CN101392057A - Method for preparing crystalline thermoplastic polyimide moulding powder - Google Patents
Method for preparing crystalline thermoplastic polyimide moulding powder Download PDFInfo
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- CN101392057A CN101392057A CNA2008100513721A CN200810051372A CN101392057A CN 101392057 A CN101392057 A CN 101392057A CN A2008100513721 A CNA2008100513721 A CN A2008100513721A CN 200810051372 A CN200810051372 A CN 200810051372A CN 101392057 A CN101392057 A CN 101392057A
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Abstract
The invention pertains to the field of polymer material, in particular to a preparation technology of novel polyimide molding powder. The materia has wide application in the aspect of thermoplastic material with high performance. Under the protection of nitrogen gas, a dianhydride monomer and one or two diamine monomers are mixed and dissolved in a solvent and the solid content of the solution ranges from 5 percent to 40 percent, and then the mixture is stirred at room temperature for 2 hours to 24 hours to obtain a polyamide acid solution; then a water-borne solvent is added into the system while the volume of the water-borne accounts for 10 percent to 60 percent of the used solvent; stirring is carried out under the condition of temperature rise, and backflow with water is maintained for 2 hours to 24 hours. After water in the system is removed completely, heating backflow is carried out for 2 hours to 12 hours; and then the solvent in a distilling system is condensed and filtered to obtain a product. After washing, the product is dried in a vacuum oven at 100 DEG C to 300 DEG C to obtain novel thermoplastic polyimide molding powder material combining low processing molding temperature and excellent performances of calorifics and mechanics.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of technology of preparing of new type polyimide molding powder, this material has aspect high performance thermoplastic widely to be used.
Background technology
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.These plastics are generally classified according to working method, can be divided into two classes, and a class is the thermoset engineering plastics, and another kind of is thermoplastic engineering plastic.The thermoset engineering plastics have higher use temperature, but have certain difficulty when the foundry goods of fixed processing size shape; Thermoplastic engineering plastic has excellent processing characteristics, but use temperature is lower, and relative processing temperature is then higher.Polyimide material commonly used adopts the polyamic acid of liquid form further to process as intermediate more, is unfavorable for storing, and in succession the performance that evaporating solvent stays in the hot imidization process pore usually reduces product that adds.And the polyimide of powder state is commonly called as the molding powder, is easy to be stored in transportation, can be by mold pressing, extrude or inject the block materials that is processed into plate, sheet, bar and different shape complexity, and solvent-free existence helps optimizing complete processing and enhances product performance.
Summary of the invention
The objective of the invention is to prepare a kind of novel thermoplastic polyimide molding powder material and preparation method thereof.The characteristics of this patent:
(1) the present invention selects by different ratios blended diamines and a kind of dianhydride random copolymerization (or the random copolymerization of blended dianhydride and a kind of diamines is reacted in varing proportions).
(2) polyimide preparation involved in the present invention comprises following two steps: preparation two portions of the synthetic and polyimide molding powder of polyamic acid.
Polyimide is to be raw material with diamines and dianhydride, with strong polar aprotic solvent such as N, and N`-dimethyl formamide (DMF), N, N`-N,N-DIMETHYLACETAMIDE (DMAc), N-methyl isophthalic acid-pyrrolidone (NMP) etc. are as solvent, and its structure and preparation method are:
N represents mole number, 0≤n≤1.
Wherein Ar1 is:
Wherein Ar2, Ar3 can be identical, also can be inequality, for:
The preparation method of molding powder is as follows:
Under the nitrogen protection, get under a kind of dianhydride monomer induction stirring and be dissolved in the solvent, slowly add diamine monomer then, diamines and dianhydride mol ratio be 0.1～5:1, 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%, solid content is 5～40% in the solution, stirring at room is 2～24 hours then, obtains light yellow transparent thick liquid, i.e. polyamic acid solution;
Then, add the band water solvent in above-mentioned system, the volume of band water solvent is 10%～60% of the solvent that uses; Heat up stirring down, reflux and be with water 2～24 hours, reheat refluxed 2～12 hours behind the water in the most system of band; Concentrate the solvent in the distillation system then, suction filtration obtains product, and product washing back 100～300 degrees centigrade of oven dry down, obtains yellow powder in vacuum drying oven, be crystalline thermoplastic polyimide moulding powder.
Diamine monomer 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, 1,3,-(4-amino-benzene oxygen) benzene or benzene generation 1,4 ,-(4-amino-benzene oxygen) benzene, can be wherein a kind of, also can be wherein any two kinds combination, further, the molar ratio that a kind of diamine monomer accounts for hybrid diamine is 10～90%.
Dianhydride monomer 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 or 2,3 ', 2,3 '-BPDA.
Solvent described in the aforesaid method is N-Methyl pyrrolidone (NMP), N, dinethylformamide (DMF) or N,N-dimethylacetamide (DMAc), or two or three mixed solvent of above-mentioned solvent.
Band water solvent described in the aforesaid method is toluene, dimethylbenzene, oil of mirbane or meta-cresol.
Cleaning solvent described in the aforesaid method is methyl alcohol, ethanol or water, or two or three mixed solvent of above-mentioned cleaning solvent.
The present invention removes the water that generates in the imidization process and the solvent in the polyamic acid system by the system of the band water that heats up, and obtains a kind of novel thermoplastic polyimide molding powder material of taking into account low machine-shaping temperature and calorifics, good mechanical performance.
Description of drawings
The infrared spectrogram of the polyimide molding powder that obtains of Fig. 1: embodiment 1～embodiment 11;
The DSC scintigram of the polyimide molding powder that obtains of Fig. 2: embodiment 1～embodiment 11.
Fig. 1 be 11 kinds of different diamines ratios (4,4 '-diaminodiphenyl ether (4,4 '-ODA) and 1,3-(4-Amino-benzene oxygen) benzene (the TPER)) infrared spectrogram of polyimide molding powder. We can see from figure At 1780cm-1The distinctive absworption peak of polyimides, 2900-3200cm have appearred in the place-1The polyamic acid spy at place Levy the peak and disappear, confirmed the existence of aromatic imide group, illustrate that simultaneously the imidization degree is more complete.
Fig. 2 is the DSC scintigram of 11 kinds of different diamines ratio polyimide molding powders. Therefrom we can See glass transition temperature Tg between 200 ℃～260 ℃, proved that this polyimide molding powder has kept Good hot property has higher serviceability temperature. But along with the variation of two kinds of diamines ratios, the absworption peak of melting Position and the variation of intensity pests occurrence rule have illustrated the variation along with two kinds of diamines ratios, and be corresponding, the molding powder Variation has all taken place in crystalline texture, will produce very big impact to its hot property.
To sum up, structure and thermal property test by film is carried out prove that our prepared random copolymerization is poly-Acid imide molding powder thermal property is fine, and possesses special crystal property, have good application may with prospect.
Embodiment
Embodiment 1:
Under mechanical stirring, under the nitrogen atmosphere, in three-necked bottle, add 2.98g (0.01mol) 3,3 ', 4,4 '-BPDA (s-BPDA) is dissolved in 52ml N-methyl isophthalic acid-pyrrolidone (NMP), slowly add 2.94g (0.01mol) 1 again, 3-(4-amino-benzene oxygen) benzene (TPER), stirring at room 4 hours obtains light yellow transparent thick liquid-polyamic acid solution (solid content is 10%).
Then, in system, add 10ml dimethylbenzene, be warming up under 180 ℃ of stirrings, reflux and be with water 2 hours.Band to the greatest extent behind the water in the system, steams dimethylbenzene under 185 ℃, 200 ℃ of following reflux 4 hours, concentrate down at 130 ℃ more then, goes out partial solvent in the system by underpressure distillation.Cooling back suction filtration obtains yellow powder shape product, methyl alcohol and water washing product each three times, and (vacuum tightness obtains molding powder 1 less than-0.1MPa) 150 degrees centigrade of oven dry, and quality is 5.5 grams, and second-order transition temperature is 210 ℃ to place vacuum drying oven.
Embodiment 2:
Method such as embodiment 1, diamines is become 4,4 '-diaminodiphenyl oxide (4,4 '-ODA) 0.2007g (0.001mol) and 1, the mixture of 3-(4-amino-benzene oxygen) benzene (TPER) 2.628g (0.009mol) (ratio of two kinds of diamines is 1:9), the step of continuation embodiment 1 obtains molding powder 2, quality is 5.48 grams, and second-order transition temperature is about about 210 ℃.
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 molding powder 3, and quality is 5.39 grams.Two obvious melting peaks appear in the DSC curve.
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 molding powder 4, and quality is 5.30 grams.Three obvious melting peaks appear in the DSC curve.
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 molding powder 5, and quality is 5.22 grams.The glass transition temperature is about 210 ℃
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 molding powder 6, and quality is 5.13 grams.Second-order transition temperature is about about 230 ℃.
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 molding powder 7, and quality is 5.04 grams.Second-order transition temperature is about about 226 ℃.
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 molding powder 8, and quality is 4.96 grams.Second-order transition temperature is about about 248 ℃.
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 molding powder 9, and quality is 4.87 grams.Second-order transition temperature is about about 251 ℃.
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 molding powder 10, and quality is 4.78 grams.Second-order transition temperature is 260 ℃.
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 molding powder 11, and quality is 5.57 grams.The glass transition temperature is about 270 ℃.
Embodiment 12:
Method such as embodiment 1 change dianhydride into pyromellitic acid dianhydride (PMDA), change two kinds of diamines into benzene respectively for 1,4 ,-(4-amino-benzene oxygen) benzene and 1,3, and-(4-amino-benzene oxygen) benzene, solvent is changed to N, dinethylformamide (DMF).Wherein the amount of pyromellitic acid dianhydride is 0.01mol (2.1812g), the amount of two kinds of diamines is respectively 0.00891mol (3.2827g), 0.00099mol (0.2894g), and the mol ratio of acid anhydride and amine is that the mol ratio of 100:99, two kinds of diamines is 9:1, obtain molding powder 12, quality is 5.75 grams.Second-order transition temperature is about about 276 ℃.
Embodiment 13:
Method such as embodiment 1 change dianhydride into pyromellitic acid dianhydride (PMDA), make into two kinds of diamines a kind of: benzene generation 1,4, and-(4-amino-benzene oxygen) benzene, solvent is changed to N, dinethylformamide (DMF).Wherein the amount of pyromellitic acid dianhydride is 0.01mol (2.1812g), and benzene is for 1,4, and the amount of-(4-amino-benzene oxygen) benzene is 0.0098mol (3.6106g), and the mol ratio of acid anhydride and amine is 100:98, obtains molding powder 13, and quality is 3.79 grams.Second-order transition temperature is about about 276 ℃.
Claims (7)
1, the preparation method of crystalline thermoplastic polyimide moulding powder, its step is as follows:
A: under the nitrogen protection, get under a kind of dianhydride monomer induction stirring and be dissolved in the solvent, slowly add diamine monomer then, diamines and dianhydride mol ratio be 0.1～5:1, 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%, and solid content is 5～40% in the solution, and stirring at room is 2～24 hours then, obtain light yellow transparent thick liquid, i.e. polyamic acid solution;
B: then, add the band water solvent in above-mentioned system, the volume of band water solvent is 10%～60% of the solvent that uses; Heat up stirring down, reflux and be with water 2～24 hours, reheat refluxed 2～12 hours behind the water in the most system of band; Concentrate the solvent in the distillation system then, suction filtration obtains product, and product washing back 100～300 degrees centigrade of oven dry down, obtains yellow powder in vacuum drying oven, be crystalline thermoplastic polyimide moulding powder.
2, the preparation method of crystalline thermoplastic polyimide moulding powder as claimed in claim 1 is characterized in that: diamine monomer 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.
3, the preparation method of crystalline thermoplastic polyimide moulding powder as claimed in claim 1, it is characterized in that: dianhydride monomer is 3,3 ', 4,4 '-BPDA, pyromellitic acid dianhydride (PMDA), phenyl ether tetracarboxylic dianhydride (ODPA), benzophenone tetracarboxylic dianhydride (BTDA), 2,3 ', 3,4 '-BPDA or 2,3 ', 2,3 '-BPDA.
4, the preparation method of crystalline thermoplastic polyimide moulding powder as claimed in claim 1, it is characterized in that: solvent is N-Methyl pyrrolidone, N, dinethylformamide or N,N-dimethylacetamide, or two or three mixed solvent of above-mentioned solvent.
5, the preparation method of crystalline thermoplastic polyimide moulding powder as claimed in claim 1 is characterized in that: the band water solvent is toluene, dimethylbenzene, oil of mirbane or meta-cresol.
6, the preparation method of crystalline thermoplastic polyimide moulding powder as claimed in claim 1 is characterized in that: cleaning solvent is methyl alcohol, ethanol or water, or two or three mixed solvent of above-mentioned cleaning solvent.
7, as the preparation method of any one described crystalline thermoplastic polyimide moulding powder of claim 1～6, it is characterized in that: to account for the molar ratio of hybrid diamine be 10～90% to a kind of diamine monomer in the mixture of two kinds of diamines.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108124A (en) * | 2010-12-30 | 2011-06-29 | 上海市合成树脂研究所 | Preparation method of meltable polyimide moulding compound |
| WO2013143288A1 (en) * | 2012-03-26 | 2013-10-03 | 长春高琦聚酰亚胺材料有限公司 | Preparation method of polyimide |
| CN104710789A (en) * | 2015-03-16 | 2015-06-17 | 吉林大学 | Preparation method of polyimide molding powder |
| CN105838239A (en) * | 2016-04-13 | 2016-08-10 | 中国科学院宁波材料技术与工程研究所 | Polyimide composite coating and preparation method thereof and application thereof |
| CN107936248A (en) * | 2017-11-27 | 2018-04-20 | 长沙新材料产业研究院有限公司 | A kind of preparation method of polyimide resin |
| CN111533907A (en) * | 2020-06-28 | 2020-08-14 | 合肥工业大学 | Preparation method of heat-resistant polyimide molding powder containing benzimidazole structure |
| WO2023164085A1 (en) * | 2022-02-23 | 2023-08-31 | Honeywell International Inc. | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
-
2008
- 2008-11-03 CN CNA2008100513721A patent/CN101392057A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108124A (en) * | 2010-12-30 | 2011-06-29 | 上海市合成树脂研究所 | Preparation method of meltable polyimide moulding compound |
| WO2013143288A1 (en) * | 2012-03-26 | 2013-10-03 | 长春高琦聚酰亚胺材料有限公司 | Preparation method of polyimide |
| US10414868B2 (en) | 2012-03-26 | 2019-09-17 | Changchun Hipolyking Co., Ltd. | Preparation method of polyimide |
| CN104710789A (en) * | 2015-03-16 | 2015-06-17 | 吉林大学 | Preparation method of polyimide molding powder |
| CN105838239A (en) * | 2016-04-13 | 2016-08-10 | 中国科学院宁波材料技术与工程研究所 | Polyimide composite coating and preparation method thereof and application thereof |
| CN107936248A (en) * | 2017-11-27 | 2018-04-20 | 长沙新材料产业研究院有限公司 | A kind of preparation method of polyimide resin |
| CN111533907A (en) * | 2020-06-28 | 2020-08-14 | 合肥工业大学 | Preparation method of heat-resistant polyimide molding powder containing benzimidazole structure |
| WO2023164085A1 (en) * | 2022-02-23 | 2023-08-31 | Honeywell International Inc. | Foamable thermoplastic compositions, thermoplastic foams and methods of making same |
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