CN101392066A - Method for preparing hemicrystalline and thermoplastic polyimide film - Google Patents
Method for preparing hemicrystalline and thermoplastic polyimide film Download PDFInfo
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- CN101392066A CN101392066A CNA2008100513736A CN200810051373A CN101392066A CN 101392066 A CN101392066 A CN 101392066A CN A2008100513736 A CNA2008100513736 A CN A2008100513736A CN 200810051373 A CN200810051373 A CN 200810051373A CN 101392066 A CN101392066 A CN 101392066A
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Abstract
The invention pertains to the field of polymer materials and more particularly relates to a preparation method of a semi-crystalline and thermoplastic polyimide film. The polyimide film prepared by the method has special crystallization performance, good potential application and prospect and wide application in the aspect of thermoplastic material with high performance. The method of the technology includes the following steps: firstly, two diamines are mixed and then dissolved in a solvent to obtain a transparent solution, wherein, the mole ratio between one of the two diamines and the mixed diamines ranges from 0 percent to 100 percent. Secondly, dianhydride is added slowly and the mol ratio between the dianhydride and the mixed diamines is 0.1:1 to 5:1, and the solid content of the solution is 5 percent to 40 percent and then the solution is stirred at the room temperature for 2h to 24h to obtain light yellow, transparent and viscous liquid, namely, the polyamide acid solution; a film is prepared by a method that a drawknife is used for knife-coating on a backing plate, and then the backing plate and the film are put into an oven under the conditions of the temperature of 20 DEG C to 400 DEGC and the vacuum degree of less than 0.1MPa for the treatment of temperature programming to obtain the polyimide film.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to the preparation method of a kind of hemicrystalline and thermoplastic polyimide film.The polyimide film of this method preparation has aspect high performance thermoplastic widely to be used.
Background technology
Along with science and technology development, people are more and more higher to the requirement of material, and general-purpose plastics can not satisfy the increasingly extensive and urgent requirement of people, and this makes some high molecular scholars' work develop towards the polymkeric substance direction that preparation has excellent use properties.High performance engineering plastics is the special plastic of the excellent performance of being used widely in various engineerings field that grows up in the sixties.Wherein polyimide is with its good thermotolerance, radiation resistance, resistance to chemical reagents and good comprehensive mechanical performance, electric property and be widely used in aerospace, field of electronics.Many studies show that, crystallinity TPI often has better solvent resistance than amorphism TPI, shows higher mechanical property conservation rate more than the Tg temperature, and therefore development and exploitation hemicrystalline thermoplastic polyimide become and study one of focus in the last few years.
Structure, chain length difference on the thermoplastic polymer molecules main chain, the crystal property of the direct impact polymer of meeting, therefore the variation meeting of repeating unit arrangement mode exerts an influence to polymer crystallization and melting behavior and crystalline texture on the molecular chain, thereby thermal characteristics is exerted an influence.The present invention is based on this design philosophy, with blended diamines and dianhydride random copolymerization in varing proportions, because the reactive behavior difference of diamine monomer, repeat unit structure is different with length in the random copolymers, therefore resulting polymkeric substance has different crystal properties, and then obtain a kind of not only low to the machine-shaping temperature requirement, the more excellent novel thermoplastic polyimide material of performance simultaneously.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing hemicrystalline and thermoplastic polyimide film.
The method of the invention is characterized in:
(1) the present invention selects by two kinds of diamines of different ratios blended and a kind of dianhydride random copolymerization;
(2) polyimide preparation involved in the present invention comprises synthesizing and temperature programming hot imidization two portions of polyamic acid.
With diamines and dianhydride is raw material, and as solvent, the preparation feedback formula of polyimide is as follows with strong polar aprotic solvent such as DMF, DMAc, NMP etc.:
N represents mole number, 0≤n≤1;
Wherein Ar1 is:
Wherein Ar2, Ar3 can be identical, also can be inequality, for:
Or
(3) among the present invention because monomer reaction is active different, the random copolymers of gained is along with the variation of the ratio of different diamine monomers, the repeating unit arrangement mode changes on the molecular chain, thereby polymer crystallization, crystalline structure and melting behavior are exerted an influence, make the transparency of film have clear regularity, thermal characteristics and mechanical property also present regular the variation.
Described hemicrystalline of this patent and thermoplastic polyimide film preparation method are as follows:
Diamines is dissolved in (induction stirring) solvent and obtains clear solution, slowly adding is the dianhydride of 0.1～5:1 with the hybrid diamine mol ratio again, diamines can be a kind of diamine monomer, it also can be the mixture of two kinds of diamine monomers, when being the mixture of two kinds of diamine monomers, the molar ratio that wherein a kind of diamine monomer accounts for hybrid diamine is 1～99%, and solid content is 5～40% in the solution, then stirring at room 2～24h obtains light yellow transparent thick liquid-polyamic acid solution;
The method that goes up with the scraper blade coating in back up pad (as sheet glass, iron plate, steel plate, alloy sheets etc.) prepares film (scraper is the instrument that a kind of commonly used being used for prepares film), then back up pad and film are put in the lump baking oven and handled less than temperature programming under the-0.1MPa condition, then obtain Kapton in 20 ℃～400 ℃, vacuum tightness.
Further, the process that temperature programming is handled is, in a conventional oven, under 50～70 ℃ of conditions, handled 1～3 hour, under 80～120 ℃ of conditions, handled 1～3 hour, under 130～160 ℃ of conditions, handled 1～3 hour, under 170～220 ℃ of conditions, handled 1～3 hour; In vacuum drying oven, under 230～270 ℃ of conditions, handled 1～3 hour then, under 280～320 ℃ of conditions, handled 1～3 hour, under 330～370 ℃ of conditions, handled 1～3 hour.
Diamines described in the aforesaid method is 3,3 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide or 1,3 ,-(3-amino-benzene oxygen) benzene, 1,4 ,-(4-amino-benzene oxygen) benzene, 1,4,-(3-amino-benzene oxygen) benzene and 1,3 ,-(4-amino-benzene oxygen) benzene, benzene are for 1,4 ,-(4-amino-benzene oxygen) benzene, wherein combination in twos gets final product arbitrarily, further, to account for the monomeric molar ratio of hybrid diamine be 10～90% to a kind of diamine monomer.
Dianhydride described in the aforesaid method is 3,3 ', 4,4 '-BPDA, pyromellitic acid dianhydride (PMDA), phenyl ether tetracarboxylic dianhydride (ODPA), benzophenone tetracarboxylic dianhydride (BTDA), 2,3 ', 3,4 '-BPDA, 2,3 ', 2,3 '-BPDA.
Solvent described in the aforesaid method is N, dinethylformamide (DMF), N,N-dimethylacetamide (DMAc) or N-Methyl pyrrolidone (NMP), or two or three mixed solvent wherein.
Description of drawings
The infrared spectrogram of the Kapton that obtains of Fig. 1: embodiment 1～embodiment 11;
The ultraviolet of the Kapton that obtains of Fig. 2: embodiment 1～embodiment 11 sees through figure;
The DSC scintigram of the Kapton that obtains of Fig. 3: embodiment 1～embodiment 11;
The TGA scintigram of the Kapton that obtains of Fig. 4: embodiment 1～embodiment 11;
The XRD scintigram of the Kapton that Fig. 5: embodiment 1, embodiment 2, embodiment 5 and embodiment 6 obtain.
Fig. 1 is the infrared spectrogram of 11 kinds of different proportion diamines Kaptons. We can see through after the temperature programming imidization, 2900-3200cm-1The polyamic acid characteristic peak at place disappears, 1780cm-1The distinctive absworption peak of polyimides has appearred in the place, has confirmed the existence of aromatic imide group, illustrates that simultaneously the imidization degree is more complete.
Fig. 2 is that the ultraviolet of 11 kinds of different proportion diamines Kaptons sees through figure. When wavelength was 800nm, we can see that the transparency of 11 kinds of films is different by transmitance, and this causes owing to its internal crystal structure is different.
Fig. 3 is the DSC scintigram of 11 kinds of different proportion diamines Kaptons. We can see glass transition temperature Tg between 200 ℃～260 ℃, have proved that this Kapton has kept good hot property, and higher serviceability temperature is arranged. But along with the variation of two kinds of diamines ratios, the absworption peak position of melting and the variation of intensity pests occurrence rule have illustrated the variation along with two kinds of diamines ratios, and variation has all occured the crystalline texture of respective films, will have a huge impact its hot property.
Fig. 4 is the TGA scintigram of 11 kinds of different proportion diamines Kaptons. We can see that the temperature that 11 kinds of film thermal decompositions begin is about about 450 ℃, and temperature is all greater than 540 ℃ during 5% thermal weight loss, so they all have excellent heat endurance.
Fig. 5 is the XRD scintigram of the Kapton that obtains of embodiment 1, embodiment 2, embodiment 5 and embodiment 6. Among embodiment 1 and the embodiment 2, two kinds of diamines ratios differ large (being respectively 0:10 and 1:9),, their XRD curve is about 16 degree places at 2 θ obvious spike, and this has illustrated that there is crystalline texture in these film inside; And in embodiment 5 and embodiment 6, two kinds of diamines ratios close (being respectively 4:6 and 5:5) be can't see obvious spike on the XRD curve, illustrate not have obvious crystalline texture in these films, and other embodiment also meet above-mentioned rule. These phenomenons and our design philosophy match because the reactivity of diamine monomer is different, when two kinds of diamines ratios not simultaneously, repeat unit structure is different with length in the random copolymer, so resulting polymer has different crystal properties.
To sum up, by film is carried out the test of calorifics and mechanical property, prove that we prepared random copolymerization polyimide film mechanics and thermal property are fine, and possess special crystal property, have good application may with prospect.
Embodiment
Embodiment 1:
On electromagnetic mixing apparatus, add 1 in the beaker, 3-(4-amino-benzene oxygen) benzene (TPER) 2.94g (0.01mol) is dissolved in 52ml N,N-dimethylacetamide (DMAc) and obtains colourless transparent liquid (solid content is 10%), slowly adds 3 again, 3 ', 4,4 '-BPDA (s-BPDA) 2.98g, (0.01mol), then stirring at room is 4 hours, obtains light yellow transparent thick liquid-polyamic acid solution.
On sheet glass, scrape 500 μ m thick films with scraper, put into a conventional oven: 60 ℃/1 hour, 100 ℃/1 hour, 150 ℃/1 hour, 180 ℃/1 hour, put into vacuum drying oven again: vacuum condition (0.1MPa) following 250 ℃/1 hour, 300 ℃/1 hour, carry out temperature programming in 350 ℃/1 hour and handle, then obtain the film 1 that thickness is about 50 μ m.
Embodiment 2:
Method such as embodiment 1, add 4 in the beaker, 4 '-diaminodiphenyl oxide (4,4 '-ODA) 0.2007g (0.001mol) and 1,3-(4-amino-benzene oxygen) benzene (TPER) 2.628g (0.009mol) (molar ratio of two kinds of diamines is 1:9) is dissolved in 51ml N, N-N,N-DIMETHYLACETAMIDE (DMAc) obtains colourless transparent liquid (solid content is 10%), slowly add 3 again, 3 ', 4,4 '-BPDA (s-BPDA) 2.98g (0.01mol) continues the step of embodiment 1 afterwards, obtain film 2, thickness is about 44 μ m.
Embodiment 3:
Method such as embodiment 1, with two kinds of diamines 4, (4,4 '-ODA) and 1, the ratio of 3-(4-amino-benzene oxygen) benzene (TPER) becomes 2:8 to 4 '-diaminodiphenyl oxide, obtains film 3.As shown in Figure 1, two obvious melting peaks appear in the DSC curve, and thickness is about 43 μ m.
Embodiment 4:
Method such as embodiment 1, with two kinds of diamines 4, (4,4 '-ODA) and 1, the ratio of 3-(4-amino-benzene oxygen) benzene (TPER) becomes 3:7 to 4 '-diaminodiphenyl oxide, obtains film 4.Three obvious melting peaks appear in the DSC curve, and thickness is about 41 μ m.
Embodiment 5:
Method such as embodiment 1, with two kinds of diamines 4, (4,4 '-ODA) and 1, the ratio of 3-(4-amino-benzene oxygen) benzene (TPER) becomes 4:6 to 4 '-diaminodiphenyl oxide, obtains film 5, and thickness is about 42 μ m.
Embodiment 6:
Method such as embodiment 1, with two kinds of diamines 4, (4,4 '-ODA) and 1, the ratio of 3-(4-amino-benzene oxygen) benzene (TPER) becomes 5:5 to 4 '-diaminodiphenyl oxide, obtains film 6, and thickness is about 45 μ m.
Embodiment 7:
Method such as embodiment 1, with two kinds of diamines 4, (4,4 '-ODA) and 1, the ratio of 3-(4-amino-benzene oxygen) benzene (TPER) becomes 6:4 to 4 '-diaminodiphenyl oxide, obtains film 7, and thickness is about 42 μ m.
Embodiment 8:
Method such as embodiment 1, with two kinds of diamines 4, (4,4 '-ODA) and 1, the ratio of 3-(4-amino-benzene oxygen) benzene (TPER) becomes 7:3 to 4 '-diaminodiphenyl oxide, obtains film 8, and thickness is about 44 μ m.
Embodiment 9:
Method such as embodiment 1, with two kinds of diamines 4, (4,4 '-ODA) and 1, the ratio of 3-(4-amino-benzene oxygen) benzene (TPER) becomes 8:2 to 4 '-diaminodiphenyl oxide, obtains film 9, and thickness is about 42 μ m.
Embodiment 10:
Method such as embodiment 1, with two kinds of diamines 4, (4,4 '-ODA) and 1, the ratio of 3-(4-amino-benzene oxygen) benzene (TPER) becomes 9:1 to 4 '-diaminodiphenyl oxide, obtains film 10, and thickness is about 42 μ m.
Embodiment 11:
Method such as embodiment 1, with two kinds of diamines 4, (4,4 '-ODA) and 1, the ratio of 3-(4-amino-benzene oxygen) benzene (TPER) becomes 10:0 to 4 '-diaminodiphenyl oxide, obtains film 11, and thickness is about 35 μ m.
The mechanical property experimental data of embodiment 1～11 product is as shown in table 1:
Table 1: the measuring mechanical property result of different ratios diamines Kapton
| ODA:TPER | 0:10 | 1:9 | 2:8 | 3:7 | 4:6 | 5:5 | 6:4 | 7:3 | 8:2 | 9:1 | 10:0 |
| Modulus (GPa) | 3.37 | 3.40 | 3.46 | 3.63 | 3.35 | 3.30 | 3.41 | 3.28 | 3.21 | 3.32 | 3.26 |
| Breaking tenacity (MPa) | 125 | 126 | 130 | 133 | 122 | 125 | 135 | 133 | 133 | 147 | 157 |
| Elongation at break (%) | 15 | 7 | 7 | 6 | 17 | 6 | 8 | 33 | 42 | 89 | 90 |
(annotate:. the tensile property of polymeric film is measured by the omnipotent test machine of SHIMADZU AE-1 type.)
Claims (6)
1, hemicrystalline and thermoplastic polyimide film preparation method is characterized in that:
Diamines is dissolved in obtains clear solution in the solvent, slowly adding is the dianhydride of 0.1～5:1 with the hybrid diamine mol ratio again, diamines is the mixture of a kind of diamine monomer or two kinds of diamine monomers, when being the mixture of two kinds of diamine monomers, the molar ratio that wherein a kind of diamine monomer accounts for hybrid diamine is 1～99%, solid content is 5～40% in the solution, and then stirring at room 2～24h obtains light yellow transparent thick liquid-polyamic acid solution;
Method with the scraper blade coating on back up pad prepares film, then back up pad and film is put in the lump baking oven and is handled less than temperature programming under the-0.1MPa condition in 20 ℃～400 ℃, vacuum tightness, then obtains Kapton.
2, hemicrystalline as claimed in claim 1 and thermoplastic polyimide film preparation method, it is characterized in that: it is earlier in a conventional oven that temperature programming is handled, under 50～70 ℃ of conditions, handled 1～3 hour, under 80～120 ℃ of conditions, handled 1～3 hour, under 130～160 ℃ of conditions, handled 1～3 hour, under 170～220 ℃ of conditions, handled 1～3 hour; In vacuum drying oven, under 230～270 ℃ of conditions, handled 1～3 hour then, under 280～320 ℃ of conditions, handled 1～3 hour, under 330～370 ℃ of conditions, handled 1～3 hour.
3, hemicrystalline as claimed in claim 1 and thermoplastic polyimide film preparation method is characterized in that: diamines is 3,3 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, 4,4 '-diaminodiphenyl oxide, 1,3,-(3-amino-benzene oxygen) benzene, 1,4 ,-(4-amino-benzene oxygen) benzene, 1,4,-(3-amino-benzene oxygen) benzene, 1,3 ,-(4-amino-benzene oxygen) benzene or benzene are for 1,4 ,-(4-amino-benzene oxygen) benzene.
4, hemicrystalline as claimed in claim 1 and thermoplastic polyimide film preparation method, it is characterized in that: dianhydride is 3,3 ', 4,4 '-BPDA, pyromellitic acid dianhydride, phenyl ether tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, 2,3 ', 3,4 '-BPDA or 2,3 ', 2,3 '-BPDA.
5, hemicrystalline as claimed in claim 1 and thermoplastic polyimide film preparation method is characterized in that: solvent is N, dinethylformamide, N,N-dimethylacetamide or N-Methyl pyrrolidone, or two or three mixed solvent wherein.
6, as any one described hemicrystalline of claim 1～5 and thermoplastic polyimide film preparation method, it is characterized in that: in the mixture of two kinds of diamine monomers, the molar ratio that a kind of diamines accounts for hybrid diamine is 10～90%.
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| CNA2008100513736A CN101392066A (en) | 2008-11-03 | 2008-11-03 | Method for preparing hemicrystalline and thermoplastic polyimide film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108841003A (en) * | 2018-06-12 | 2018-11-20 | 中国科学院电工研究所 | A kind of polyimide dielectric film and the preparation method and application thereof |
| CN109648970A (en) * | 2018-01-18 | 2019-04-19 | 深圳瑞华泰薄膜科技股份有限公司 | A kind of Kapton of ultralow dielectric loss |
-
2008
- 2008-11-03 CN CNA2008100513736A patent/CN101392066A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109648970A (en) * | 2018-01-18 | 2019-04-19 | 深圳瑞华泰薄膜科技股份有限公司 | A kind of Kapton of ultralow dielectric loss |
| CN108841003A (en) * | 2018-06-12 | 2018-11-20 | 中国科学院电工研究所 | A kind of polyimide dielectric film and the preparation method and application thereof |
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