CN1098878C - Process for preparing high-molecular polyamide ester - Google Patents
Process for preparing high-molecular polyamide ester Download PDFInfo
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- CN1098878C CN1098878C CN98118957A CN98118957A CN1098878C CN 1098878 C CN1098878 C CN 1098878C CN 98118957 A CN98118957 A CN 98118957A CN 98118957 A CN98118957 A CN 98118957A CN 1098878 C CN1098878 C CN 1098878C
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Abstract
The present invention provides a method for preparing high molecular polyesteramide, which comprises: diacid diester which is obtained by the reaction of aromatic dibasic anhydride and monobasic alcohol is acetylized and chlorinated in a solvent with a high melting point; the solid solution of diester and diacid chloride is formed by lowering temperature; the solution of the aprotic polar solvent of the diacid chloride and diamine existing in the form of the solid solution carries out condensation and polymerization reaction between liquid-solid two phases between-5 and-10 DEG C.
Description
The invention belongs to the preparation method of high-molecular polyamide ester.
Polyesteramide (PAE) is a kind of important as precursors (precursor) form of polyimide (PI).(PAA) compares with polyamic acid, and PAE can prepare the more solution of high solids content, and better stability in storage is arranged, and when imidization, molecule interchain imidization do not take place generally.With the PAE solution of flexible chain and the PAE solution blending of stiff chain, during imidization, intermolecular commentaries on classics amidation (transamidation) can not take place, can form flexible chain PI on the molecular level and the matrix material of stiff chain PI well, and improve the performance of two kinds of PI; Another important application of PAE is ester type photosensitive polyimide (ester-type PSPI), ester-type PSPI storge quality is good, solid content is high, be easy to form thick glued membrane, not only be widely used in the microelectronics manufacturing, and be used in the micromechanics manufacturing, forming miniature electroforming mould, is one of very important high-performance photoetching glue.
PAE synthetic generally is the esterification, chloride by dianhydride and finishes with three steps of diamines polycondensation.The preparation side that Chinese patent 97105274.3 discloses a kind of ester type photosensitive polyimide is sent out, and this method is carried out the liquid liquld interfacial polycondensation reaction by the diamines of diester diacid chloride in the organic phase and aqueous phase, obtains polyesteramide.But the water-soluble diamines that can be used as the polycondensation raw material is very limited, and commonly used have only mphenylenediamine and Ursol D, limited the use of this method; Pukun Zhu et al. is published in journal of applied (J of Applied Polymer Science, Vol.55:1111 (1995)) " poly-imido preparation of silica of negative light-sensitive and the characteristic " paper on has been described the solution polycondensation reaction method in a kind of three steps an of still, because the reaction between diacid chloride and the diamines is too fierce, or because hydrolysis reaction easily takes place in diacid chloride, or owing to the diacid chloride monomer is difficult for being purified, during batching, difficulty is accomplished two kinds of mol ratios such as monomeric, make that obtained product PAE molecular weight is very low, the polymer property viscosity of weighing molecular weight standard is lower than 0.16dL/g.Though also some method can be used for synthesizing PAE, is not that the limitation problem is arranged, and is exactly unfavorable factors such as synthetic cost height.For example use dicyclohexyl carbodiimide (DCC), diphenyl (2,3-dihydro-2-thioxo-3-benzoxazo-lyl) condensing agent of phosphonate (DDTBP) and so on makes two acid diesters and diamines be condensed into its limiting viscosity of PAE and generally is no more than 0.65dL/g, and condensing agent is too expensive, should not be used for producing.
The preparation method who the purpose of this invention is to provide a kind of high-molecular polyamide ester.This method is come the PAE of synthetic macromolecule amount by controls reaction speed, inhibition hydrolytic side reactions and " adjusting automatically " function of reaction monomers proportioning.
The object of the present invention is achieved like this, active diester diacid chloride monomer is dispersed in the solvent (as tetramethylene sulfone) of higher melt, form solid solution at low temperatures, as this diester diacid chloride that exists with the solid solution form and the N of diamines, N-N,N-DIMETHYLACETAMIDE (DMAc) Gu or the solution of other aprotic polar solvent carry out liquid--during the reaction of-two alternate solution polycondensations, reaction be along with solid solution in DMAc dissolving gradually and carry out gradually, the active high component of control enters the speed of reactive system effectively, and slows down speed and inhibition hydrolytic side reactions that reaction is carried out; On the other hand, because diacid chloride progresses into reaction system, and once entering reaction system, just complete with diamine reactant at once.Therefore, in the reaction system for some time two kinds monomericly be near the equivalent than regular meeting, promptly regulate monomeric proportioning automatically.So can obtain the high-molecular weight product.
The present invention adopts following component synthesizing polyamides ester.
(1) aromaticity tetracarboxylic dianhydride:
(2) diamine: H
2N-R-NH
2 
(3) monohydroxy-alcohol:
HO-R
*
R
*:-CH
3-CH
2CH
3Or-CH
2CH
2OOCCH=CH
2
The solvent that uses among the present invention is:
(1) high-melting-point solvent: tetramethylene sulfone or sym-trimethylbenzene
(2) aprotic polar solvent: N,N-dimethylacetamide, N, dinethylformamide, N-
N-methyl-2-2-pyrrolidone N-, HMPA
The chlorine hydride absorbent of using among the present invention is: pyridine and triethylamine
Concrete synthesis step is as follows:
Aromatic dianhydride and monohydroxy-alcohol are added in dystectic solvent by one to two molar weight,, obtain the solution of the high-melting-point solvent of two acid diesters 50--65 ℃ of reaction 6-12 hour; In this solution, dripping an amount of SOCl under 10--25 ℃
2After, keep under this temperature and reacted 2-3.5 hour, and at room temperature remove hydrogenchloride and form waste gas of sulfur dioxide and the superfluous SOCl that remains in the system with two hours high vacuum
2, the solution of the high-melting-point solvent of acquisition diester diacid chloride; Cool the temperature to below-15 ℃, make this solution solidifies, obtain to contain the solid solution of diester diacid chloride; To be added on the above-mentioned solid solution with the DMAc solution of the diamines of dianhydride equal molar quantities, keep-5--10 ℃ between stirring reaction 2-3 hour, go out product with ethanol, water precipitation, the limiting viscosity of gained polyesteramide is at 0.60-1.42dL/g.
Because the present invention has adopted the diester diacid chloride that reactive behavior is strong to be dispersed into solid solution, the polycondensation of diacid chloride and diamines is occurred between their liquid, the solid two phase liquid, and carry out gradually with the progressively dissolving of solid solution, controlled the fierce degree of reaction effectively and paid reaction, obtained high-molecular weight PAE with the hydrolysis that has suppressed diacid chloride.When more particularly two acid diesters or diester diacid chloride are difficult for separation and purification, adopt this method, carry out the polycondensation in three steps an of still, more demonstrate its advantage, the limiting viscosity of product P AE is generally at 0.6-1.42dL/g.
Embodiment provided by the invention is as follows:
Embodiment 1:
20.1160g (0.05mol) triphen diether tetracarboxylic dianhydride (HQDPA), 10.1lml (0.25mol) methyl alcohol and 45ml tetramethylene sulfone are added in the 350ml tubular reactor, under agitation, and in 65 ℃ of reaction 4h; Vacuum drips 10.92ml (0.15mol) SOCl after removing clear superfluous methyl alcohol
2, stir 2.5h under the room temperature; Under the room temperature, vacuum 2h, Ex-all residual gas SO
2With HCl and responseless SOCl
2System is cooled to below-15 ℃, reaction mixture is solidified after, slowly add 10.0070g (0.05mol) ether diamine (ODA) and 160ml N, the solution of dinethylformamide and 8ml pyridine maintains the temperature at～-8 ℃ of stirring reaction 2h; The heavy-gravity reaction mixture is thread pours in the 2500ml distilled water, the decompress filter collecting precipitation soaks, washs repeatedly through alcohol, methyl alcohol, drain, and at 40 ℃ of vacuum-drying 24h.Product 37.73g (productive rate 97.5), limiting viscosity be 0.92dL/g (30 ℃, 0.5g/dL, DMAc).
Embodiment 2:
The biphenyl acid dimethyl ester 17.9152g (0.05mol) that open loop obtains in methyl alcohol is added in the 40ml tetramethylene sulfone by biphenyl dianhydride (BPDA), drips 10.92ml (0.15mol) SOCl down in 25 ℃
2And keep 25 ℃ and react 2h; Under the room temperature, vacuum 2h, Ex-all entrap bubble SO
2With HCl and responseless SOCl
2System temperature is reduced to below-15 ℃, make reaction mixture condense into solid after, slowly add the solution that 5.4070g Ursol D (p-PDA) and 120ml N-N-methyl-2-2-pyrrolidone N-and 8ml pyridine are formed, maintenance～-5 ℃ of stirring reaction 3h; The heavy-gravity reaction mixture is thread pours in the 2000ml distilled water, decompress filter, collecting precipitation is drained after alcohol, methyl alcohol fully soak, wash, and in 40 ℃ of vacuum-drying 24h.20.85g (productive rate 96%) limiting viscosity be 0.75dL/g (30 ℃, 0.5g/dL, the polyesteramide of stiff chain structure DMAc).
Embodiment 3:
14.7112g (0.05mol) BPDA (BPDA), 11.6120g (0.1mol) β-acrylic acid hydroxyl ethyl ester is added to 35g sym-trimethylbenzene and 10ml N, in the mixed solvent of N-N,N-DIMETHYLACETAMIDE, behind 60 ℃ of stirring reaction 12h, drip 7.48ml SOCl down in 15 ℃
2(0.103mol), and keep 15 ℃ the reaction 3.5h; Under the room temperature, vacuum 2h eliminates residual gas SO
2With HCl and responseless SOCl
2After, reactive system is cooled to below-15 ℃, make reaction mixture condense into solid; Slowly add the solution that 5.4070g mphenylenediamine (m-PDA) and 230ml N,N-dimethylacetamide and 8ml pyridine are formed, and keep～-10 ℃ of reaction 2.5h; Then the heavy-gravity reaction mixture is thread and pours in the 2000ml methyl alcohol, the decompression collecting precipitation after methyl alcohol, acetone and deionized water fully soak, wash, is drained 40 ℃ of vacuum-drying 24h.28.2g (productive rate 94%) limiting viscosity be 0.67dL/g (30 ℃, 0.5g/dL, photoactive polyamide ester DMAc).
Embodiment 4:
22.2129g (0.05mol) hexafluoro tetracarboxylic dianhydride, 11.6120g (0.1mol) β-acrylic acid hydroxyl ethyl ester is added to 45g sym-trimethylbenzene and 10ml N, in the mixed solvent of N-acetic acid dimethylamide, behind 50 ℃ of following stirring reaction 6h, reduces to room temperature, drips 7.48ml SOCl
2(0.103mol), and keep 10 ℃ of down reaction 2.5h; Under the room temperature, vacuum 2h takes out the HCl, the SO that remain in to the greatest extent in the reactive system
2And responseless SOCl
2Deng gas.System temperature is reduced to below-15 ℃, reaction mixture is solidified; Slowly add 10.0070g ether diamine (ODA) and 250ml N, the solution that N-acetic acid dimethylamide and 8ml pyridine are formed, the maintenance system temperature～-5 ℃, continue reaction 2h.Then the heavy-gravity reaction mixture is thread and pours in the 2000ml methyl alcohol, and soak, drain, wash for several times with methyl alcohol, deionized water in stirring, suction filtration is collected product, at 40 ℃ of vacuum-drying 24h.41.42g (productive rate 98%) photoactive polyamide ester, limiting viscosity be 0.78dL/g (30 ℃, 0.5g/dL, DMAc).
Embodiment 5:
The benzophenone two diethyl phthalate 20.7180g (0.05mol) that open loop obtains in ethanol are added in the 45ml tetramethylene sulfone by benzophenone dianhydride (BTDA), and 20 ℃ drip 7.48mlSOCl down
2(0.103mol), keep 20 ℃ of following stirring reaction 2.5h; Under the room temperature, vacuum 2h takes out most residual gas SO
2, HCl and responseless SOCl
2Temperature of reaction system is reduced to below-15 ℃, after making reaction mixture be frozen into solid solution, slowly add the solution that 20.5253g hexichol dihydroxyphenyl propane two ether diamines (BAPP) and 240ml N,N-dimethylacetamide and 8ml pyridine are formed, maintain～-10 ℃ of continuation stirring 2h.Then the heavy-gravity reaction mixture is thread and pours in the 2500ml distilled water, after repeatedly soaking, drain with methyl alcohol, distilled water in stirring and washing, suction filtration is collected product, 40 ℃ of vacuum 24h dryings.Limiting viscosity be 1.25dL/g (30 ℃, 0.5g/dL, polyesteramide 37.7g DMAc) (productive rate 99%).
Embodiment 6:
26.0251g (0.05mol) hexichol dihydroxyphenyl propane diether tetracarboxylic dianhydride (BPADA), 12.14ml methyl alcohol (0.3mol) is added in the 55ml tetramethylene sulfone, reacts 4h under reflux temperature; Vacuum is taken out unnecessary to the greatest extent methyl alcohol, reduces to room temperature, drips 10.92ml (0.15mol) SOCl
2, keep 15 ℃ of reaction 2.5h; Under the room temperature, vacuum 2h takes out most residual gas SO
2, HCl and responseless SOCl
2System is reduced to below-15 ℃, make reaction mixture condense into solid, slowly add the solution that 5.8097g hexanediamine (HAD) and 170ml N,N-dimethylacetamide and 8ml pyridine are formed, maintain-8 ℃ of stirring reaction 2h.Then the heavy-gravity reaction mixture is thread and pours in the 2000ml distilled water, in stirring, fully soak, drain, wash for several times with distilled water after, suction filtration is collected product, 40 ℃ of vacuum-drying 24h.Limiting viscosity be 0.93L/g (30 ℃, 0.5g/dL, flexible chain polyesteramide 34.15g (productive rate 98%) DMAc).
Embodiment 7:
16.3112g (0.05mol) diphenyl sulfide tetracarboxylic dianhydride (TDPA), 11.6120g (0.1mol) β-acrylic acid hydroxyl ethyl ester is added in the 40ml tetramethylene sulfone, in 55 ℃ of stirring reaction 12h; Reduce to room temperature, drip 7.48ml (0.103mol) SOCl
2, remain on 25 ℃ of reaction 2h; Under the room temperature, vacuum 2h takes out the HCl, the SO that remain in to the greatest extent in the reaction system
2Deng gas and responseless SOCl
2Cool the temperature to below-15 ℃, make reaction mixture condense into solid.Slowly add the solution that 10.0070g ether diamine (ODA) and 200ml HMPA and 8ml triethylamine are formed then, and maintain～-5 ℃ of reaction 2h.Reaction mixture is thread pours in the 2000ml industrial spirit, in stirring, soak, drain, wash for several times, soak, drain 40 ℃ of vacuum-drying 24h with deionized water again.Limiting viscosity be 0.95dL/g (30 ℃, 0.5g/dL, photoactive polyamide ester 35.95g (productive rate 99%) DMAc).
Embodiment 8:
The equal phthalic acid dimethyl ester 14.3080g (0.05mol) that open loop obtains in methyl alcohol is added in the 40ml tetramethylene sulfone by equal benzene dianhydride (PMDA), drips 10.92ml (0.15mol) SOCl
2, 18 ℃ of following stirring reaction 2.5h; Under the room temperature, vacuum 2h eliminates the entrap bubble SO in the system
2, HCl and responseless SOCl
2Cool the temperature to below-15 ℃, make reaction mixture condense into solid after, slowly add the solution that 14.6163g triphen two ether diamines (TPEQ) and 250ml N,N-dimethylacetamide and 8ml pyridine are formed, holding temperature is at～-10 ℃ of stirring reaction 2h.Then the heavy-gravity reaction mixture is thread and pours in the 2000ml industrial spirit, under agitation use methyl alcohol, distilled water immersion, washing for several times, drain 40 ℃ of vacuum-drying 24h.Limiting viscosity be 1.15dL/g (30 ℃, 0.5g/dL, polyesteramide 26.92g DMAc) (productive rate 98.5%)
Embodiment 9:
15.5112g (0.05mol) phenyl ether tetracarboxylic dianhydride (HQDPA) and 17.52ml ethanol (0.3mol) are added in the 45ml tetramethylene sulfone, react 4h under reflux temperature; High vacuum is taken out the ethanol of most surplus, reduces to room temperature, drips 10.92ml (0.15mol) SOCl
2, and keep 25 ℃ of stirring reaction 2h.Vacuum is taken out most residual gas SO
2, HCl and responseless SOCl
2After, cool the temperature to below-15 ℃, make reaction mixture condense into solid, slowly add 11.3154g 3,3 '-dimethyl-4,4 '-diaminodiphenylmethane (4MMDA3) and 180ml N, the solution that N-N,N-DIMETHYLACETAMIDE and 8ml pyridine are formed maintains～10 ℃ of stirring reaction 2h.The heavy-gravity reaction mixture is thread pours in the industrial spirit, in stirring, fully soak, wash, drain, 40 ℃ of vacuum-drying 24h with methyl alcohol, distilled water.Limiting viscosity be 0.89dL/g (30 ℃, 0.5g/dL, polyesteramide 28.79g DMAc) (productive rate 96.5%).
Embodiment 10:
By triphen two ether dianhydrides (HQDPA) the triphen diether that open loop obtains in methyl alcohol two dimethyl phthalate 23.3200g (0.05mol), be added among the 50ml, drip 10.92ml (0.15mol) SOCl
2At room temperature react 2h.Vacuum is taken out gas SO remaining in the most system
2, HCl and responseless SOCl
2After, cool the temperature to below-15 ℃, slowly add 12.4070g 4, (solution that p, p '-DDS) and 200 N,N-dimethylacetamide and 8ml pyridine form maintains～-10 ℃ of stirring reaction 2.5h 4 '-sulfobenzide diamines.The heavy-gravity reaction mixture is thread pours in the 2000ml industrial spirit, in stirring, fully soak, wash, drain, 40 ℃ of vacuum-drying 24h with methyl alcohol, distilled water.Limiting viscosity be 1.42dL/g (30 ℃, 0.5g/dL, polyesteramide 33.79g DMAc) (productive rate 99%).
Claims (1)
1. the preparation method of a high-molecular polyamide ester is characterized in that adopting following component synthetic:
(1) aromaticity tetracarboxylic dianhydride:
(2) diamine:
H
2N-R-NH
2 
(3) monohydroxy-alcohol:
HO-R
*
R
*:-CH
3-CH
2CH
3Or-CH
2CH
2OOCCH=CH
2
The solvent that uses among the present invention is:
(1) high-melting-point solvent: tetramethylene sulfone or sym-trimethylbenzene
(2) aprotic polar solvent: N,N-dimethylacetamide, N, dinethylformamide, N-
N-methyl-2-2-pyrrolidone N-, HMPA
The chlorine hydride absorbent of using among the present invention is: pyridine and triethylamine
Concrete synthesis step is as follows:
Aromatic dianhydride and monohydroxy-alcohol are added in dystectic solvent by one to two molar weight,, obtain the solution of the high-melting-point solvent of two acid diesters 50--65 ℃ of reaction 6-12 hour; In this solution, dripping an amount of SOCl under 10--25 ℃
2After, keep under this temperature and reacted 2-3.5 hour, and at room temperature remove hydrogenchloride and form waste gas of sulfur dioxide and the superfluous SOCl that remains in the system with two hours high vacuum
2, the solution of the high-melting-point solvent of acquisition diester diacid chloride; Cool the temperature to below-15 ℃, make this solution solidifies, obtain to contain the solid solution of diester diacid chloride; To be added on the above-mentioned solid solution with the DMAc solution of the diamines of dianhydride equal molar quantities, keep-5--10 ℃ between stirring reaction 2-3 hour, go out product with ethanol, water precipitation, the limiting viscosity of gained polyesteramide is at 0.60-1.42dL/g.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98118957A CN1098878C (en) | 1998-09-10 | 1998-09-10 | Process for preparing high-molecular polyamide ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98118957A CN1098878C (en) | 1998-09-10 | 1998-09-10 | Process for preparing high-molecular polyamide ester |
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|---|---|
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| CN1098878C true CN1098878C (en) | 2003-01-15 |
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| CN104592756B (en) * | 2015-02-10 | 2017-03-01 | 中国电子科技集团公司第四十九研究所 | A kind of polyimides humidity-sensitive material and preparation method thereof |
| CN110183637B (en) * | 2019-04-30 | 2021-08-31 | 珠海派锐尔新材料有限公司 | Thermotropic liquid crystal polymer and preparation method thereof |
| CN111303792A (en) * | 2020-04-09 | 2020-06-19 | 中天电子材料有限公司 | Hot-melt polyimide adhesive film and preparation method and application thereof |
| CN113851730A (en) * | 2021-08-20 | 2021-12-28 | 佛山(华南)新材料研究院 | High-temperature-resistant polymer electrolyte membrane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0181603A2 (en) * | 1984-11-08 | 1986-05-21 | Takeda Chemical Industries, Ltd. | A cross-linked resin, a process for producing the same, and a resin composition including the same |
| US4659849A (en) * | 1984-11-09 | 1987-04-21 | Ceskoslovenska Akademie Ved | Macromolecular coordination compound containing platinum with antitumor activity in rodents |
| US4812532A (en) * | 1987-07-29 | 1989-03-14 | Bio-Affinity Systems, Inc. | Solid phase oxime reagent |
-
1998
- 1998-09-10 CN CN98118957A patent/CN1098878C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0181603A2 (en) * | 1984-11-08 | 1986-05-21 | Takeda Chemical Industries, Ltd. | A cross-linked resin, a process for producing the same, and a resin composition including the same |
| US4659849A (en) * | 1984-11-09 | 1987-04-21 | Ceskoslovenska Akademie Ved | Macromolecular coordination compound containing platinum with antitumor activity in rodents |
| US4812532A (en) * | 1987-07-29 | 1989-03-14 | Bio-Affinity Systems, Inc. | Solid phase oxime reagent |
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