CN105131284A - High-heat-resistant thermal-sealable polyimide thin film, preparation method and application thereof - Google Patents
High-heat-resistant thermal-sealable polyimide thin film, preparation method and application thereof Download PDFInfo
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- CN105131284A CN105131284A CN201510419363.3A CN201510419363A CN105131284A CN 105131284 A CN105131284 A CN 105131284A CN 201510419363 A CN201510419363 A CN 201510419363A CN 105131284 A CN105131284 A CN 105131284A
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- BZMWYTDVUYRVEI-UHFFFAOYSA-N Cc(cc1)ccc1Oc(cc1)ccc1Oc1ccc(C)cc1 Chemical compound Cc(cc1)ccc1Oc(cc1)ccc1Oc1ccc(C)cc1 BZMWYTDVUYRVEI-UHFFFAOYSA-N 0.000 description 1
- LNKZBMIHRCNPID-UHFFFAOYSA-N Cc(cc1)ccc1Oc1cccc(Oc2ccc(C)cc2)c1 Chemical compound Cc(cc1)ccc1Oc1cccc(Oc2ccc(C)cc2)c1 LNKZBMIHRCNPID-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a high-heat-resistant thermal-sealable polyimide thin film, a preparation method and an application thereof. A structure general formula of the polymer is represented as the formula 1. The polymer is prepared through chemical imidization from following raw materials including p-phenylenediamine, aromatic diamines containing ether and 2,3,3',4'-diphenyl ether tetracarboxylic acid dianhydride. By means of control of ratio of the p-phenylenediamine to other aromatic diamines, the high-heat-resistant performance and thermal-sealability strength of the polyimide material represented as the formula 1 can be adjusted and controlled. The material can be used in the high-technology fields of aerospace, electronic and electric products, automobiles and the like as a coating or a thin film.
Description
Technical field
The invention belongs to Material Field, relate to a kind of high heat-resisting copoly type heat sealability polyimide and preparation method thereof and application.
Background technology
Polyimide (PI) film has a wide range of applications in the fields such as electric, advanced display, the energy and aerospace with the over-all properties of excellence.In actual applications, it often needs to carry out the bonding with self or other materials.But traditional PI film is because also existing the feature that intermolecular interaction is strong, surface energy is low and active group is few, directly or (Awaja cannot be combined with other materials by heat seal process, F., M.Gilbert, etal.ProgressinPolymerScience.2009,34 (9): 948-968).For this reason, people take the methods such as chemical conversion treatment, Cement Composite Treated by Plasma and surface-coated to improve PI surface with by the consistency of surface of adherence.But these methods often cause damage to the bulk properties of PI material, or have impact on the application reliability of material monolithic due to problems such as the resistance toheat applying caking agent are low.Thus, the PI research with intrinsic hot melt sealing characteristic receives the concern of people day by day.Wherein, flexible structure and the introducing of isomerization structure in PI molecular chain are two kinds of main methods.
Flexible structure can reduce in PI molecule and intermolecular reactive force, improves the motor capacity of molecular chain, thus is conducive to the raising of PI hot melt sealing property.United States Patent (USP) (USA5298331A, 1994) passing through will containing ether type dianhydride 3,3', 4,4'-oxydiphthalic (ODPA) and 1, two (4-amino-benzene oxygen) benzene (144APB) of 4-, 1,3-two (4-amino-benzene oxygen) benzene (134APB) etc. are incorporated into the PI system of non-heat salable containing ether type aromatic diamines, prepared the heat sealability PI with good heat seal strength.E.I.Du Pont Company is business-like
kJ product is based on said structure.
The space structure of asymmetric isomerization aromatic dianhydride distortion can give polymkeric substance higher free volume, thus thermoplasticity (the Hasegawa of PI can more effectively be improved, etal.Macromolecules.1999,, thus preparation has the PI of good heat sealability 32 (2): 387-396).Japanese Patent (JP2004285103A) openly reports in a kind of structure and contains ether type dianhydride 2 containing asymmetric, 3, the PI system of 3', 4'-oxydiphthalic (aODPA) and 3 above aromatic diamines of phenyl ring quantity, itself and Copper Foil etc. have good bond strength.Space development mechanism of Japan is based on aODPA with containing ether type aromatic diamines 4,4'-diaminodiphenyl oxide (4,4'ODA), prepare the ISAS-TPI with heat seal property, it was successfully applied to (Yokota in IKAROS solar sail in 2010, R.etal.:Developmentofheatsealablepolyimidethinfilmswithh ighspaceenvironmentalstabilityforsolarsailIKAROSmembrane .AstrophysSpaceSciProc.2013,32:303 – 316).
But too much the introducing of flexible structure, often causes very large infringement to the resistance toheat of PI.Such as, E.I.Du Pont Company
kJ and second-order transition temperature (T
g) only have 220 DEG C.
Summary of the invention
The object of this invention is to provide a kind of high heat-resisting copoly type heat sealability polyimide and preparation method thereof and application.
Height provided by the invention heat-resisting copoly type heat sealability polyimide, its general structure such as formula shown in I,
In described formula I, Ar be selected from following radicals any one:
M be 0-200 and be not 0 integer, n is the integer of 0-200;
And n is not when being 0, m:n=0:100 ~ 100:0; Particularly, m:n=10:90,20:80,30:70,40:60,50:50 or 60:40.
In described formula I, preferred m:n=40:60 ~ 60:40; Particularly, m:n=40:60,50:50 or 60:40;
M specifically can be 16,27,37,50,51,152 or 150-180;
N specifically can be 146,111,86,76,51,102,
When n is 0, m specifically can be 100;
Compound described in above-mentioned formula I can obtain according to following method preparation provided by the invention.
Shown in the above-mentioned formula I of preparation provided by the invention, the method for polyimide, comprises the steps:
By Ursol D (PDA), containing ether type aromatic diamine and 2,3,3', 4'-oxydiphthalic (aODPA) is mixed in solvent and carries out polyreaction, add diacetyl oxide after completion of the reaction and pyridine carries out chemical imidization reaction, react the described formula I polyimide that the complete n of obtaining is not 0;
Or, Ursol D and 2,3,3', 4'-oxydiphthalic are mixed in solvent and carry out polyreaction, add diacetyl oxide after completion of the reaction and pyridine carries out chemical imidization reaction, react the complete n that obtains for polyimide shown in the formula I of 0.
In aforesaid method, the described ether type aromatic diamine that contains all is selected from 4,4'-diaminodiphenyl oxide (4,4'ODA), 3,4'-diaminodiphenyl oxide, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 1,3-two (4-amino-benzene oxygen) benzene, 1, at least one in two (3-amino-benzene oxygen) benzene of 3-and two (4-amino-benzene oxygen) phenyl ether of 4,4'-.
Preparation n is not in the method for described formula I polyimide of 0, and the molfraction of described Ursol D is 0-100 part, and the described molfraction containing ether type aromatic diamines is 0-100 part, and described Ursol D and the molfraction containing ether type aromatic diamines are not all 0;
Described Ursol D and the molar ratio containing always feed intake mole dosage and described 2,3,3', the 4'-oxydiphthalic of ether type aromatic diamine are (0.97 ~ 1.00): 1.00, preferably (0.99 ~ 1.00): 1.00;
Described Ursol D and the molar ratio containing always feed intake mole dosage and the described diacetyl oxide of ether type aromatic diamine are 1.00:(3.00 ~ 10.00), preferred 5.00:1.00;
The molar ratio of described diacetyl oxide and described pyridine is 1.00:1.00;
Preparation n is in the method for described formula I polyimide of 0, described Ursol D feeds intake mole dosage and described 2,3,3', the molar ratio of 4'-oxydiphthalic is (0.97 ~ 1.00): 1.00, preferably (0.99 ~ 1.00): 1.00;
The molar ratio of described Ursol D and described diacetyl oxide is 1.00:(3.00 ~ 10.00), preferred 5.00:1.00;
The molar ratio of described diacetyl oxide and described pyridine is 1.00:1.00.
Described solvent is all selected from least one in N-Methyl pyrrolidone, meta-cresol, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) and gamma-butyrolactone;
The consumption of described solvent is and makes the mass percentage of solid in reaction system be 10%-30%, is preferably 15%-20%, specifically can be 18%;
In described polymerization procedure, the time is 12 hours-30 hours, preferably 20 hours-25 hours, more preferably 24 hours; Temperature is 0-35 DEG C, preferred 20-25 DEG C;
In described chemical imidization reactions steps, the time is 15 hours-30 hours, preferably 20 hours-25 hours, more preferably 24 hours; Temperature is 0-35 DEG C, preferred 20-25 DEG C.
In actually operating, the compound product system that can will be obtained by above-mentioned preparation method as required, precipitates with ethanol, obtains thread polyimide resin after washing drying; Also can by this resin product conveniently film prepare corresponding film.
In addition; the resin or film that polyimide prepares is stated by above-mentioned; and this resin or the application of film in the heat sealability coating or heat sealability film of fabricate devices; and the heat sealability coating of device containing described polyimide or described resin or film or heat sealability film, also belong to protection scope of the present invention.Wherein said device is the thermal protection device of spacecraft, the substrate of solar battery array, antenna reflector, antenna collector or solar sail.
The invention provides high heat-resisting copoly type heat sealability polyimide and preparation method thereof shown in a kind of formula I and application.This polymkeric substance be with Ursol D, other aromatic diamines and 2,3,3', 4'-oxydiphthalic for raw material, prepared by chemical imidization.By controlling the proportioning of Ursol D and other aromatic diamines, the regulation and control to the resistance toheat of polyimide material shown in formula I and heat seal strength can be realized.This material can be used as coating or film and is applied to aerospace, electronics, electrically and the high-tech sector such as automobile.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram that embodiment 1-7 prepares gained Kapton.
Fig. 2 is the DSC spectrogram that embodiment 1-7 prepares gained Kapton.
Fig. 3 is thermal weight loss (TGA) curve that embodiment 1-7 prepares gained polyimide.
Fig. 4 is the DMA curve that embodiment 1-7 prepares gained Kapton.
Fig. 5 is second-order transition temperature and the heat seal strength histogram that embodiment 1-7 prepares gained Kapton thing.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.Following embodiment carries out the method for stuctures and properties detection if no special instructions to products therefrom compound or polymkeric substance, is common detection methods.Described material all can obtain from open commercial sources if no special instructions.Described room temperature is 20-25 DEG C.The molecular weight of following embodiment resulting polymers is measured by laser light scattering (LLS) GPC, is absolute number average molecular.
Calorimetric differential scanning method (DSC).(beautiful TA company, Q100 series) on the Kapton calorimetric differential scanning instrument of preparation is tested, heat-up rate: 10 DEG C/min.
Dynamic thermomechanical analysis (DMA).The Kapton of preparation dynamic thermomechanical analysis apparatus (TA company of the U.S., Q800 series) is tested, heat-up rate: 5 DEG C/min, frequency 1Hz.
Thermogravimetry (TGA).The Kapton of preparation thermogravimetric analyzer (TA company of the U.S., Q50 series) is tested, heat-up rate: 20 DEG C/min, measurement atmosphere is nitrogen.
Heat sealability evaluation method.Heat-sealing is carried out on the L0001 laboratory heat sealing machine of Australian IDM instrument company, and heat-sealing pressure is 0.3MPa, and heat-sealing temperature is set in more than DMA curve rubber platform starting point about 20 ~ 50 DEG C.Heat sealing performance test is carried out according to national light industry industry standard QB/T2358-98.
Embodiment 1, the polyimide (CPI-1) shown in PDA and 44ODA and aODPA preparation formula I that is 10:90 by molar ratio
Under room temperature, be furnished with in the 250mL there-necked flask of nitrogen inlet at one, add the ODA of PDA and 8.1097g (40.5mmol) of 0.4866g (4.5mmol), and add the N-Methyl pyrrolidone (NMP) of 50g.After it dissolves completely, add the aODPA of 13.9595g (45mmol), and add the NMP of 53g, solid content (weight fraction) is adjusted to 18%.After stirred at ambient temperature carries out polyreaction 24h, add the diacetyl oxide of 22.97g (225mmol) and the pyridine of 17.80g (225mmol), continue stirring under room temperature and carry out chemical imidization reaction 24h, obtain clear yellow viscous solution.This solution is precipitated in 1000mL dehydrated alcohol, obtains yellow stringy solids.By this solid with after washing with alcohol three times, vacuum-drying at 140 DEG C, finally obtains CPI-1 resin.
Get dry filament resin 4g, be dissolved in the NMP of 18g, after solid dissolves completely, filter with G1 sand core funnel, obtain the polyimide solution that solid content is 18%.This solution is coated on clean sheet glass, and is placed in baking oven, with the heat-up rate of 2 DEG C/min, by 80 DEG C/2h, 120 DEG C/1h, 160 DEG C/1h, 180 DEG C/1h, 240 DEG C/2h, the program of 280 DEG C/30min heats up.After naturally cooling, sheet glass is placed in deionized water, peels off the yellow CPI-1 film obtaining self-supporting.
The structural formula of this polyimide is as follows, wherein m:n=10:90;
Infrared spectra (cm
-1): 1779,1725,1606,1502,1381,1243,746;
Infrared spectra as shown in Figure 1;
Molecular weight (g/mol): 75530, corresponding m is 16, n is 146;
DSC curve as shown in Figure 2;
TGA curve as shown in Figure 3;
DMA curve as shown in Figure 4;
The heat decomposition temperature of the film of CPI-1, second-order transition temperature (T
g) and heat seal strength as shown in table 1;
From ir data, this compound structure is correct, is compound shown in formula I.
Embodiment 2, the polyimide (CPI-2) shown in PDA and 44ODA and aODPA preparation formula I that is 20:80 by molar ratio
Under room temperature, be furnished with in the 250mL there-necked flask of nitrogen inlet at one, add the ODA of PDA and 7.2086g (36.0mmol) of 0.9733g (9.0mmol), and add the N-Methyl pyrrolidone (NMP) of 50g.After it dissolves completely, add the aODPA of 13.9595g (45mmol), and add the NMP of 51g, solid content (weight fraction) is adjusted to 18%.After stirred at ambient temperature carries out polyreaction 24h, add the diacetyl oxide of 22.97g (225mmol) and the pyridine of 17.80g (225mmol), continue stirring under room temperature and carry out chemical imidization reaction 24h, obtain clear yellow viscous solution.This solution is precipitated in 1000mL dehydrated alcohol, obtains yellow stringy solids.By this solid with after washing with alcohol three times, vacuum-drying at 140 DEG C, finally obtains CPI-2 resin.
Get dry filament resin 4g, be dissolved in the NMP of 18g, after solid dissolves completely, filter with G1 sand core funnel, obtain the polyimide solution that solid content is 18%.This solution is coated on clean sheet glass, and is placed in baking oven, with the heat-up rate of 2 DEG C/min, by 80 DEG C/2h, 120 DEG C/1h, 160 DEG C/1h, 180 DEG C/1h, 240 DEG C/2h, the program of 280 DEG C/30min heats up.After naturally cooling, sheet glass is placed in deionized water, peels off the yellow CPI-1 film obtaining self-supporting.
The structural formula of this polyimide is as follows, wherein m:n=20:80;
Infrared spectra (cm
-1): 1778,1724,1606,1505,1379,1243,746;
Infrared spectra as shown in Figure 1;
Molecular weight (g/mol): 63440, corresponding m is 27, n is 111;
DSC curve as shown in Figure 2;
TGA curve as shown in Figure 3;
DMA curve as shown in Figure 4;
The heat decomposition temperature of the film of CPI-2, second-order transition temperature (T
g) and heat seal strength as shown in table 1;
From ir data, this compound structure is correct, is compound shown in formula I.
Embodiment 3, the polyimide (CPI-3) shown in PDA and 44ODA and aODPA preparation formula I that is 30:70 by molar ratio
Under room temperature, be furnished with in the 250mL there-necked flask of nitrogen inlet at one, add the ODA of PDA and 6.3076g (31.5mmol) of 1.4599g (13.5mmol), and add the N-Methyl pyrrolidone (NMP) of 50g.After it dissolves completely, add the aODPA of 13.9595g (45mmol), and add the NMP of 49g, solid content (weight fraction) is adjusted to 18%.After stirred at ambient temperature carries out polyreaction 24h, add the diacetyl oxide of 22.97g (225mmol) and the pyridine of 17.80g (225mmol), continue stirring under room temperature and carry out chemical imidization reaction 24h, obtain clear yellow viscous solution.This solution is precipitated in 1000mL dehydrated alcohol, obtains yellow stringy solids.By this solid with after washing with alcohol three times, vacuum-drying at 140 DEG C, finally obtains CPI-3 resin.
Get dry filament resin 4g, be dissolved in the NMP of 18g, after solid dissolves completely, filter with G1 sand core funnel, obtain the polyimide solution that solid content is 18%.This solution is coated on clean sheet glass, and is placed in baking oven, with the heat-up rate of 2 DEG C/min, by 80 DEG C/2h, 120 DEG C/1h, 160 DEG C/1h, 180 DEG C/1h, 240 DEG C/2h, the program of 280 DEG C/30min heats up.After naturally cooling, sheet glass is placed in deionized water, peels off the yellow CPI-3 film obtaining self-supporting.
The structural formula of this polyimide is as follows, wherein m:n=30:70;
Infrared spectra (cm
-1): 1778,1724,1606,1506,1378,1243,746;
Infrared spectra as shown in Figure 1;
Molecular weight (g/mol): 55060, corresponding m is 37, n is 86;
DSC curve as shown in Figure 2;
TGA curve as shown in Figure 3;
DMA curve as shown in Figure 4;
The heat decomposition temperature of the film of CPI-3, second-order transition temperature (T
g) and heat seal strength as shown in table 1;
From ir data, this compound structure is correct, is compound shown in formula I.
Embodiment 4, the polyimide (CPI-4) shown in PDA and 44ODA and aODPA preparation formula I that is 40:60 by molar ratio
Under room temperature, be furnished with in the 250mL there-necked flask of nitrogen inlet at one, add the ODA of PDA and 5.7669g (19.2mmol) of 2.0763g (19.2mmol), and add the N-Methyl pyrrolidone (NMP) of 50g.After it dissolves completely, add the aODPA of 14.8901g (48mmol), and add the NMP of 54g, solid content (weight fraction) is adjusted to 18%.After stirred at ambient temperature carries out polyreaction 24h, add the pyridine of the diacetyl oxide and 18.98 (240mmol) of 24.50g (240mmol), continue stirring under room temperature and carry out chemical imidization reaction 24h, obtain clear yellow viscous solution.This solution is precipitated in 1000mL dehydrated alcohol, obtains yellow stringy solids.By this solid with after washing with alcohol three times, vacuum-drying at 140 DEG C, finally obtains CPI-4 resin.
Get dry filament resin 4g, be dissolved in the NMP of 18g, after solid dissolves completely, filter with G1 sand core funnel, obtain the polyimide solution that solid content is 18%.This solution is coated on clean sheet glass, and is placed in baking oven, with the heat-up rate of 2 DEG C/min, by 80 DEG C/2h, 120 DEG C/1h, 160 DEG C/1h, 180 DEG C/1h, 240 DEG C/2h, the program of 280 DEG C/30min heats up.After naturally cooling, sheet glass is placed in deionized water, peels off the yellow CPI-4 film obtaining self-supporting.
The structural formula of this polyimide is as follows, wherein m:n=40:60;
Infrared spectra (cm
-1): 1778,1724,1607,1507,1375,1243,746;
Infrared spectra as shown in Figure 1;
Molecular weight (g/mol): 55510, corresponding m is 50, n is 76;
DSC curve as shown in Figure 2;
TGA curve as shown in Figure 3;
DMA curve as shown in Figure 4;
The heat decomposition temperature of the film of CPI-4, second-order transition temperature (T
g) and heat seal strength as shown in table 1;
From ir data, this compound structure is correct, is compound shown in formula I.
Embodiment 5, the polyimide (CPI-5) shown in PDA and 44ODA and aODPA preparation formula I that is 50:50 by molar ratio
Under room temperature, be furnished with in the 250mL there-necked flask of nitrogen inlet at one, add the ODA of PDA and 4.8058g (24.0mmol) of 2.5954g (24.0mmol), and add the N-Methyl pyrrolidone (NMP) of 50g.After it dissolves completely, add the aODPA of 14.8901g (48mmol), and add the NMP of 51g, solid content (weight fraction) is adjusted to 18%.After stirred at ambient temperature carries out polyreaction 24h, add the pyridine of the diacetyl oxide and 18.98 (240mmol) of 24.50g (240mmol), continue stirring under room temperature and carry out chemical imidization reaction 24h, obtain clear yellow viscous solution.This solution is precipitated in 1000mL dehydrated alcohol, obtains yellow stringy solids.By this solid with after washing with alcohol three times, vacuum-drying at 140 DEG C, finally obtains CPI-5 resin.
Get dry filament resin 4g, be dissolved in the NMP of 18g, after solid dissolves completely, filter with G1 sand core funnel, obtain the polyimide solution that solid content is 18%.This solution is coated on clean sheet glass, and is placed in baking oven, with the heat-up rate of 2 DEG C/min, by 80 DEG C/2h, 120 DEG C/1h, 160 DEG C/1h, 180 DEG C/1h, 240 DEG C/2h, the program of 280 DEG C/30min heats up.After naturally cooling, sheet glass is placed in deionized water, peels off the yellow CPI-5 film obtaining self-supporting.
The structural formula of this polyimide is as follows, wherein m:n=50:50;
Infrared spectra (cm
-1): 1778,1725,1607,1508,1372,1243,746;
Infrared spectra as shown in Figure 1;
Molecular weight (g/mol): 43760, corresponding m is 51, n is 51;
DSC curve as shown in Figure 2;
TGA curve as shown in Figure 3;
DMA curve as shown in Figure 4;
The heat decomposition temperature of the film of CPI-5, second-order transition temperature (T
g) and heat seal strength as shown in table 1;
From ir data, this compound structure is correct, is compound shown in formula I.
Embodiment 6, the polyimide (CPI-6) shown in PDA and 44ODA and aODPA preparation formula I that is 60:40 by molar ratio
Under room temperature, be furnished with in the 250mL there-necked flask of nitrogen inlet at one, add the ODA of PDA and 3.8446g (19.2mmol) of 3.1144g (28.8mmol), and add the N-Methyl pyrrolidone (NMP) of 50g.After it dissolves completely, add the aODPA of 14.8901g (48mmol), and add the NMP of 50g, solid content (weight fraction) is adjusted to 18%.After stirred at ambient temperature carries out polyreaction 24h, add the pyridine of the diacetyl oxide and 18.98 (240mmol) of 24.50g (240mmol), continue stirring under room temperature and carry out chemical imidization reaction 24h, obtain clear yellow viscous solution.This solution is precipitated in 1000mL dehydrated alcohol, obtains yellow stringy solids.By this solid with after washing with alcohol three times, vacuum-drying at 140 DEG C, finally obtains CPI-6 resin.
Get dry filament resin 4g, be dissolved in the NMP of 18g, after solid dissolves completely, filter with G1 sand core funnel, obtain the polyimide solution that solid content is 18%.This solution is coated on clean sheet glass, and is placed in baking oven, with the heat-up rate of 2 DEG C/min, by 80 DEG C/2h, 120 DEG C/1h, 160 DEG C/1h, 180 DEG C/1h, 240 DEG C/2h, the program of 280 DEG C/30min heats up.After naturally cooling, sheet glass is placed in deionized water, peels off the yellow CPI-6 film obtaining self-supporting.
The structural formula of this polyimide is as follows, wherein m:n=60:40;
Infrared spectra (cm
-1): 1778,1725,1607,1508,1369,1244,746;
Infrared spectra as shown in Figure 1;
Molecular weight (g/mol): 106300, corresponding m is 152, n is 102;
DSC curve as shown in Figure 2;
TGA curve as shown in Figure 3;
DMA curve as shown in Figure 4;
The heat decomposition temperature of the film of CPI-6, second-order transition temperature (T
g) and heat seal strength as shown in table 1;
From ir data, this compound structure is correct, is compound shown in formula I.
Embodiment 7, the polyimide (CPI-7) shown in PDA and 44ODA and aODPA preparation formula II that is 100:0 by molar ratio
Under room temperature, be furnished with in the 250mL there-necked flask of nitrogen inlet at one, add the PDA of 5.407g (45.0mmol), and the N-Methyl pyrrolidone of 50g (NMP).After it dissolves completely, add the aODPA of 15.5105g (50mmol), and add the NMP of 45g, solid content (weight fraction) is adjusted to 18%.After stirred at ambient temperature carries out polyreaction 24h, add the pyridine of the diacetyl oxide and 19.78 (250mmol) of 25.52g (250mmol), continue stirring under room temperature and carry out chemical imidization reaction 24h, obtain clear yellow viscous solution.This solution is precipitated in 1000mL dehydrated alcohol, obtains yellow stringy solids.By this solid with after washing with alcohol three times, vacuum-drying at 140 DEG C, finally obtains CPI-7 resin.
Get dry filament resin 4g, be dissolved in the NMP of 18g, after solid dissolves completely, filter with G1 sand core funnel, obtain the polyimide solution that solid content is 18%.This solution is coated on clean sheet glass, and is placed in baking oven, with the heat-up rate of 2 DEG C/min, by 80 DEG C/2h, 120 DEG C/1h, 160 DEG C/1h, 180 DEG C/1h, 240 DEG C/2h, the program of 280 DEG C/30min heats up.After naturally cooling, sheet glass is placed in deionized water, peels off the yellow CPI-7 film obtaining self-supporting.
The structural formula of this polyimide is as follows, wherein m=15-180;
Infrared spectra (cm
-1): 1778,1728,1608,1517,1370,1270,744;
Infrared spectra as shown in Figure 1;
DSC curve as shown in Figure 2;
TGA curve as shown in Figure 3;
DMA curve as shown in Figure 4;
The heat decomposition temperature of the film of CPI-7, second-order transition temperature (T
g) and heat seal strength as shown in table 1;
From ir data, this compound structure is correct, is compound shown in formula II.
Comparative example 1, prepare polyimide by aODPA and ODA
Under room temperature, be furnished with in the 250mL there-necked flask of nitrogen inlet at one, add the ODA of 10.012g (50mmol), and the N-Methyl pyrrolidone of 50g (NMP).After it dissolves completely, add the aODPA of 15.5105g (50mmol), and add the NMP of 56g, solid content (weight fraction) is adjusted to 18%.After stirred at ambient temperature 24h, add the pyridine of the diacetyl oxide and 19.78 (250mmol) of 25.52g (250mmol), continue under room temperature to stir 24h, obtain clear yellow viscous solution.This solution is precipitated in 1000mL dehydrated alcohol, obtains yellow stringy solids.By this solid with after washing with alcohol three times, vacuum-drying at 140 DEG C, finally obtains CPI-10 resin.
Get dry filament resin 4g, be dissolved in the NMP of 18g, after solid dissolves completely, filter with G1 sand core funnel, obtain the polyimide solution that solid content is 18%.This solution is coated on clean sheet glass, and is placed in baking oven, with the heat-up rate of 2 DEG C/min, by 80 DEG C/2h, 120 DEG C/1h, 160 DEG C/1h, 180 DEG C/1h, 240 DEG C/2h, the program of 280 DEG C/30min heats up.After naturally cooling, sheet glass is placed in deionized water, peels off the yellow film obtaining self-supporting.
The structural formula of this polyimide is as follows:
The heat decomposition temperature of this film, second-order transition temperature (T
g) and heat seal strength as shown in table 1;
From ir data, this compound structure is correct, is compound shown in formula I.
In embodiment 1-7, the performance data of Kapton is summarized in table 1, and be convenient to directly perceived, its second-order transition temperature and heat seal strength are done in Fig. 5 with bar graph form.
Compare can find out with comparative example 1 (not containing PDA in diamine components), in diamines, in the present invention, introduce the second-order transition temperature that PDA component improves Kapton effectively.Meanwhile, when the molar content of PDA in diamines is between 40%-60%, the second-order transition temperature of PI reaches more than 300 DEG C, and Kapton has good heat seal strength simultaneously.
The performance of table 1, Kapton
Claims (10)
1. polyimide shown in formula I,
In described formula I, Ar be selected from following radicals any one:
M be 0-200 and be not 0 integer, n is the integer of 0-200;
And n is not when being 0, m:n=0:100 ~ 100:0.
2. polyimide according to claim 1, is characterized in that: in described formula I, m:n=40:60 ~ 60:40.
3. prepare a method for polyimide shown in the arbitrary described formula I of claim 1 or 2, comprise the steps:
By Ursol D, to be mixed in solvent containing ether type aromatic diamine and 2,3,3', 4'-oxydiphthalic and to carry out polyreaction, add diacetyl oxide after completion of the reaction and pyridine carries out chemical imidization reaction, react the described formula I polyimide that the complete n of obtaining is not 0;
Or, Ursol D and 2,3,3', 4'-oxydiphthalic are mixed in solvent and carry out polyreaction, add diacetyl oxide after completion of the reaction and pyridine carries out chemical imidization reaction, react the complete n that obtains for polyimide shown in the formula I of 0.
4. method according to claim 3, it is characterized in that: the described ether type aromatic diamine that contains is selected from 4,4'-diaminodiphenyl oxide, 3,4'-diaminodiphenyl oxide, 1, two (4-amino-benzene oxygen) benzene, 1 of 4-, at least one in two (4-amino-benzene oxygen) benzene of 3-, 1,3-two (3-amino-benzene oxygen) benzene and two (4-amino-benzene oxygen) phenyl ether of 4,4'-.
5. the method according to claim 3 or 4, it is characterized in that: preparation n is not in the method for described formula I polyimide of 0, the molfraction of described Ursol D is 0-100 part, the described molfraction containing ether type aromatic diamines is 0-100 part, and described Ursol D and the molfraction containing ether type aromatic diamines are not all 0;
Described Ursol D and the molar ratio containing always feed intake mole dosage and described 2,3,3', the 4'-oxydiphthalic of ether type aromatic diamine are (0.97 ~ 1.00): 1.00, preferably (0.99 ~ 1.00): 1.00;
Described Ursol D and the molar ratio containing always feed intake mole dosage and the described diacetyl oxide of ether type aromatic diamine are 1.00:(3.00 ~ 10.00), preferred 5.00:1.00;
The molar ratio of described diacetyl oxide and described pyridine is 1.00:1.00;
Preparation n is in the method for described formula I polyimide of 0, described Ursol D feeds intake mole dosage and described 2,3,3', the molar ratio of 4'-oxydiphthalic is (0.97 ~ 1.00): 1.00, preferably (0.99 ~ 1.00): 1.00;
The molar ratio of described Ursol D and described diacetyl oxide is 1.00:(3.00 ~ 10.00), preferred 5.00:1.00;
The molar ratio of described diacetyl oxide and described pyridine is 1.00:1.00.
6., according to described method arbitrary in claim 3-5, it is characterized in that: described solvent is all selected from least one in N-Methyl pyrrolidone, meta-cresol, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO) and gamma-butyrolactone;
The consumption of described solvent is and makes the mass percentage of solid in reaction system be 10%-30%, is preferably 15%-20%.
7., according to described method arbitrary in claim 3-6, it is characterized in that: in described polymerization procedure, the time is 12 hours-30 hours, preferably 20 hours-25 hours, more preferably 24 hours; Temperature is 0-35 DEG C, preferred 20-25 DEG C;
In described chemical imidization reactions steps, the time is 15 hours-30 hours, preferably 20 hours-25 hours, more preferably 24 hours; Temperature is 0-35 DEG C, preferred 20-25 DEG C.
8. the resin prepared by polyimide described in claim 1 or 2 or film.
9. resin or the application of film in the heat sealability coating or heat sealability film of fabricate devices described in polyimide shown in formula I described in claim 1 or 2 or claim 8;
The heat sealability coating of the device containing resin described in polyimide described in claim 1 or 2 or claim 8 or film or heat sealability film.
10. application according to claim 9 or heat sealability coating or heat sealability film, is characterized in that: described device is the thermal protection device of spacecraft, the substrate of solar battery array, antenna reflector, antenna collector or solar sail.
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| CN116003794A (en) * | 2022-12-29 | 2023-04-25 | 中国科学院化学研究所 | High-frequency high-heat-resistance heat-sealable poly (aryl ester-imide) resin and preparation method and application thereof |
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| CN102167824A (en) * | 2011-01-24 | 2011-08-31 | 中国科学院化学研究所 | Polyimide film and preparation method and applications thereof |
| CN102532543A (en) * | 2011-12-20 | 2012-07-04 | 中国科学院化学研究所 | Copolymerization hot-sealing polyimide and preparation method and application thereof |
| CN103724623A (en) * | 2013-12-16 | 2014-04-16 | 上海市合成树脂研究所 | Method for preparing soluble meltable copolymerized polyimide molding plastic |
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| US5310625A (en) * | 1992-03-13 | 1994-05-10 | International Business Machines Corporation | Process for forming negative tone images of polyimides using base treatment of crosslinked polyamic ester |
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| CN102532543A (en) * | 2011-12-20 | 2012-07-04 | 中国科学院化学研究所 | Copolymerization hot-sealing polyimide and preparation method and application thereof |
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