CN103509167A - Anti-droplet and high temperature resistant polyimide type polyurethane and preparation method thereof - Google Patents
Anti-droplet and high temperature resistant polyimide type polyurethane and preparation method thereof Download PDFInfo
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- CN103509167A CN103509167A CN201310315037.9A CN201310315037A CN103509167A CN 103509167 A CN103509167 A CN 103509167A CN 201310315037 A CN201310315037 A CN 201310315037A CN 103509167 A CN103509167 A CN 103509167A
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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
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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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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Abstract
The invention relates to an anti-droplet and high temperature resistant polyimide type polyurethane and a preparation method thereof, and belongs to the technical fields of exotic material and flame retardant high-molecular material. The preparation method is as below: mixing liquid polyether diol and liquid diisocyanate, heating for an addition reaction, then adding a pyromellitic anhydride solution, heating for a polycondensation reaction and drying the solvent to obtain the polyimide type polyurethane. The invention has the advantages of mild and stable reaction conditions, good repeatability, high yield and short cycle, and is suitable for expansive production.
Description
Technical field
The present invention relates to a kind of anti-molten drop fire resistant polyimide type polyurethane and preparation method thereof, belong to high temperature material, flame retarded polymeric material technical field.
Background technology
Polyurethane Thermoplastic Elastomer (TPU) is a kind of resilient material between ordinary rubber and plastics, the carbamate segment that contains repetition on its main chain, macromolecular main chain is that lower than the soft segment of room temperature and second-order transition temperature, the rigid chain segment block higher than room temperature forms by second-order transition temperature, as the comparatively comprehensive material of a class performance, it had both had the high strength of plastics, the snappiness again with rubber, high elongation rate, can be made into porous plastics, rubber, coating, tackiness agent, fiber, a series of products such as water-proof material, therefore be widely used in automobile, machinery, the fields such as medical treatment and space flight.But owing to containing the poor carbamate groups of thermotolerance in traditional TPU, make its thermal stability poor, life-time service temperature is only 80 ℃, short-term use temperature is no more than 120 ℃, when temperature is during higher than 200 ℃, can there is thermal destruction in PU, therefore greatly limited its range of application.Except TPU resistance toheat is poor, it very easily burns in air as a kind of organic polymer material, during burning, flame is very violent and with black smoke, have serious molten drop phenomenon, its limiting oxygen index(LOI) (LOI) is only, between 18-20, to have serious disaster hidden-trouble simultaneously.Therefore to the heat-resisting and flame-retardant modified of TPU, be a very urgent problem.
At present, to TPU, heat-resisting and fire-retardant modification is mainly by the mode of physical blending and synthetic essential flame-proofed polymer material.Physical blending mode is scattered in additive flame retardant in polymeric substrate exactly, give base material flame retardant properties, feature is that chemical reaction does not occur other components in fire retardant and base material and base material, complete processing is simple, application is general, but need to improve the consistency between the components such as fire retardant and base material, improve the mechanical property of flame-proofed polymer material, avoid fire retardant to move out.In order effectively to address these problems, research concentrates on the mode essential fire-retardant, thermally stable polymer material of synthesizing more and more.By chemical reaction, fire-retardant, heat-resisting group is incorporated in polymer molecular structure, makes that it has that decomposition temperature is high, good heat resistance, do not allow incendive character.
Polyimide (PI) refers to the base polymer that main chain contains imide ring, rigidity imide structure is given the thermotolerance that polyimide is good, and himself has higher flame retardant properties, and the rate of being fuming is low, belong to self-extinguishing, can meet the fire-retardant requirement of most fields.At present, existing several different methods is successfully improved its resistance toheat by PI or imide functionality introducing PU main chain.Early stage method is by following the PI of end-blocking to react to prepare urethane with glycol isocyanic acid.Avadhani etc. once reported, the vulcabond that contains imide by utilization and polyethers are prepared novel poly-(ammonia ester-imide).At present, more research is mainly that heterocyclic group (imide, oxazolidone, triazine or phosphonitrile unit etc.) is incorporated on chainextender, thereby the thermostability of PU is carried out to modification.The people such as Qin once reported that synthetic a kind of diol chain-extension agent that contains sulfuryl and imide improved the thermostability of PU.Urethane thermostability is poor is exactly that the method for above-mentioned modification is just introduced heat-resisting group substantially on PU main chain, its carbamate chain link is not carried out to modification because contain the poor carbamate groups chain link of thermotolerance on its main chain.
Summary of the invention
The object of the invention is in order to propose a kind of anti-molten drop fire resistant polyimide type polyurethane and preparation method thereof, urethane prepared by the method is containing imide functionality, and high temperature resistant, contain imide ring simultaneously, polyethers, isocyanic ester, makes its constructional feature with polyimide and urethane, has effect fire-retardant, high temperature resistant, high strength in polymer composites.
The object of the invention is to be achieved through the following technical solutions.
A kind of anti-molten drop fire resistant polyimide type polyurethane of the present invention, its structural formula is:
Wherein Ar is
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
2---, n=20-500;
Or B is
n=10-70;
X is the polymerization degree, x=1-10, and y is the polymerization degree, y=2-15, a is the polymerization degree, a=20-90, b is the polymerization degree, b=35-150.
The preparation method of a kind of anti-molten drop fire resistant polyimide type polyurethane of the present invention, step is:
1) liquid anhydrous polyether glycol is mixed with liquid diisocyanate, protection of inert gas, stirs, and addition reaction is carried out in heating, and Heating temperature is 70-90 ℃, and be 1-15h heat-up time; The mol ratio of liquid anhydrous polyether glycol and liquid diisocyanate is 0.1-1:1
2) product that adds step 1) to obtain pyromellitic dianhydride and solvent, protection of inert gas, stirs, and polycondensation is carried out in heating, and Heating temperature is 60-100 ℃, and be 2-24h heat-up time; In pyromellitic dianhydride and step 1), the mol ratio of liquid anhydrous polyether glycol is 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 the product that obtains after finishing of reaction removes and obtains polyimide type polyurethane.
In step 1), liquid anhydrous polyether glycol is a kind of 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.
In step 1), liquid diisocyanate is: 4, and 4 '-diphenylmethanediisocyanate, Toluene-2,4-diisocyanate, 4-vulcabond or Toluene-2,4-diisocyanate, a kind of in 6-vulcabond.
Liquid state 4 in step 1), the preparation method of 4 '-diphenylmethanediisocyanate is: by solid 4,4 '-diphenylmethanediisocyanate joins in reaction vessel, heating makes its thawing; Heating temperature is 40-80 ℃.
In step 1), the preparation method of liquid anhydrous polyether glycol is: polyether glycol, in the vacuum drying oven of high temperature, is removed to moisture under vacuum condition; The temperature of vacuum drying oven is 100-120 ℃, and time 0.5-20h dewaters; Be less than-0.02MPa of vacuum tightness.
Step 2) in, solvent is a kind of in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF).
Beneficial effect
The features such as reaction conditions of the present invention is gentle stable, reproducible, and productive rate is high, the cycle is short, are applicable to expansion property to produce; Through test, learn the polyimide modified value that has improved temperature of initial decomposition and the limiting oxygen index(LOI) of urethane, and the melting drip phenomenon of the urethane suppressing when UL-94 vertical combustion, in addition polyimide modified total hot burst size and the heat release rate peak value that has also reduced urethane.
Accompanying drawing explanation
Infrared spectra adopts NICOLET6700IR type determination of infrared spectroscopy; Thermal weight loss (TG) adopts NETZSCH209F1 thermogravimetric analyzer to measure, nitrogen atmosphere, 10 ° of C/min of temperature rise rate; Limiting oxygen index(LOI) (rheology science company limited) is tested according to GB/T2406.2-2009; 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 polyimide type polyurethane of embodiment 2 preparations;
Fig. 2 is thermogravimetric curve figure and the differential curve figure thereof of the polyimide type polyurethane of embodiment 1,2,3 preparations; 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 that mass loss rate unit is %/min;
Fig. 3 is the heat release rate curve figure of the polyimide type polyurethane of embodiment 1,2,3 preparations, and its ordinate zou represents heat release rate, and unit is KW/m
2;
Total hot releasing curve diagram of the polyimide type polyurethane of Fig. 4 embodiment 1,2,3 preparations, its ordinate zou represents total hot burst size, unit is MJ/m
2.
Embodiment
Below by embodiment, the invention will be further described, but embodiment does not limit the scope of the invention.
Embodiment 1
Preparation MDI(4,4 '-diphenylmethanediisocyanate): PTMG(PTMG, molecular weight is 2000 ± 50): the polyimide type polyurethane that the molar ratio of PMAD is 2:1:1, is called PIU211;
Raw material is: MDI is 7.50g, and PTMG is 30.00g, and PMAD is 3.26g, DMF solvent 150mL;
1) by 30.00g PTMG in the vacuum drying oven of 110 ℃ of high temperature, under vacuum condition, remove moisture 2h, be less than-0.02MP of vacuum tightness
a;
2) the liquid MDI of 3.92g is joined in reaction vessel, under 60 ℃ of conditions, make its thawing;
3) in the liquid PTMG of the 30.00g that step 1) obtained with step 2) in the liquid MDI of 3.92g that obtains, stir, under 80 ℃ of conditions, carry out addition reaction, after 1h, reaction finishes;
4) product step 3) being obtained adds the 150mL solution that contains 1.63g PMAD, and protection of inert gas is stirred, and under 80 ℃ of conditions, carries out polycondensation 10h; In solution, solvent is DMF;
5) solvent of the product obtaining after reaction is finished is removed, and obtains polyimide type polyurethane PIU211.
Above-mentioned steps 3) and 4) reaction scheme as follows:
Embodiment 2
Preparation MDI(4,4 '-diphenylmethanediisocyanate): PTMG(PTMG, molecular weight is 2000 ± 50): the polyimide type polyurethane that the molar ratio of PMAD is 3:1:2, is called PIU312;
Raw material is: MDI is 11.25g, and PTMG is 30.00g, and PMAD is 6.54g, DMF solvent 150mL;
Preparation method, with embodiment 1, obtains polyimide type polyurethane PIU312.
Embodiment 3
Preparation TDI(Toluene-2,4-diisocyanate, 4-vulcabond): PTMG(PTMG, molecular weight is 2000 ± 50): the polyimide type polyurethane that the molar ratio of PMAD is 3:2:1, is called PIU321;
Raw material is: TDI is 3.92g, and PTMG is 30.00g, and PMAD is 1.63g, DMF solvent 150mL;
Preparation method, with embodiment 1, obtains polyimide type polyurethane PIU321.
UL-94 vertical combustion, limiting oxygen index(LOI) and the mechanical strength of table 1 polyimide type polyurethane
The thermal weight loss related data of table 2 polyimide type polyurethane
T
5%: corresponding temperature during sample thermal weight loss 5%;
T
maxs: sample thermal weight loss corresponding temperature when the fastest.
Claims (10)
1. an anti-molten drop fire resistant polyimide type polyurethane, is characterized in that 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;
X is the polymerization degree, x=1-10, and y is the polymerization degree, y=2-15, a is the polymerization degree, a=20-90, b is the polymerization degree, b=35-150.
2. a preparation method for anti-molten drop fire resistant polyimide type polyurethane, is characterized in that step is:
1) liquid anhydrous polyether glycol is mixed with liquid diisocyanate, protection of inert gas, stirs, and addition reaction is carried out in heating, and Heating temperature is 70-90 ℃, and be 1-15h heat-up time; The mol ratio of liquid anhydrous polyether glycol and liquid diisocyanate is 0.1-1:1
2) product that adds step 1) to obtain pyromellitic dianhydride and solvent, protection of inert gas, stirs, and polycondensation is carried out in heating, and Heating temperature is 60-100 ℃, and be 2-24h heat-up time; In pyromellitic dianhydride and step 1), the mol ratio of liquid anhydrous polyether glycol is 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 the product that obtains after finishing of reaction removes and obtains polyimide type polyurethane.
3. the preparation method of a kind of anti-molten drop fire resistant polyimide type polyurethane according to claim 2, is characterized in that: in step 1), liquid anhydrous polyether glycol is a kind of in PTMG, polyoxyethylene glycol or polyethylene oxide-tetrahydrofuran (THF) ether glycol.
4. the preparation method of a kind of anti-molten drop fire resistant polyimide type polyurethane 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 anti-molten drop fire resistant polyimide type polyurethane 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 anti-molten drop fire resistant polyimide type polyurethane 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 anti-molten drop fire resistant polyimide type polyurethane according to claim 2, it is characterized in that: in step 1), liquid diisocyanate is: 4,4 '-diphenylmethanediisocyanate, Toluene-2,4-diisocyanate, 4-vulcabond or Toluene-2,4-diisocyanate, a kind of in 6-vulcabond.
8. the preparation method of a kind of anti-molten drop fire resistant polyimide type polyurethane according to claim 7, it is characterized in that: liquid state 4 in step 1), the preparation method of 4 '-diphenylmethanediisocyanate is: by solid 4,4 '-diphenylmethanediisocyanate joins in reaction vessel, and heating makes its thawing; Heating temperature is 40-80 ℃.
9. the preparation method of a kind of anti-molten drop fire resistant polyimide type polyurethane according to claim 2, it is characterized in that: in step 1), the preparation method of liquid anhydrous polyether glycol is: polyether glycol, in the vacuum drying oven of high temperature, is removed to moisture under vacuum condition; The temperature of vacuum drying oven is 100-120 ℃, and time 0.5-20h dewaters; Be less than-0.02MPa of vacuum tightness.
10. the preparation method of a kind of anti-molten drop fire resistant polyimide type polyurethane of stating according to claim 2, it is characterized in that: step 2) in solvent be N, a kind of in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or tetrahydrofuran (THF).
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877336A (en) * | 2015-05-07 | 2015-09-02 | 北京市射线应用研究中心 | Polyurethane-imide-base multifunctional composite damping material and preparation method thereof |
| CN104945903A (en) * | 2015-07-14 | 2015-09-30 | 苏州科淼新材料有限公司 | Fold-resistant composite material |
| CN105062342A (en) * | 2015-08-12 | 2015-11-18 | 河南卓立膜材料股份有限公司 | Synthetic resin and back-coating solution prepared from same |
| CN104193953B (en) * | 2014-09-02 | 2017-01-11 | 北京理工大学 | Polyimide-type polyurethane containing DOPO group and preparation method of polyimide-type polyurethane |
| CN109824860A (en) * | 2019-03-07 | 2019-05-31 | 中国科学院长春应用化学研究所 | A kind of polyurethane polyureas acid imide foam material and preparation method thereof |
| CN111100317A (en) * | 2019-12-11 | 2020-05-05 | 山东省科学院新材料研究所 | Flexible polyimide aerogel and preparation method thereof |
| CN111607058A (en) * | 2020-06-12 | 2020-09-01 | 绍兴诺鼎卫浴洁具股份有限公司 | High-thermal-conductivity thermoplastic imidized polyurethane material and preparation method thereof |
| CN111848903A (en) * | 2019-10-16 | 2020-10-30 | 宁波途锐达休闲用品有限公司 | Microporous polyurethane foam material and its production process |
| CN112390926A (en) * | 2020-11-16 | 2021-02-23 | 黑龙江省科学院高技术研究院 | Preparation method of ternary-structure liquid copolymer resin |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104193953B (en) * | 2014-09-02 | 2017-01-11 | 北京理工大学 | Polyimide-type polyurethane containing DOPO group and preparation method of polyimide-type polyurethane |
| CN104877336A (en) * | 2015-05-07 | 2015-09-02 | 北京市射线应用研究中心 | Polyurethane-imide-base multifunctional composite damping material and preparation method thereof |
| CN104877336B (en) * | 2015-05-07 | 2018-01-09 | 北京市射线应用研究中心 | A kind of imide-urethane Quito function and service damping material and preparation method thereof |
| CN104945903A (en) * | 2015-07-14 | 2015-09-30 | 苏州科淼新材料有限公司 | Fold-resistant composite material |
| CN105062342A (en) * | 2015-08-12 | 2015-11-18 | 河南卓立膜材料股份有限公司 | Synthetic resin and back-coating solution prepared from same |
| CN109824860A (en) * | 2019-03-07 | 2019-05-31 | 中国科学院长春应用化学研究所 | A kind of polyurethane polyureas acid imide foam material and preparation method thereof |
| CN111848903A (en) * | 2019-10-16 | 2020-10-30 | 宁波途锐达休闲用品有限公司 | Microporous polyurethane foam material and its production process |
| CN111100317A (en) * | 2019-12-11 | 2020-05-05 | 山东省科学院新材料研究所 | Flexible polyimide aerogel and preparation method thereof |
| CN111607058A (en) * | 2020-06-12 | 2020-09-01 | 绍兴诺鼎卫浴洁具股份有限公司 | High-thermal-conductivity thermoplastic imidized polyurethane material and preparation method thereof |
| CN111607058B (en) * | 2020-06-12 | 2021-12-10 | 苏州宝乾新材料科技股份有限公司 | High-thermal-conductivity thermoplastic imidized polyurethane material and preparation method thereof |
| CN112390926A (en) * | 2020-11-16 | 2021-02-23 | 黑龙江省科学院高技术研究院 | Preparation method of ternary-structure liquid copolymer resin |
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