodiment 1, obtains the polyurethane PU 211 containing DOPO group.
Embodiment 3
The molar ratio of preparation MDI:PTMG:DOPO-NQ is the urethane containing DOPO group of 3:1:2, is called PU321;
Raw material is: MDI is 75.0g, PTMG be 100.0g, DOPO-NQ 74.8g is that DMF solvent is 500mL;
Preparation method, with embodiment 1, obtains the polyurethane PU 312 containing DOPO group.
Table 1

Claims (10)

1., containing a urethane for DOPO group, it is characterized in that: the structural formula of this urethane is as follows:
Wherein Ar is or or in any one; N is the polymerization degree of B,
B is-CH 2cH 2cH 2cH 2o-, n=10-45;
Or B is-CH 2cH 2o-, n=20-500;
Or B is n=10-70;
D is or or in any one;
X is the polymerization degree, and x=1-10, y are the polymerization degree, and y=2-15, a are the polymerization degree, and a=20-90, b are the polymerization degree, b=35-150.
2., containing a preparation method for the urethane of DOPO group, it is characterized in that step is:
1) mixed with liquid diisocyanate by liquid anhydrous polyether glycol, stir, addition reaction is carried out in heating, and Heating temperature is 70-90 DEG C, and heat-up time is 1-15h; The mol ratio of liquid anhydrous polyether glycol and liquid diisocyanate is 0.1-1:1
2) corresponding DOPO derivative and solvent being joined step 1) in the product that obtains, stir, polycondensation is carried out in heating, and Heating temperature is 60-100 DEG C, and heat-up time is 2-24h; DOPO derivative and step 1) in the mol ratio of liquid anhydrous polyether glycol be 0.1-1:1; The quality summation of liquid anhydrous polyether glycol, liquid diisocyanate, DOPO derivative and the mass ratio of solvent are not more than 1;
3) by step 2) solvent of product that obtains after terminating of reaction removes the urethane obtained containing DOPO group.
3. the preparation method of a kind of urethane containing DOPO group according to claim 2, is characterized in that: step 1) in liquid anhydrous polyether glycol be one in PTMG, polyoxyethylene glycol or polyethylene oxide-tetrahydrofuran (THF) ether glycol.
4. the preparation method of a kind of urethane containing DOPO group according to claim 3, is characterized in that: the number-average molecular weight of PTMG is 1000 ± 50,1400 ± 50,1800 ± 50,2000 ± 50 or 3000 ± 100.
5. the preparation method of a kind of urethane containing DOPO group according to claim 3, is characterized in that: the number-average molecular weight of polyoxyethylene glycol is 1000 ± 50,1400 ± 50,2000 ± 200,4000 ± 400 and 6000 ± 500; 8000 ± 500,10000 ± 1500 or 20000 ± 1500.
6. the preparation method of a kind of urethane containing DOPO group according to claim 3, is characterized in that: the number-average molecular weight of polyethylene oxide-tetrahydrofuran (THF) ether glycol is 1800-6200.
7. the preparation method of a kind of urethane containing DOPO group according to claim 2, it is characterized in that: step 1) in liquid diisocyanate be 4,4 '-diphenylmethanediisocyanate, Toluene-2,4-diisocyanate, 4-vulcabond or Toluene-2,4-diisocyanate, the one in 6-vulcabond.
8. the preparation method of a kind of urethane containing DOPO group according to claim 7, it is characterized in that: step 1) middle liquid 4, the preparation method of 4 '-diphenylmethanediisocyanate is: by solid 4,4 '-diphenylmethanediisocyanate joins in reaction vessel, and heating makes it melt; Heating temperature is 40-80 DEG C.
9. the preparation method of a kind of urethane containing DOPO group according to claim 2, is characterized in that: step 1) in the preparation method of liquid anhydrous polyether glycol be: by polyether glycol in the vacuum drying oven of high temperature, under vacuum condition, remove moisture; The temperature of vacuum drying oven is 100-120 DEG C, and dewater time 0.5-20h; Vacuum tightness is less than-0.02MPa.
10. according to a kind of preparation method containing the urethane of DOPO group that claim 2 is stated, it is characterized in that: step 2) in solvent be N, one in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF).
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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN104945597A (en) * 2015-06-18 2015-09-30 福建师范大学泉港石化研究院 Synthetic method for somatotype-crosslinked and repairable polyurethane with flame retardant property
CN107057036A (en) * 2017-04-05 2017-08-18 福建师范大学泉港石化研究院 A kind of side chain cross-linking flame-retardant can repair the synthetic method of polyurethane
CN109593173A (en) * 2018-11-20 2019-04-09 高鼎精细化工(昆山)有限公司 Have the silicon substrate thermoplastic sulfurized rubber and its synthetic method of anti-flammability
CN109776746A (en) * 2019-01-10 2019-05-21 江苏新淮河医药科技有限公司 Biology base flame retardant polyurethane and preparation method thereof
CN117417717A (en) * 2023-12-18 2024-01-19 烟台隆达树脂有限公司 Preparation method of modified polyurethane toughened epoxy resin electronic adhesive

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CN103965247A (en) * 2014-05-23 2014-08-06 厦门大学 Phosphor-containing nitrogen-containing structural type flame retardant polyhydric alcohol as well as preparation method and application thereof
CN103965432A (en) * 2014-05-21 2014-08-06 厦门大学 Halogen-free phosphorus containing flame retardant polyurethane foaming plastic and preparation method thereof
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CN104945597B (en) * 2015-06-18 2017-06-23 福建师范大学泉港石化研究院 A kind of build crosslinking with fire resistance can repair the synthetic method of polyurethane
CN107057036A (en) * 2017-04-05 2017-08-18 福建师范大学泉港石化研究院 A kind of side chain cross-linking flame-retardant can repair the synthetic method of polyurethane
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CN117417717A (en) * 2023-12-18 2024-01-19 烟台隆达树脂有限公司 Preparation method of modified polyurethane toughened epoxy resin electronic adhesive
CN117417717B (en) * 2023-12-18 2024-02-20 烟台隆达树脂有限公司 Preparation method of modified polyurethane toughened epoxy resin electronic adhesive

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