CN104017212A - Polyimide resin, preparation method thereof and polyimide foam - Google Patents

Polyimide resin, preparation method thereof and polyimide foam Download PDF

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CN104017212A
CN104017212A CN201310066152.7A CN201310066152A CN104017212A CN 104017212 A CN104017212 A CN 104017212A CN 201310066152 A CN201310066152 A CN 201310066152A CN 104017212 A CN104017212 A CN 104017212A
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polyimide resin
polyimide
foam
preparation
dianhydride
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CN104017212B (en
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赵婷婷
宋宇
吴波
金启明
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BYD Co Ltd
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BYD Co Ltd
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Abstract

The invention provides polyimide resin which contains structural units represented by a formula I or II or III shown in descriptions. The invention further provides a method for preparing the polyimide resin, wherein the method comprises the steps of adding R1(NH2)3, polylactide and dianhydride into a solvent, and removing the solvent after reaction, thereby obtaining the polyimide resin. Finally, the invention further provides polyimide foam which is prepared through crushing the polyimide resin provided by the invention, then, tabletting, and then, carrying out heated foaming. An imide structural unit contained by the polyimide resin provided by the invention has good reaction activity, so that the polyimide foam with good thermal stability, chemical stability and mechanical properties and relatively long service life can be obtained after heated foaming.

Description

A kind of polyimide resin and preparation method thereof and a kind of polyimide foam
Technical field
The invention belongs to polyimide material field, relate in particular to a kind of polyimide resin and preparation method thereof and a kind of polyimide foam.
Background technology
Along with the appearance of polymer artificial synthetic materials, porous material is used widely in synthetic plastics industry, and each type of foam is seen everywhere.Compared to transmission foam materialss such as urethane, polyethylene, polystyrene, polyimide foam has excellent resistance toheat, high temperature barrier, noise reduction, shock resistance, dimensional stability, wave penetrate capability and flame retardant properties, can be used as heat insulation, sound insulation and flame retardant properties, in field application such as aircraft, spacecraft, weaponry, naval vessel, bullet train and automobiles.
At present, the polyimide foam of available technology adopting, is generally by adding fatty alcohol to foam and make as whipping agent in methacrylic acid and methacrylonitrile monomer mixture.But because self-polymerization all can occur for methacrylic acid and these two kinds of monomers of methacrylonitrile, cause the imide rate of the two lower, the use temperature of the foam materials obtaining is lower, and mechanical property is also poor.
Summary of the invention
The invention solves the polyimide foam of being prepared by methacrylic acid and methacrylic nitrile monomer in prior art and have that use temperature is low, the technical problem of bad mechanical property, propose a kind of novel polyimide resin and preparation method thereof and a kind of polyimide foam.
Particularly, the invention provides a kind of polyimide resin, in described polyimide resin, contain the structural unit shown in formula I, formula II or formula III:
Wherein, X is n is 20～50 integer;
R 1for or
R 2be selected from any one in O, S or lower array structure:
The present invention also provides the preparation method of described polyimide resin, comprises R 1(NH 2) 3, polylactide, dianhydride add in solvent, after reaction, except desolventizing, obtains described polyimide resin;
Wherein, described dianhydride is or
Finally, the invention provides a kind of polyimide foam, described polyimide foam is by compressing tablet after polyimide resin provided by the invention is pulverized, and then foamable obtains.
Polyimide resin provided by the invention, contained imide structure unit has good reactive behavior, it can decompose the homodisperse nanometer foam of generation in the time of foamable, thereby obtain polyimide foam provided by the invention, this polyimide foam at high temperature also has good thermostability, chemical stability, mechanical property, and work-ing life is longer.Meanwhile, in the preparation method of polyimide resin provided by the invention, by synthesis material (is comprised to aromatic amine R 1(NH 2) 3, polylactide and dianhydride) species structure specifically select, while ensureing reaction, there is higher imide rate.
Embodiment
The invention provides a kind of polyimide resin, in described polyimide resin, contain the structural unit shown in formula I, formula II or formula III:
Wherein, X is n is 20～50 integer;
R 1for
R 2be selected from any one in O, S or lower array structure:
Polyimide resin provided by the invention, contained imide structure unit has good reactive behavior, it can decompose the homodisperse nanometer foam of generation in the time of foamable, thereby obtain polyimide foam provided by the invention, this polyimide foam at high temperature also has good thermostability, chemical stability, mechanical property, and work-ing life is longer.
In the present invention, the second-order transition temperature of described polyimide resin is more than 300 DEG C, is even more than 350 DEG C, thereby can ensure follow-up foamable time, serious softening transform can not occur resin.Accordingly, the number-average molecular weight of described polyimide resin is 70000～500000.
As a kind of preferred implementation of the present invention, R 1for r 2for but be not limited to this.
The present invention also provides the preparation method of described polyimide resin, comprises R 1(NH 2) 3, polylactide, dianhydride add in solvent, after reaction, except desolventizing, obtains described polyimide resin;
Wherein, described dianhydride is (pyromellitic acid anhydride), or
Wherein, aromatic amine R 1(NH 2) 3structure as shown in the formula shown in IV, it is three amine structures, is specially the compound shown in formula V or formula VI.In the present invention, described aromatic amine R 1(NH 2) 3the preferably compound shown in employing formula V, it is three (4-aminophenyl) amine (being called for short TAPA), but is not limited to this.
Polylactide, has another name called poly(lactic acid), and its structural formula is
Preparation in accordance with the present invention, aromatic amine R 1(NH 2) 3first react in solvent with polylactide, reaction mechanism is:
Wherein, be
Above-mentioned reaction is carried out in solvent, described solvent is the conventional all kinds of SOLVENTS of those skilled in the art, for example can be selected from N, dinethylformamide (DMF), N, one or more in N-N,N-DIMETHYLACETAMIDE (DMAc), dimethyl sulfoxide (DMSO), tetramethylene sulfone, dioxane, METHYLPYRROLIDONE (NMP), NVP, meta-cresol, benzene,toluene,xylene, tetrahydrofuran (THF), but be not limited to this.
Preparation in accordance with the present invention, then dianhydride and above-mentioned reaction product continue to react, and reaction mechanism now comprises following three classes according to the different sorts of dianhydride:
In the present invention, described aromatic amine R 1(NH 2) 3with the mol ratio of polylactide, dianhydride be 1:0.8～1.2:0.98～3.15.Under preferable case, the reaction times is 2～12h.
As a kind of preferred implementation of the present invention, be also included in and in reaction process, control the step that the viscosity of reaction system is 10000-100000CP.In reaction process, control for further improving the transformation efficiency (improving imide rate) of above-mentioned reaction, being also included in the step that the solid content of reaction system is 10-60wt%.
As previously mentioned, R 1be preferably now corresponding aromatic amine is three (4-aminophenyl) (compound shown in formula V).R 2be preferably now corresponding dianhydride is 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, and its structure is as shown in the formula shown in VII.
In the preparation method of polyimide resin provided by the invention, by synthesis material (is comprised to aromatic amine R 1(NH 2) 3, polylactide and dianhydride) structure carry out preferably, while ensureing reaction, there is higher imide rate.
Finally, the invention provides a kind of polyimide foam, described polyimide foam is by compressing tablet after polyimide resin provided by the invention is pulverized, and then foamable obtains.
The step of described foamable is those skilled in the art's common practise.As previously mentioned, the second-order transition temperature of polyimide resin that the present invention improves is more than 300 DEG C, polyimide resin generation softening transform when preventing from foaming, and therefore the temperature of foamable is unsuitable too high.Under preferable case, the step of described foamable comprises: first preheating 10～30min at 80～120 DEG C, at 150～180 DEG C, heat 3～15min again, then in 30min, be warming up to 300～350 DEG C and keep 5～25min, finally in 10min, be warming up to 380～400 DEG C and keep 5～25min, obtain described polyimide foam.
In foaming process, polyimide resin generation thermolysis, produces rare gas element, thereby in resin structure, forms equally distributed bubble structure, and in this bubble structure, rear extended meeting is filled by air, obtains described polyimide foam.Because air is the material that specific inductivity is minimum, so the specific inductivity of the Polyimide foams obtaining is also lower.The density of described polyimide foam is 0.03-0.10g/cm3, and relative permittivity is less than 3.0.
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.Embodiment is that in comparative example, the raw material that adopts is all commercially available.
Embodiment 1
(1) solvent DMF that accurately takes 350mL is placed in there-necked flask, add the aromatic amine (TAPA) of 28.55g, reflux 1h, then add the dianhydride (pyromellitic acid anhydride) of 21.46g and the polylactide (molecular weight 1962 of 177.21g, be n=27), the mol ratio that is aromatic amine, polylactide and dianhydride is 1:0.9:1, reaction 4h.Then underpressure distillation, except desolventizing, continues vacuum-drying, obtains the faint yellow polyimide resin solid of the present embodiment, is designated as S1, and it contains the structural unit shown in formula I, wherein R 1for x is n=27.
(2) S1 is pulverized, and be at room temperature pressed into thin slice, preheating 30min at 120 DEG C, at 180 DEG C, heat 5min again, in 30min, be warming up to 330 DEG C and keep 10min, finally in 10min, be warming up to 400 DEG C and keep 10min, obtain the polyimide foam S10 of the present embodiment.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare polyimide resin S2 and the polyimide foam S20 of the present embodiment, difference is:
In step (1), adopt as the pyromellitic acid anhydride in the dianhydride alternate embodiment 1 of the present embodiment, and the mol ratio of TAPA, polylactide (molecular weight is 1962, i.e. n=27) and dianhydride is 1:0.9:1.2;
The polyimide resin S2 obtaining by above-mentioned steps, obtains it and contains the structural unit shown in formula II, wherein R 1for x is n=27.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare polyimide resin S3 and the polyimide foam S30 of the present embodiment, difference is:
In step (1), adopt and R 2for as the pyromellitic acid anhydride in the dianhydride alternate embodiment 1 of the present embodiment, and the mol ratio of TAPA, polylactide (molecular weight is 1962, i.e. n=27) and dianhydride is 1:0.9:3;
The polyimide resin S3 obtaining by above-mentioned steps, obtains it and contains the structural unit shown in formula III, wherein R 1for x is n=27, R 2for
Embodiment 4
Adopt the method identical with embodiment 1 to prepare polyimide resin S4 and the polyimide foam S40 of the present embodiment, difference is:
In step (1), aromatic amine R 1(NH 2) 3middle R 1for dianhydride structural formula is and R 2for aromatic amine, polylactide (molecular weight is 1458, i.e. n=20) are 1:1:1 with the mol ratio of dianhydride;
The polyimide resin S4 obtaining by above-mentioned steps, obtains it and contains the structural unit shown in formula III, wherein R 1for x is n=20, R 2for
Embodiment 5
Adopt the method identical with embodiment 1 to prepare polyimide resin S5 and the polyimide foam S50 of the present embodiment, difference is:
In step (1), aromatic amine R 1(NH 2) 3middle R 1for dianhydride structural formula is and R 2for aromatic amine, polylactide (molecular weight is 3618, i.e. n=50) are 1:1:2.5 with the mol ratio of dianhydride;
The polyimide resin S5 obtaining by above-mentioned steps, obtains it and contains the structural unit shown in formula III, wherein R 1for x is n=50, R 2for
Comparative example 1
330g Virahol and 100g methane amide are joined in the mixture being made up of 5700g methacrylic acid, 4380g methacrylonitrile and 31g propyl methacrylate as whipping agent, by this mixture at 40 DEG C being of a size of polymerization 68h in the sheet glass of 50*50cm and chamber that the thick edge seal thing of 18.5mm forms by two.Polymerisate stands the heating schedule 32h from 32 DEG C to 115 DEG C subsequently, completes final polyreaction; Then foamable 2h25min at 205 DEG C.
By above-mentioned steps, obtain the polyimide foam DS10 of this comparative example.
Performance test
(1) density measurement
With reference to GB1033 plastic density and relative density testing method, adopt pycnometric method to test polyimide foam S10-S50 and DS10.
(2) specific inductivity
With reference to GB/T1408.1 insulating material electrical strength test method, adopt dielectrometer to test polyimide foam S10-S50 and DS10.
(3) mechanical property
With reference to GB/T1040 plastic tensile method for testing performance, GB/T9341 plastics bend test method, adopts electronic universal tester to test polyimide foam S10-S50 and DS10.
Test result is as shown in table 1.
Table 1
Can find out from the test result of upper table 1, polyimide foam S10-S50 density provided by the invention is 0.032～0.908g/cm 3, specific inductivity, lower than 3.0, has good mechanical property simultaneously, is obviously better than the foam sample DS10 of comparative example, and therefore its work-ing life is also corresponding longer.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (10)

1. a polyimide resin, is characterized in that, contains the structural unit shown in formula I, formula II or formula III in described polyimide resin:
Wherein, X is n is 20～50 integer;
R 1for or
R 2be selected from any one in O, S or lower array structure:
2. polyimide resin according to claim 1, is characterized in that, the number-average molecular weight of described polyimide resin is 70000～500000.
3. polyimide resin according to claim 1, is characterized in that, R 1for r 2for
4. the preparation method of polyimide resin claimed in claim 1, is characterized in that, comprises R 1(NH 2) 3, polylactide, dianhydride add in solvent, after reaction, except desolventizing, obtains described polyimide resin;
Wherein, described dianhydride is or
5. preparation method according to claim 4, it is characterized in that, described solvent is selected from N, one or more in dinethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), tetramethylene sulfone, dioxane, METHYLPYRROLIDONE, NVP, meta-cresol, benzene,toluene,xylene, tetrahydrofuran (THF).
6. preparation method according to claim 4, is characterized in that, R 1(NH 2) 3with the mol ratio of polylactide, dianhydride be 1:0.8～1.2:0.98～3.15, the time of reaction is 2～12h.
7. preparation method according to claim 4, is characterized in that, is also included in and in reaction process, controls the step that the viscosity of reaction system is 10000-100000CP.
8. according to the preparation method described in claim 4 or 7, it is characterized in that, be also included in and in reaction process, control the step that the solid content of reaction system is 10-60wt%.
9. a polyimide foam, is characterized in that, described polyimide foam is by compressing tablet after polyimide resin claimed in claim 1 is pulverized, and then foamable obtains.
10. polyimide foam according to claim 9, it is characterized in that, the step of described foamable comprises: first preheating 10～30min at 80～120 DEG C, at 150～180 DEG C, heat 3～15min again, then in 30min, be warming up to 300～350 DEG C and keep 5～25min, finally in 10min, be warming up to 380～400 DEG C and keep 5～25min, obtain described polyimide foam.
CN201310066152.7A 2013-02-28 2013-02-28 A kind of polyimide resin and preparation method thereof and a kind of polyimide foam Active CN104017212B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101107291A (en) * 2005-01-21 2008-01-16 三菱瓦斯化学株式会社 Polyimide resin, polyimide film, and polyimide laminate
CN102267940A (en) * 2011-05-31 2011-12-07 湖北大学 Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101107291A (en) * 2005-01-21 2008-01-16 三菱瓦斯化学株式会社 Polyimide resin, polyimide film, and polyimide laminate
CN102267940A (en) * 2011-05-31 2011-12-07 湖北大学 Synthesis of triamine containing symmetrical triaryl pyridine structure and hyperbranched polyimide thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHA-WEN CHANG等: ""Novel Organosoluble Aromatic Polyimides Bearing Pendant"", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 *
YOSHLYUKL OISHI等: ""Preparation and Properties of Novel Soluble Aromatic Polyimides from 4,4-Diaminotriphenylamine and Aromatic Tetracarboxylic Dianhydrides"", 《JOURNAL OF POLYMER SCIENCE》 *

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