CN104211900B - Polyurethane containing DOPO groups and preparation method thereof - Google Patents
Polyurethane containing DOPO groups and preparation method thereof Download PDFInfo
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- CN104211900B CN104211900B CN201410444119.8A CN201410444119A CN104211900B CN 104211900 B CN104211900 B CN 104211900B CN 201410444119 A CN201410444119 A CN 201410444119A CN 104211900 B CN104211900 B CN 104211900B
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- diisocyanate
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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
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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
- C08G18/30—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
Technical field
The present invention relates to a kind of polyurethane containing DOPO group and preparation method thereof, belong to fire proofing technical field.
Background technology
Polyurethane Thermoplastic Elastomer (TPU) is to contain the carbamate segment repeating, macromole on its main chain a kind of
Main chain be the soft segment of room temperature is less than by vitrification point and vitrification point be higher than room temperature rigid chain segment block,
It had both had the high intensity of plastics, had the high resiliency of rubber, high elongation rate again, can be made into foam plasticss, binding agent, fiber,
A series of product such as waterproof material, is therefore widely used in the fields such as automobile, medical treatment and space flight.But it is organic as one kind
Macromolecular material, easily burns in atmosphere, and during burning, flame, very acutely and with black smoke, has serious molten drop existing simultaneously
As its limited oxygen index (LOI) is only between 18-20, has serious disaster hidden-trouble.Therefore heat-resisting and its fire-retardant to TPU
Modification is a very urgent problem.
At present, physical blending and synthesis inherent flame retardant polymeric material are mainly passed through in the modification heat-resisting and fire-retardant to TPU
Mode.Physical blending mode exactly additive flame retardant is scattered in polymeric substrate, gives base material fire resistance, processing
Process is simple, application is universal, but needs to improve the interface compatibility between the components such as fire retardant and base material, improves flame-retardant polymer material
The mechanical property of material, it is to avoid fire retardant is moved out.In order to efficiently solve these problems, research more and more concentrates on synthesis originally
The mode of matter flame-proofed polymer material.
P elements are a kind of generally acknowledged ignition-proof elements.Phosphorus flame retardant is that a class has very much in flame resistance polyurethane elastomer
The fire retardant of effect, this is because phosphorus flame retardant can play fire retardation in condensed phase and gas phase simultaneously.In condensed phase, contain
Phosphorus fire retardant burning can make oxygen-bearing organic matter rapid dehydration carbonization, and the carbide of generation has three-dimensional compact texture and not
Easy firing, very sticky, it is covered in by combustion things surface, forms one layer of good film like material, hinder oxygen to expand to reaction zone
Dissipate, played isolation effect.In the gas phase, phosphonium flame retardant can decomposite fire retardant gas, so that the concentration of fuel gas is reduced, and
And, during phosphonium flame retardant burning the free radical such as P and PO of releasing can be quenched Polymer-pyrolysis generation high activity H and
HO free radical, so that the chain reaction of burning is interrupted and is reached fire retardation.9,10 one dihydro, one 9 one oxa- 1 phosphorus
Miscellaneous luxuriant and rich with fragrance one 10 monoxide (DOPO) are that a kind of cyclic phosphate is cruel, and itself has higher heat stability and non-oxidizability, it
Have in the polymeric material with its derivant and be widely applied, such as in ethoxyline resin antiflaming.Set by molecule
Meter, using the glycol containing DOPO as chain extender, with PTMG (PTMG) and 4,4- diphenyl methane two isocyanide
Acid esters (MDI) reacts, and prepares the new polyurethane (PU) containing DOPO group.
Content of the invention
The purpose of the present invention is to prepare a kind of polyurethane containing DOPO group, and proposes its preparation method.This polyurethane
Material contains DOPO group, polyethers, isocyanates simultaneously, has good fire retardation in polymer composites.
The purpose of the present invention is achieved through the following technical solutions.
A kind of polyurethane containing DOPO group of the present invention, its structural formula is：
Wherein Ar isOrOrIn
Any one；N is the degree of polymerization of B,
B is CH2CH2CH2CH2O, n=10-45；
Or B is CH2CH2O, n=20-500；
Or B isN=10-70；
D isOrOrIn any one.
X is the degree of polymerization, and x=1-10, y are the degree of polymerization, and y=2-15, a are the degree of polymerization, and a=20-90, b are the degree of polymerization, b=
35-150.
A kind of preparation method of polyurethane containing DOPO group of the present invention, step is：
1) liquid anhydrous PTMEG is mixed with liquid diisocyanate, inert gas shielding, stirring, heating carries out adding
Become reaction, heating-up temperature is 70-90 DEG C, and heat time heating time is 1-15h；Liquid anhydrous PTMEG is rubbed with liquid diisocyanate
That ratio is 0.1-1:1
2) corresponding DOPO derivant and solvent are added step 1) product that obtains, stirring, heating carries out polycondensation reaction,
Heating-up temperature is 60-100 DEG C, and heat time heating time is 2-24h；DOPO derivant and step 1) in liquid anhydrous PTMEG mole
Than for 0.1-1:1；Liquid anhydrous PTMEG, liquid diisocyanate, the quality summation of pyromellitic dianhydride and the matter of solvent
Amount ratio no more than 1；
3) by step 2) solvent of product that obtains after terminating of reaction removes the polyurethane polyureas urethane obtaining containing DOPO group.
Step 1) in liquid anhydrous PTMEG be PTMG, Polyethylene Glycol or poly(ethylene oxide)-tetrahydrochysene
One of furan ether glycol.The number-average molecular weight of PTMG be 1000 ± 50,1400 ± 50,1800 ± 50,
2000 ± 50 or 3000 ± 100.The number-average molecular weight of Polyethylene Glycol be 1000 ± 50,1400 ± 50,2000 ± 200,4000 ±
400 and 6000 ± 500；8000 ± 500,10000 ± 1500 or 20000 ± 1500.Poly(ethylene oxide)-oxolane ether glycol
Number-average molecular weight is 1800-6200.
Step 1) in liquid diisocyanate be：4,4 '-methyl diphenylene diisocyanate, Toluene-2,4-diisocyanate, 4- bis- Carbimide.
Ester or Toluene-2,4-diisocyanate, one of 6- diisocyanate.
Step 1) in liquid 4, the preparation method of 4 '-methyl diphenylene diisocyanate is：By solid 4,4 '-diphenylmethyl
Alkane diisocyanate is added in reaction vessel, and heating makes it melt；Heating-up temperature is 40-80 DEG C.
Step 1) in the preparation method of liquid anhydrous PTMEG be：By PTMEG in the vacuum drying oven of high temperature, very
Moisture is removed under empty condition；The temperature of vacuum drying oven is 100-120 DEG C, eliminating water time 0.5-20h；Vacuum be less than-
0.02MPa.
Step 2) in solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl
One of sulfoxide or oxolane.
Beneficial effect
The reaction condition of the present invention is gently stable, reproducible, yield is high, cycle is short the features such as, be suitable for expansion property and produce；
Learn that DOPO modification improves the value of the limited oxygen index of polyurethane through test, and also it is vertical in UL-94 to improve polyurethane
The grade of burning, additionally, DOPO modification also reduces total Heat liberation unit and the HRR peak value of polyurethane.
Brief description
Infrared spectrum adopts NICOLET 6700 IR type determination of infrared spectroscopy；Thermal weight loss (TG) adopts NETZSCH 209
F1 thermogravimetric analyzer measures, nitrogen atmosphere, 10 DEG C/min of heating rate；Limited oxygen index (rheology science company limited) according to
GB/T 2406.2-2009 tests；UL-94 testing vertical flammability is carried out according to UL94-09, and standard sample size 125 × 12.5 ×
3.2mm3；Test result is as shown in Table 1 and Table 2.
Fig. 1 is the FT-IR spectrogram of the polyurethane containing DOPO group of embodiment 2 preparation；
Fig. 2 is the thermogravimetric curve figure of the polyurethane containing DOPO group and its differential curve figure of embodiment 1,2,3 preparation；
In Fig. 2, draw above is thermogravimetric curve figure, and vertical coordinate is mass loss percentage ratio, and figure below is differential curve figure, and it is indulged
Coordinate is %/min for mass loss rate unit；
Fig. 3 is the heat release rate curve figure of the polyurethane containing DOPO group of embodiment 1,2,3 preparation, its vertical coordinate table
Show HRR, unit is kW/m2；
Total hot releasing curve diagram of the polyurethane containing DOPO group of Fig. 4 embodiment 1,2,3 preparation, its vertical coordinate represents
Total Heat liberation unit, unit is MJ/m2.
Table 1 contains the UL-94 vertical combustion of polyurethane, limited oxygen index and the mechanical strength of DOPO group.
Specific embodiment
Below by embodiment, the invention will be further described, but embodiment is not intended to limit protection scope of the present invention.
Embodiment 1
Preparation MDI：PTMG：The molar ratio of DOPO-NQ is 3:2:1 polyurethane containing DOPO group, referred to as PU321；
The number-average molecular weight of PTMG is 2000；DOPO-NQ molecular formula is：
Raw material is：MDI is 75.0g, and PTMG is 400.0g, and 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, under vacuum condition, remove moisture 3h；
2) 75.0g solid MDI is added in reaction vessel, so that it is melted under the conditions of 50 DEG C；
3) by step 1) add step 2 in 400.0g liquid PTMG that obtains) in 75.0g liquid MDI that obtains, vacuum bar
Stir under part, carry out additive reaction, 1h under the conditions of 80 DEG C, release vacuum；
4) the DMF solution containing 37.4g DOPO-NQ is added to step 3) in the product that obtains,
Stirring, carries out chain extending reaction 24h, obtains the polyurethane PU 321 containing DOPO group under the conditions of 70 DEG C.
Above-mentioned steps 3) and 4) reaction scheme as follows：
X=10, y=5.
Embodiment 2
Preparation MDI：PTMG：The molar ratio of DOPO-NQ is 2:1:1 polyurethane containing DOPO group, referred to as PU211；
Raw material is：MDI is 50.0g, and PTMG is 200.0g, and 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
Preparation MDI：PTMG：The molar ratio of DOPO-NQ is 3:1:2 polyurethane containing DOPO group, referred to as PU321；
Raw material is：MDI is 75.0g, and PTMG is 100.0g, and 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 (9)
1. a kind of preparation method of the polyurethane containing DOPO group, the structural formula of this polyurethane is as follows：
Wherein Ar is
In any one；N is the degree of polymerization of B,
B is-CH2CH2CH2CH2O-, n=10-45；
Or B is CH2CH2O, n=20-500；
Or B isN=10-70；
D isIn any one；
X is the degree of polymerization, and x=1-10, y are the degree of polymerization, and y=2-15, a are the degree of polymerization, and a=20-90, b are the degree of polymerization, b=35-
150；
It is characterized in that steps of the method are：
1) liquid anhydrous PTMEG is mixed with liquid diisocyanate, stirring, heating carries out additive reaction, and heating-up temperature is
70-90 DEG C, heat time heating time is 1-15h；Liquid anhydrous PTMEG is 0.1-1 with the mol ratio of liquid diisocyanate:1；
2) corresponding DOPO derivant and solvent are added to step 1) in the product that obtains, stirring, heating carries out polycondensation reaction,
Heating-up temperature is 60-100 DEG C, and heat time heating time is 2-24h；DOPO derivant and step 1) in liquid anhydrous PTMEG mole
Than for 0.1-1:1；Liquid anhydrous PTMEG, liquid diisocyanate, the quality summation of DOPO derivant and the quality of solvent
Ratio no more than 1；
3) by step 2) solvent of product that obtains after terminating of reaction removes the polyurethane obtaining containing DOPO group.
2. a kind of polyurethane containing DOPO group according to claim 1 preparation method it is characterised in that：Step 1) in
Liquid anhydrous PTMEG is in PTMG, Polyethylene Glycol or poly(ethylene oxide)-oxolane ether glycol
Kind.
3. a kind of polyurethane containing DOPO group according to claim 2 preparation method it is characterised in that：Poly- tetrahydrochysene furan
Mutter ether glycol number-average molecular weight be 1000 ± 50,1400 ± 50,1800 ± 50,2000 ± 50 or 3000 ± 100.
4. a kind of polyurethane containing DOPO group according to claim 2 preparation method it is characterised in that：Polyethylene Glycol
Number-average molecular weight be 1000 ± 50,1400 ± 50,2000 ± 200,4000 ± 400 and 6000 ± 500；8000±500、
10000 ± 1500 or 20000 ± 1500.
5. a kind of polyurethane containing DOPO group according to claim 2 preparation method it is characterised in that：Polycyclic oxygen second
The number-average molecular weight of alkane-oxolane ether glycol is 1800-6200.
6. a kind of polyurethane containing DOPO group according to claim 1 preparation method it is characterised in that：Step 1) in
Liquid diisocyanate is 4,4 '-methyl diphenylene diisocyanate, Toluene-2,4-diisocyanate, 4- diisocyanate or Toluene-2,4-diisocyanate, and 6- bis- is different
One of cyanate.
7. a kind of polyurethane containing DOPO group according to claim 6 preparation method it is characterised in that：Step 1) in
Liquid 4, the preparation method of 4 '-methyl diphenylene diisocyanate is：By solid 4,4 '-methyl diphenylene diisocyanate adds
To in reaction vessel, heating makes it melt；Heating-up temperature is 40-80 DEG C.
8. a kind of polyurethane containing DOPO group according to claim 1 preparation method it is characterised in that：Step 1) in
The preparation method of liquid anhydrous PTMEG is：By PTMEG in the vacuum drying oven of high temperature, under vacuum condition, remove moisture；
The temperature of vacuum drying oven is 100-120 DEG C, eliminating water time 0.5-20h；Vacuum is less than -0.02MPa.
9. a kind of polyurethane containing DOPO group according to claim 1 preparation method it is characterised in that：Step 2) in
Solvent is in N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide or oxolane
One kind.
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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 |
| CN107057036B (en) * | 2017-04-05 | 2019-11-12 | 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 |
| CN109593173B (en) * | 2018-11-20 | 2022-03-18 | 高鼎精细化工(昆山)有限公司 | Silicon-based thermoplastic vulcanized rubber with flame retardance and synthetic method thereof |
| CN109776746B (en) * | 2019-01-10 | 2021-03-23 | 江苏新淮河医药科技有限公司 | Bio-based flame-retardant polyurethane and preparation method thereof |
| 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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| CN103694434A (en) * | 2013-12-16 | 2014-04-02 | 中国林业科学研究院林产化学工业研究所 | Halogen-free reaction type flame retardant for polyurethane foam as well as preparation method and application thereof |
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| CN103382266A (en) * | 2013-07-02 | 2013-11-06 | 中国林业科学研究院林产化学工业研究所 | Polyurethane foam fire retardant, and preparation method and applications thereof |
| CN103833947B (en) * | 2014-02-21 | 2017-02-08 | 华东理工大学 | Synthesis and application of reaction type halogen-free phosphorus-containing flame retardant for polyurethane |
| 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 |
| CN104004171B (en) * | 2014-06-16 | 2016-01-27 | 旭川化学（苏州）有限公司 | A kind of preparation method of phosphor-containing halogen-free environmental protection flame retardant polyester polyol |
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| CN103694434A (en) * | 2013-12-16 | 2014-04-02 | 中国林业科学研究院林产化学工业研究所 | Halogen-free reaction type flame retardant for polyurethane foam 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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