CN105622936A - Preparation method for polyamide acid solution - Google Patents
Preparation method for polyamide acid solution Download PDFInfo
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Abstract
The invention relates to a preparation method for a polyamide acid solution for preparing polyimide fibers, and is used for mainly solving the problems in the prior art that when a two-step method is adopted for preparing polyimide fibers, the polyamide acid solution has unstable viscosity control and too large viscosity in the preparation process to cause spinning difficulty. The problems are relatively well solved by adopting the technical schemes that the preparation method comprises the following steps: a) proportioning diamine and tetracarboxylic dianhydride according to the total molar ratio of 1 to X; b) under the protection of an inert gas, stirring diamine at low temperature to be completely dissolved in an organic solvent; and c) slowly adding tetracarboxylic dianhydride with the Y quantity ratio to the solution with the feeding time of 20-60 minutes, after the feeding is finished, continuing to carry out a reaction for 30-120 minutes, adding tetracarboxylic dianhydride with the Z quantity ratio to the reaction system, continuing to carry out a reaction for 0.5-10 hours, and thus obtaining the polyamic acid solution which can be used for industrial production of polyimide materials.
Description
Technical field
The present invention relates to a kind of preparation method preparing polyimide fiber polyamic acid solution, the particularly preparation method of the polyamic acid solution that a kind of viscosity is controlled.
Background technology
Polyimide fiber is primarily referred to as the high-performance fiber spinned by polyamic acid or polyimide solution, its excellent heat resistance, dielectric properties, resistance to low temperature, mechanical property, radiation resistance, it can be widely used in the very harsh field of the conditions such as Aero-Space, electric insulation, atomic energy industry, national defense construction, Environmental Industry, protection industry, health care, particularly in some high leading-edge fields. Its advantageous characteristic makes one of high technical fibre of most development prospect.
Polyimide fiber can be prepared by two-step method by polyamic acid or be prepared by one-step method by polyimides, so its polymerization technique includes the polymerization of polyamic acid and the polymerization of polyimides. One-step method is that not via polyamic acid, direct polymerization becomes PI to monomer. Major downside is that employing phenol solvent, toxicity is big, and the polyimide fiber that will obtain higher force performance is relatively difficult. Therefore, two step method spinning polyimide fiber is to develop the method always commonly used since polyimide fiber. Its synthetic method is the polyamic acid solution that dianhydride and diamidogen are progressively polymerized formation solubility at relatively low temperature, the first step is that through wet method or wet-dry change spray webbing, the concentrated solution of polyamic acid is obtained polyamic acid fiber, second step is that the polyamic acid fiber first step spinned forms polyimide fiber again through thermal dehydration cyclisation (imidization), or addition catalyst cyclodehydration obtains polyimide fiber.
The polyimide fiber of excellent needs based on the polyamic acid precursor solution of excellence, diamidogen and tetracarboxylic dianhydride are often carried out equivalent proportioning by polyamic acid solution in the course of the polymerization process, adopt traditional disposable method fed intake, owing to polymerization speed is too fast, the heat that polymerization produces not easily spreads at short notice, easily caused by topical gel, thus causing final polymer solution viscosity to control instability, the problems such as viscosity is excessive. Needed for this high viscosity solution can make polymerization on the one hand, power of agitator increases, and increases equipment energy consumption, is unfavorable for spinning moulding on the other hand, and therefore, most people all adopts the method for quiescence in high temperature to make solvent portions degraded reach to spin range of viscosities. Additionally, such as Japanese Laid-Open Patent number: described in 1982-131248, it is also possible to by adding water in polymer solvent, form carboxylic acid group by being hydrolyzed dianhydride monomer polymer molecular chain is terminated, thus reaching to control the purpose of polymer solution viscosity. Although, in this polymerization methods, Diamines and the total mole of tetracarboxylic dianhydride's class monomer are equal, but in this approach owing to the reaction between diamines monomer and tetracarboxylic dianhydride's class monomer and the reaction between water and tetracarboxylic dianhydride's class monomer belong to competitive reaction, the hydrolysis degree of dianhydride monomer is uncontrollable, thus causing that the viscosity of polymer solution in the course of the polymerization process is difficult to control to stablize.
Summary of the invention
When the technical problem to be solved is that in prior art, existence adopts two-step method to prepare polyimide fiber, the problem that polyamic acid solution is unstable in the control of preparation process medium viscosity and viscosity is excessive and causes difficulty in spinning, it is provided that the preparation method of the polyamic acid solution that a kind of viscosity is controlled. Polyamic acid solution prepared by the method has suitable spinning viscosity, and in solution, gel is less and the advantage of viscosity stabilization.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: the preparation method of the polyamic acid solution that a kind of viscosity is controlled:
A) it is that 1:X carries out proportioning by diamidogen and tetracarboxylic dianhydride by total mol ratio;
B) under the protection of noble gas, diamidogen is stirred at low temperatures and make it be dissolved completely in organic solvent;
The tetracarboxylic dianhydride that c) Y measures ratio is slowly added in above-mentioned solution continuously, feed time is 20��60 minutes, continuing reaction 30��120 minutes after reinforced end, the tetracarboxylic dianhydride that Z measures ratio joins in reaction system, obtains polyamic acid solution after continuing reaction 0.5��10 hour.
Wherein, 0.98��X��1.02,0.9��Y��0.98, Z=X-Y, the scheme being more highly preferred to is 0.99��X��1.01,0.95��Y��0.98.
In technique scheme, at least one in described tetracarboxylic dianhydride preferably structure as shown in formula (1):
Wherein, Ar1Preferably comprise the tetravalence aromatic residue of at least one carbon hexatomic ring, it is more preferable to be the aromatic residue shown in following structural formula (3):
In above-mentioned formula (3), R1Better selectDeng group.
In technique scheme, at least one in described diamidogen preferably structure as shown in formula (2):
H2N-Ar2-NH2Formula (2)
Wherein, Ar2Preferably comprise the tetravalence aromatic residue of at least one carbon hexatomic ring, it is more preferable to be the aromatic residue shown in following structural formula (4):
In structure above (4), R2Better select H-, CH3-��Cl-��Br-��F-��CH3Any one group such as O-.
In technique scheme, described organic solvent at least one in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide and sulfolane.
In technique scheme, the mixture of the described organic solvent at least one and N-Methyl pyrrolidone in DMF, N,N-dimethylacetamide, dimethyl sulfoxide and sulfolane; Wherein, N-Methyl pyrrolidone is 0.010��0.30:1 with at least one in DMF, N,N-dimethylacetamide, dimethyl sulfoxide and sulfolane by weight.
In technique scheme, in described organic solvent, water content is preferably less than 1500ppmw, more preferably 200ppmw��800ppmw.
In technique scheme, the temperature of described reaction is-10��40 DEG C, it is preferred to 0��30 DEG C; The solid content of gained polyamic acid solution is 5��30%, more preferably 10��20%.
At least one in technique scheme, in the preferred nitrogen of described noble gas, argon or helium.
In technique scheme, described reaction mixing speed is generally at 50��600 revs/min, it is preferred to 100��400 revs/min.
The method preparing polyamic acid solution of the present invention is first to be dissolved in organic solvent by diamidogen, then most dianhydride slowly it is continuously added to, after reaction a period of time, dianhydride property again a small amount of for residue is added, finally gives the polyamic acid solution of excellent performance. With traditional disposable feed intake compared with, the method is owing to being that polymerization speed is controlled, and therefore in course of reaction, system temperature change is inconspicuous, not easily causes topical gel by very slow to dianhydride continuous charging and speed. This technical process is initially charged major part dianhydride so as to add after fully reacting a period of time with diamidogen and remain dianhydride on a small quantity, such technical process can make system carry out the slow growth of strand under relatively low viscosity after homogenizing again, is therefore easier to obtain the polyamic acid solution that viscosity is controlled. Additionally, by described organic solvent selected from N, dinethylformamide, N, the mixture of at least one and N-Methyl pyrrolidone in N-dimethyl acetylamide, dimethyl sulfoxide and sulfolane, making N-Methyl pyrrolidone play the effect of viscosity modifier in a solvent, the intrinsic viscosity making gained polyamic acid is less, it is possible to make spinning solution molecular weight suitably decline, viscosity degradation, effective control system molecular weight and viscosity, improve spinnability.
In technique scheme, the assay method of described intrinsic viscosity is Shanghai Si Erda scientific instrument company limited NCY-4 type automatic viscosity instrument, adopts the capillary tube of diameter of phi=0.58mm to test at 25 DEG C, and test solution concentration is 0.5g/dL; The assay method of apparent viscosity is U.S. BROOKFIELDDV-III ULTRAPROGRAMMABLERHEOMETER, adopts LV-4 rotor to test at 25 DEG C.
Adopt polyamic acid stock solution prepared by method of the present invention, liquid in transparent and homogeneous, produces without gel through filtering test, and at 25 DEG C, solution apparent viscosity is not higher than 300Pa s, intrinsic viscosity can control at below 2.5dL/g, achieves good technique effect.
Below by specific embodiment, the present invention is further described.
Detailed description of the invention
[embodiment 1]
By p-phenylenediamine and 3,3 ', 4,4 '-BPDA is that 1:0.99 carries out proportioning by total mol ratio, the p-phenylenediamine of 10.0807g (0.1mol) and 225.6gN, N-dimethyl acetylamide are added in four-hole bottle (water content 410ppm), is stirred at room temperature and at N2Under protection, after being completely dissolved, ice-water bath is cooled to 0 DEG C; it is slowly added to 28.8120g (0.098mol) 3,3 ', 4; 4 '-BPDA powder, feed time is 20 minutes, and low whipping speed is after continuing reaction under 200 revs/min 30 minutes; by 0.296g (0.001mol) 3; 3 ', 4,4 '-BPDA powder adds in above-mentioned solution system; continue stirring 0.5 hour, obtain the required polyamic acid solution that solid content is 14.8%. This solution produces without gel through filtering test, and solution apparent viscosity is 116Pa S at 25 DEG C, and intrinsic viscosity is 1.40dL/g at 25 DEG C.
[embodiment 2]
By p-phenylenediamine and 3,3 ', 4,4 '-BPDA is that 1:1.01 carries out proportioning by total mol ratio, by the p-phenylenediamine of 10.0807g (0.1mol) and 358.0gN, dinethylformamide adds in four-hole bottle (water content 410ppm), is stirred at room temperature and at N2Under protection, after being completely dissolved, ice-water bath is cooled to 10 DEG C; it is slowly added to 27.9300g (0.095mol) 3,3 ', 4; 4 '-BPDA powder, feed time is 30 minutes, and low whipping speed is after continuing reaction under 250 revs/min 45 minutes; by 1.764g (0.006mol) 3; 3 ', 4,4 '-BPDA powder adds in above-mentioned solution system; continue stirring 1.5 hours, obtain the required polyamic acid solution that solid content is 10%. This solution produces without gel through filtering test, and solution apparent viscosity is 80Pa S at 25 DEG C, and intrinsic viscosity is 1.15dL/g at 25 DEG C.
[embodiment 3]
By p-phenylenediamine and 3,3 ', 4,4 '-BPDA is that 1:1 carries out proportioning by total mol ratio, the p-phenylenediamine of 10.0807g (0.1mol) and 118.4gN, N-dimethyl acetylamide are added in four-hole bottle (water content 410ppm), is stirred at room temperature and at N2Under protection, after being completely dissolved, at 35 DEG C, it is slowly added to 28.224g (0.096mol) 3; 3 ', 4,4 '-BPDA powder; feed time is 60 minutes; low whipping speed is after continuing reaction under 250 revs/min 120 minutes, by 1.176g (0.004mol) 3,3 '; 4; 4 '-BPDA powder adds in above-mentioned solution system, continues stirring 5 hours, obtains the required polyamic acid solution that solid content is 25%. This solution produces without gel through filtering test, and solution apparent viscosity is 212Pa S at 25 DEG C, and intrinsic viscosity is 2.03dL/g at 25 DEG C.
[embodiment 4]
By 4, 4 '-diphenyldiamine and 3, 3 ', 4, 4 '-BPDA is that 1:1.005 carries out proportioning by total mol ratio, by 20.0090g (0.1mol) 4, 4 '-diphenyldiamine and 115.6gN-methyl pyrrolidone add in four-hole bottle (water content 700ppm), it is stirred at room temperature and under argon shield, after being completely dissolved, 28.8120g (0.098mol) 3 it is slowly added at 40 DEG C, 3 ', 4, 4 '-BPDA powder, feed time is 40 minutes, low whipping speed is after continuing reaction under 250 revs/min 100 minutes, by 0.7350g (0.0025mol) 3, 3 ', 4, 4 '-BPDA powder adds in above-mentioned solution system, continue stirring 10 hours, obtain the required polyamic acid solution that solid content is 30%. this solution produces without gel through filtering test, and solution apparent viscosity is 240Pa S at 25 DEG C, and intrinsic viscosity is 2.31dL/g at 25 DEG C.
[embodiment 5]
By 4,4 '-diphenyldiamine and 3,3 ', 4,4 '-BPDA is that 1:0.98 carries out proportioning by total mol ratio, by the 4 of 20.0090g (0.1mol), 4 '-diphenyldiamine and 927.6gN-methyl pyrrolidone add in four-hole bottle (water content 450ppm), are stirred at room temperature and at N2Under protection, after being completely dissolved, ice-water bath is cooled to-10 DEG C; it is slowly added to 28.5180g (0.097mol) 3,3 ', 4; 4 '-BPDA powder, feed time is 40 minutes, and low whipping speed is after continuing reaction under 250 revs/min 110 minutes; by 0.2940g (0.001mol) 3; 3 ', 4,4 '-BPDA powder adds in above-mentioned solution system; continue stirring 8 hours, obtain the required polyamic acid solution that solid content is 5%. This solution produces without gel through filtering test, and solution apparent viscosity is 50Pa S at 25 DEG C, and intrinsic viscosity is 1.06dL/g at 25 DEG C.
[embodiment 6]
By 4, 4 '-diphenyldiamine and pyromellitic acid dianhydride are that 1:1.02 carries out proportioning by total mol ratio, by 20.0090g (0.1mol) 4, 4 '-diphenyldiamine and 228.6gN-methyl pyrrolidone add in four-hole bottle (water content 450ppm), it is stirred at room temperature and under helium is protected, after being completely dissolved, psychrolusia is cooled to 15 DEG C, it is slowly added to 21.1460g (0.097mol) pyromellitic acid dianhydride powder, feed time is 50 minutes, low whipping speed is after continuing reaction under 250 revs/min 40 minutes, 1.0900g (0.005mol) pyromellitic acid dianhydride powder is added in above-mentioned solution system, continue stirring 6 hours, obtain the required polyamic acid solution that solid content is 15.6%. this solution produces without gel through filtering test, and solution apparent viscosity is 176Pa S at 25 DEG C, and intrinsic viscosity is 1.95dL/g at 25 DEG C.
[embodiment 7]
By 4,4 '-diphenyldiamine and 3,3 ', 4,4 '-oxydiphthalic is that 1:1.003 carries out proportioning by total mol ratio, by the 4 of 20.0090g (0.1mol), 4 '-diphenyldiamine and 374.7g dimethyl sulfoxide add in four-hole bottle (water content 530ppm), are stirred at room temperature and at N2Under protection, after being completely dissolved, at 25 DEG C, it is slowly added to 30.0710g (0.097mol) 3; 3 ', 4,4 '-oxydiphthalic powder; feed time is 50 minutes; low whipping speed is after continuing reaction under 250 revs/min 120 minutes, by 1.8600g (0.006mol) 3,3 '; 4; 4 '-oxydiphthalic powder adds in above-mentioned solution system, continues stirring 2 hours, obtains the required polyamic acid solution that solid content is 12%. This solution produces without gel through filtering test, and solution apparent viscosity is 155Pa S at 25 DEG C, and intrinsic viscosity is 1.82dL/g at 25 DEG C.
[embodiment 8]
By 4,4 '-diphenyldiamine and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride is that 1:0.985 carries out proportioning by total mol ratio, by the 4 of 20.0090g (0.1mol), 4 '-diphenyldiamine and 133.0g sulfolane add in four-hole bottle (water content 680ppm), are stirred at room temperature and at N2Under protection, after being completely dissolved, at 35 DEG C, it is slowly added to 30.9130g (0.096mol) 3; 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride powder; feed time is 60 minutes; low whipping speed is after continuing reaction under 250 revs/min 30 minutes, by 0.8050g (0.0025mol) 3,3 '; 4; 4 '-benzophenone tetracarboxylic dianhydride powder adds in above-mentioned solution system, continues stirring 5 hours, obtains the required polyamic acid solution that solid content is 28%. This solution produces without gel through filtering test, and solution apparent viscosity is 206Pa S at 25 DEG C, and intrinsic viscosity is 1.99dL/g at 25 DEG C.
[embodiment 9]
By 4,4 '-diphenyldiamine and 3,3 ', 4,4 '-BPDA is that 1:1 carries out proportioning by total mol ratio, by the 4 of 20.0090g (0.1mol), and 4 '-diphenyldiamine and 280.0gN, N-dimethyl acetylamide adds in four-hole bottle (water content 540ppm), is stirred at room temperature and at N2Under protection, after being completely dissolved, at 35 DEG C, it is slowly added to 28.8120g (0.098mol) 3; 3 ', 4,4 '-BPDA powder; feed time is 20 minutes; low whipping speed is after continuing reaction under 250 revs/min 60 minutes, by 0.5880g (0.002mol) 3,3 '; 4; 4 '-BPDA powder adds in above-mentioned solution system, continues stirring 7 hours, obtains the required polyamic acid solution that solid content is 15%. This solution produces without gel through filtering test, and solution apparent viscosity is 188Pa S at 25 DEG C, and intrinsic viscosity is 1.79dL/g at 25 DEG C.
[embodiment 10]
By p-phenylenediamine and 3,3 ', 4,4 '-oxydiphthalic is that 1:0.996 carries out proportioning by total mol ratio, by 10.0807g (0.1mol) 4,4 '-diphenyldiamine and 186.6gN, N-dimethyl acetylamide add in four-hole bottle (water content 540ppm), are stirred at room temperature and at N2Under protection, after being completely dissolved, at 35 DEG C, it is slowly added to 30.3810g (0.098mol) 3; 3 ', 4,4 '-oxydiphthalic powder; feed time is 60 minutes; low whipping speed is after continuing reaction under 250 revs/min 100 minutes, by 0.4960g (0.0016mol) 3,3 '; 4; 4 '-oxydiphthalic powder adds in above-mentioned solution system, continues stirring 2 hours, obtains the required polyamic acid solution that solid content is 18%. This solution produces without gel through filtering test, and solution apparent viscosity is 178Pa S at 25 DEG C, and intrinsic viscosity is 1.86dL/g at 25 DEG C.
[embodiment 11]
By 4,4 '-diphenyldiamine and pyromellitic acid dianhydride are that 1:1.002 carries out proportioning by total mol ratio, by the 4 of 10.0807g (0.1mol), and 4 '-diphenyldiamine and 167.6gN, N-dimethyl acetylamide adds in four-hole bottle (water content 610ppm), is stirred at room temperature and at N2Under protection; after being completely dissolved; 21.3640g (0.098mol) pyromellitic acid dianhydride powder it is slowly added at 35 DEG C; feed time is 60 minutes; low whipping speed is after continuing reaction under 250 revs/min 120 minutes; 0.4796g (0.0022mol) pyromellitic acid dianhydride powder is added in above-mentioned solution system, continue stirring 4 hours, obtain the required polyamic acid solution that solid content is 16%. This solution produces without gel through filtering test, and solution apparent viscosity is 184Pa S at 25 DEG C, and intrinsic viscosity is 1.91dL/g at 25 DEG C.
[embodiment 12]
By 4, 4 '-diphenyldiamine and pyromellitic acid dianhydride are that 1:1.002 carries out proportioning by total mol ratio, by 10.0807g (0.1mol) 4, 4 '-diphenyldiamine and 152.4gN, N-dimethyl acetylamide and 15.2gN--methyl pyrrolidone add in four-hole bottle (water content 610ppm), it is stirred at room temperature and under N2 protects, after being completely dissolved, 21.3640g (0.098mol) pyromellitic acid dianhydride powder it is slowly added at 35 DEG C, feed time is 60 minutes, low whipping speed is after continuing reaction under 250 revs/min 120 minutes, 0.4796g (0.0022mol) pyromellitic acid dianhydride powder is added in above-mentioned solution system, continue stirring 4 hours, obtain the required polyamic acid solution that solid content is 16%. this solution produces without gel through filtering test, and solution apparent viscosity is 103Pa S at 25 DEG C, and intrinsic viscosity is 1.52dL/g at 25 DEG C.
[embodiment 13]
By 4, 4 '-diphenyldiamine and pyromellitic acid dianhydride are that 1:1.002 carries out proportioning by total mol ratio, by 10.0807g (0.1mol) 4, 4 '-diphenyldiamine and 167.6gN-methyl pyrrolidone add in four-hole bottle (water content 610ppm), it is stirred at room temperature and under N2 protects, after being completely dissolved, 21.3640g (0.098mol) pyromellitic acid dianhydride powder it is slowly added at 35 DEG C, feed time is 60 minutes, low whipping speed is after continuing reaction under 250 revs/min 120 minutes, 0.4796g (0.0022mol) pyromellitic acid dianhydride powder is added in above-mentioned solution system, continue stirring 4 hours, obtain the required polyamic acid solution that solid content is 16%. this solution produces without gel through filtering test, and solution apparent viscosity is 218Pa S at 25 DEG C, and intrinsic viscosity is 2.66dL/g at 25 DEG C.
Polyamic acid composition solution obtained for polymerization is obtained polyamic acid spinning liquid after filtration, deaeration, by " dry-jet wet-spinning " technique through the spinneret orifice spray webbing of �� 0.14mm, then through washing, oil, dry, receiving silk, and between 100 DEG C��600 DEG C, carry out hot imidization and hot gas spring process, obtain final polyimide fiber. The mechanical property of gained fiber is: fracture strength T=5.45cN/dtex; Rupture modulus M=91.52cN/dtex; Elongation at break E=12.38%.
[embodiment 14]
By 4, 4 '-diphenyldiamine and pyromellitic acid dianhydride are that 1:1.002 carries out proportioning by total mol ratio, by 10.0807g (0.1mol) 4, 4 '-diphenyldiamine and 159.6gN, N-dimethyl acetylamide and 8g dimethyl sulfoxide add in four-hole bottle (water content 610ppm), it is stirred at room temperature and under N2 protects, after being completely dissolved, 21.3640g (0.098mol) pyromellitic acid dianhydride powder it is slowly added at 35 DEG C, feed time is 60 minutes, low whipping speed is after continuing reaction under 250 revs/min 120 minutes, 0.4796g (0.0022mol) pyromellitic acid dianhydride powder is added in above-mentioned solution system, continue stirring 4 hours, obtain the required polyamic acid solution that solid content is 16%. this solution produces without gel through filtering test, and solution apparent viscosity is 265Pa S at 25 DEG C, and intrinsic viscosity is 2.36dL/g at 25 DEG C.
[embodiment 15]
By 4, 4 '-diphenyldiamine and pyromellitic acid dianhydride are that 1:1.002 carries out proportioning by total mol ratio, by 10.0807g (0.1mol) 4, 4 '-diphenyldiamine and 167.6gN, N-dimethyl acetylamide adds in four-hole bottle (water content 610ppm), it is stirred at room temperature and under N2 protects, after being completely dissolved, 17.4400g (0.08mol) pyromellitic acid dianhydride powder it is slowly added at 35 DEG C, feed time is 60 minutes, low whipping speed is after continuing reaction under 250 revs/min 120 minutes, 4.4036g (0.0202mol) pyromellitic acid dianhydride powder is added in above-mentioned solution system, continue stirring 4 hours, obtain the required polyamic acid solution that solid content is 16%. this solution produces without gel through filtering test, and solution apparent viscosity is 281Pa S at 25 DEG C, and intrinsic viscosity is 2.43dL/g at 25 DEG C.
[comparative example 1]
By p-phenylenediamine and 3,3 ', 4,4 '-BPDA is that 1:1 carries out proportioning by total mol ratio, the p-phenylenediamine of 10.0807g (0.1mol) and 223.7gN, N-dimethyl acetylamide are added in four-hole bottle (water content 380ppmw), at N2Being stirred at room temperature under protection, after being completely dissolved, ice-water bath is cooled to 0 DEG C; add 29.402g (0.1mol) 3,3 ', 4; 4 '-BPDA powder, stirs, mixing speed 150 revs/min in 10 DEG C of temperature ranges; after being completely dissolved; maintain reaction 3 hours, namely obtain lurid very viscous solution, very serious rod climbing phenomenon occurs in the course of the polymerization process; obtaining the required polyamic acid solution that solid content is 15.0%, polymer solution cannot be processed because of excessively thickness. After tested, kinematic viscosity is >=1000Pa S at 25 DEG C, and intrinsic viscosity is 4.85dL/g at 25 DEG C.
[comparative example 2]
By 4,4 '-diphenyldiamine and pyromellitic acid dianhydride are that 1:1 carries out proportioning by total mol ratio, by the 4 of 24.0108g (0.12mol), and 4 '-diphenyldiamine and 284.3gN, N-dimethyl acetylamide (water content 380ppmw) adds in four-hole bottle, at N2It is stirred at room temperature under protection; after being completely dissolved, ice-water bath is cooled to 0 DEG C, adds 26.1558g (0.12mol) pyromellitic acid dianhydride powder; stir in 10 DEG C of temperature ranges; mixing speed 150 revs/min, after being completely dissolved, maintains reaction 1.5 hours; namely lurid very viscous solution is obtained; occurring in the course of the polymerization process very serious pulling out pole phenomenon, obtain the required polyamic acid solution that solid content is 15.0%, polymer solution cannot be processed because of excessively thickness. After tested, kinematic viscosity is >=1000Pa S at 25 DEG C, and intrinsic viscosity is 5.25dL/g at 25 DEG C.
[comparative example 3]
By 4,4 '-diphenyldiamine and pyromellitic acid dianhydride are that 1:1.01 carries out proportioning by total mol ratio, by the 4 of 24.0108g (0.12mol), and 4 '-diphenyldiamine and 229.7gN, N-dimethyl acetylamide (water content 380ppmw) adds in four-hole bottle, at N2It is stirred at room temperature under protection; after being completely dissolved, ice-water bath is cooled to 0 DEG C, adds 26.4174g (0.1212mol) pyromellitic acid dianhydride powder; stir in 10 DEG C of temperature ranges; mixing speed 150 revs/min, after being completely dissolved, maintains reaction 1.5 hours; namely lurid very viscous solution is obtained; occurring in the course of the polymerization process very serious pulling out pole phenomenon, obtain the required polyamic acid solution that solid content is 18.0%, polymer solution cannot be processed because of excessively thickness. After tested, kinematic viscosity is 800Pa S at 25 DEG C, and intrinsic viscosity is 3.89dL/g at 25 DEG C.
[comparative example 4]
By 4,4 '-diphenyldiamine and pyromellitic acid dianhydride are that 1:0.99 carries out proportioning by total mol ratio, by 24.0108g (0.12mol) 4,4 '-diphenyldiamine and 303mlN, N-dimethyl acetylamide (adds deionized water in solvent, it is 1430ppmw to water content) add in four-hole bottle, at N2It is stirred at room temperature under protection; after being completely dissolved; ice-water bath is cooled to 0 DEG C; add 25.8943g (0.1188mol) pyromellitic acid dianhydride powder, stir in 10 DEG C of temperature ranges, mixing speed 150 revs/min; after being completely dissolved; maintaining reaction 1.5 hours, namely obtain lurid very viscous solution polyamic acid solution, the solid content of solution is 18.0%. After tested, kinematic viscosity is 300Pa S at 25 DEG C, and intrinsic viscosity is 2.83dL/g at 25 DEG C.
Claims (8)
1. a preparation method for the polyamic acid solution that viscosity is controlled, comprises the following steps:
A) it is that 1:X carries out proportioning by diamidogen and tetracarboxylic dianhydride by total mol ratio;
B) under the protection of noble gas, diamidogen is stirred at low temperatures and make it be dissolved completely in organic solvent;
The tetracarboxylic dianhydride that c) Y measures ratio is slowly added in above-mentioned solution continuously, feed time is 20��60 minutes, continuing reaction 30��120 minutes after reinforced end, the tetracarboxylic dianhydride that Z measures ratio joins in reaction system, obtains polyamic acid solution after continuing reaction 0.5��10 hour;
Wherein, 0.98��X��1.02,0.9��Y��0.98, Z=X-Y.
2. the preparation method of the polyamic acid solution that a kind of viscosity described in claim 1 is controlled, it is characterised in that described tetracarboxylic dianhydride at least one in structure shown in formula (1):
Wherein, Ar1For the tetravalence aromatic residue containing at least one carbon hexatomic ring.
3. the preparation method of the polyamic acid solution that a kind of viscosity described in claim 1 is controlled, it is characterised in that described diamidogen at least one in structure shown in formula (2):
H2N-Ar2-NH2Formula (2)
Wherein, Ar2For the O divalent aromatic residue containing at least one carbon hexatomic ring.
4. the preparation method of the polyamic acid solution that a kind of viscosity described in claim 1 is controlled, it is characterized in that, described organic solvent at least one in DMF, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide and sulfolane.
5. the preparation method of the polyamic acid solution that a kind of viscosity described in claim 1 is controlled, it is characterized in that, the mixture of the described organic solvent at least one and N-Methyl pyrrolidone in DMF, N,N-dimethylacetamide, dimethyl sulfoxide and sulfolane.
6. the preparation method of the polyamic acid solution that a kind of viscosity described in claim 1 is controlled, it is characterised in that in described organic solvent, water content is less than 1500ppmw.
7. the preparation method of the polyamic acid solution that a kind of viscosity described in claim 1 is controlled, it is characterised in that at least one in the preferred nitrogen of described noble gas, argon or helium.
8. the preparation method of the polyamic acid solution that a kind of viscosity described in claim 1 is controlled, it is characterised in that the temperature of described reaction is-10��40 DEG C; The solid content of described polyamic acid is 5��30%.
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| CN109666144A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The preparation method of polyamic acid solution |
| CN109666143A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Polyamic acid solution preparation method |
| CN112225906A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Polyamic acid salt solution and preparation method and application thereof |
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| CN103788651A (en) * | 2014-01-17 | 2014-05-14 | 四川大学 | Low-apparent-viscosity polyamide acid solution and preparation method thereof |
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| US20030215654A1 (en) * | 2002-05-17 | 2003-11-20 | Hideki Moriyama | Laminate type materials for flexible circuits or similar-type assemblies and methods relating thereto |
| CN103013114A (en) * | 2012-12-05 | 2013-04-03 | 宁波今山新材料有限公司 | Method for preparing waterproof polyimide thin film |
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| CN109666144A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | The preparation method of polyamic acid solution |
| CN109666143A (en) * | 2017-10-17 | 2019-04-23 | 中国石油化工股份有限公司 | Polyamic acid solution preparation method |
| CN109666143B (en) * | 2017-10-17 | 2021-05-11 | 中国石油化工股份有限公司 | Preparation method of polyamic acid solution |
| CN109666144B (en) * | 2017-10-17 | 2021-10-01 | 中国石油化工股份有限公司 | Method for preparing polyamic acid solution |
| CN109338499A (en) * | 2018-09-20 | 2019-02-15 | 浙江浩睿新材料科技有限公司 | A kind of polyimide fiber long filament spinning solution |
| CN109338499B (en) * | 2018-09-20 | 2021-04-20 | 义乌华鼎锦纶股份有限公司 | Spinning solution for polyimide fiber filaments |
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