Method of preparing polyelectrolytes containing amino-imide groups

专利摘要:
The invention relates to polyelectrolytes and their use in the fractionation of blood and other proteinaceous substances. …<??>The filterability, drying characteristics and physical form of water-insoluble, cross-linked polyelectrolytes containing amine-imide functional groups are employed without substantially diminishing the protein adsoprtion capacity of said polyelectrolytes by heating the polymeric starting material in inert organic solvent at a temperature ranging from about 115 DEG C to about 160 DEG C but lower than the softening point of said polymer for at least about 15 minutes and until said polymer is substantially aggregated prior to crosslinking.
公开号:SU795490A3
申请号:SU782641107
申请日:1978-07-21
公开日:1981-01-07
发明作者:Эдвард Фильдс Джозеф；Джэксен Слокомб Роберт
申请人:Монсанто Компани (Фирма)；
IPC主号:

专利说明:

(54) METHOD FOR OBTAINING POLYELECTROLYTES CONTAINING AMINO-IMID GROUPS
The product is more than three times higher than this non-aggregated product index.
Critical to the invention is the fact that the aggregation process is carried out before cross-linking and replacement by a large number of amino-imide groups. It has been found that if the formation of cross-links and / or. Substitution with an excess of amino-imide functional groups is carried out before the intended aggregation process, which is not. the benefits of the invention are lost. This fact can be considered-. unexpectedly, since it is opposite to expectation; the presence of a functional group in a polymer makes TITO softer and, therefore, easier to aggregate by simple particle fusion, a larger number means more than 50% of the amino-imide groups.
Polymerization of ethylene and maleic acid (EMA) or eel anhydride according to the invention is carried out by mixing the polymer in suspension in a heated and refluxed organic solvent and does not react with the polymer to reflux or heat at 115. but below the softening point. . Preferred solvent is xylene. Other suitable solvents include, for example, ethylbenzene, monoyl dichlorobenzene and cumene. Solvents, such as benzene and toluene with boiling points below approximately, are unsuitable for carrying out the invention. However, dioxane with a batch of 101, gives valuable results in coagulation. It has been found that, when processing the polymer in a boiling solvent, temperatures below about no significant aggregation of the product occurs, as required by reference, when using a weak solvent such as a hydrocarbon solvent. Aggregation can occur in high-boiling solvents at those temperatures below the boiling point, but temperatures above the boiling point of the polymer are unsuitable, since it is impossible to obtain a material with the required properties.
It is desirable to heat the polymer under reflux in a solvent for at least about 15 minutes, good results are obtained by heating up to about 1 hour. Longer heating, in particular for more than 1 hour, is not necessary, although the aggregates remain stable in weak solvents even the time is up to 7 hours. The stronger the use of solvents (chlorobenzene, dichlorobenzene, dioxane and N, N-dimethylamine, the less preferable they are
excessive coagulation count. during a longer aggregation time.
By performing the aggregation process, the aggregated polymer is crosslinked and replaced by the desired aminoimide functional group in a sequence optimizing the properties of the product, which is accomplished by proper distribution of specific groups within the particles.
The starting copolymers can be converted to carboxyl-containing copolymers by reacting their ammonium, alkali and alkaline earth metal salts and alkylamine salts with water by reacting with alkali and alkaline earth metal compounds, amines or ammonium. Other suitable derivatives of the above polymers include alkyl and other esters, alkylamides, dialkylamides, phenyl alkyl amides or fe 1 amides obtained by reacting the carboxyl groups of the copolymer with. selected amines with either alkyl or femylalkyl alcohol, as well as amino ester 1, hydroxy amides and oxyesters, where the functional groups are separated by alkelene, phenyl, phenyl alkyl, phenyl xylene phenyl, or other phenylalkyl or other aryl groups. A link containing amines or aminosols, including quaternary salt groups, is usually prepared by reacting the carboxyl groups of their precursors, where possible with polyfunctional amines, like dimethylaminopropylamino, at elevated temperatures to form an imide bond with the vicinal carboxyl groups. Such additional free amino groups may be converted, as appropriate, into their simple or quaternary salts.
Example, In a flask with a capacity of 5 liters, equipped with a reverse refrigeration -
5 NIKOM, a Dean-Stark trap, a stirrer, a container for adding a reagent, a thermometer and nitrogen cleaning equipment, load 193.05 g of a copolymer of the type EMKA containing
Q ethylene and maleic anhydride (1.5 mol, anhydride base) and 2,700 MP of xylene. The mixture is stirred at a rate of 200 rpm with a stirrer and heated to reflux temperature, which ranges from 135 to depending on the water content in the ECA and azeotropic removal of water during the reflux period. In this example, the slurry is refluxed.
fully within 60 min at. After 1 h, the reactor is cooled to a nitrogen atmosphere, then adding a solution of 10.89 g (0.075 mol) of methylimino-propropylamine (MIBPA) and 1.5 ml
5 water.
The mixture is heated under reflux (134 ° C) and held at this temperature for 1 h, continuously removing azeotropic water (the final temperature). The temperature of the reaction mixture is again lowered under a nitrogen atmosphere until, by adding a mixture of 153.3 g (1.5 mol) of dimethylaminopropylamine and 4.5 ml of water, the mixture is then heated to 133 s, and you are kept at this temperature until the start of reflux (after 1-10 min.). Stirring under reflux is continued until the removal of water is completed by azeotropic distillation. The final temperature is 1E9 ° C.
In order to process the free amine, the sludge is filtered in a hot state, after which the cake is again dissolved to produce a sludge in 2,700 ml of a mixture of xylene and ethanol (3: mix with a reverse cold bath for 1 hour and again filter in a hot form This procedure is repeated a second time for 2 hours and a third time for 3 hours, filter each time in a hot state. The obtained extracted cake is again dissolved in 2700 ml of hexane for 1 hour at room temperature and filtered. Extraction of hexane is repeated. 4 more times. The target product is air dried. he 30 min and then dried in a vacuum oven at.
For processing in the form of the hydrochloric salt, the target ishams are filtered hot, and the zhinah will dissolve again to form a slurry under reflux in a mixture of xylene and alcohol (3: 1 three times in the indicated manner, and then, at room temperature, they are extracted twice with 2700 ml acetone for 1 hour.The filtered product is converted into hydrochloride by redissolving either in 2700 ml of alcohol or acetone with the gradual addition, over the course of 10 minutes, of 112 ml of concentrated 12N hydrochloric acid, then stirring at room temperature. perature 2h.
The filtered product is then washed (in the case of ishama with stirring) three times with 10 l of water (deionized) for 2 hours in each case and then filtered. The filtered cake meal (salt) is redissolved twice in 2700 ml of adeton (1 hour each time to remove water, filtered, air dried for half an hour and dried in a vacuum oven at.
The dried end product, either as a free amine or as a salt, is passed through IT without crushing; wherein. 95% of the product passes through a 100 mesh screen; then it is bottled in bottles.
EXAMPLE 2 An aggregated diethylaminoethyl derivative was prepared as described in Example 1, except that the DMAPA of Example 1 was replaced with 174.32 g H1.5 mol) of dimethylaminoethylamine (DEAEA). The desired product is obtained as the free amine of example 1, according to which the reaction product is extracted with a mixture of xylene and alcohol (3: 1), and then 6 times with hexane. Pass the product through a sieve without crushing - (100 mesh, yielding 229 g of product, more than 100 mesh, and 13.0 g of product, larger than 100 mesh.
Froze In this example, the same apparatus as in Example 1 is used, as well as the same method and the same starting mixture (EMCA and xylene). After aggregation (1 hour under reflux), the temperature of the slurry is reduced to, then 10.98 (0.075 mol) MIBPA is added. The slurry is stirred at 120-125 With 1 h without reflux. After 1 hour, 7.66 g of 1 (0.075 mol) DMAPA is added, the slurry is again stirred at 120125 ° C for 1 hour without refluxing, after which the slurry is heated to reflux temperature and all the water from the condensation reaction is removed by azeotropic distillation. The final temperature. The reaction mixture is cooled until 87.0.5 g of M1-1-ethanolamine (MOETA) is added. The slurry is kept for 1 h at. The temperature is then raised to demineralization, removing all water from this final condensation reaction for 6 hours by azeotropic distillation. The final temperature. The product neipe is processed as a free amine. in Example 1. 230 g of product passing through 100 mesh openings without crushing, and 17 g of product retained on the sieve are obtained.
Example4. In order to improve the dispersion properties of the product obtained in Example 3, the sequence of addition of BWPA and DMAPA at the end of the aggregation reaction is changed.
The same amounts of amines and other products of Example 3 are used. The process is carried out identically, including the aggregation stage. After cooling the aggregated sludge until 7, 66 g of DMAPA is added, the shlgil is kept for 1 hour at a temperature of 120-125 ° C. Then 10.89 MIBPA is added, keeping the slurry again for 1 hour at 120-125 ° C. The target product is processed as a free amine. .
EXAMPLE 5 Example 4 is repeated, except that the desired product is processed as the hydrochloric acid salt of Example 1. For this purpose, only 14 ml of concentrated acid is used.
l2 n.) instead of 112 ml of example 1.
after drying, get 240 g of the target
product.
PRI me R 6. The process is conducted according to
Example 3, except that the ode from the condensation reaction is removed by azeotropic distillation
amine reaction and each extract,
i.e. after the reaction of 1U1IPPA, DMAPA
and MOETA, but not according to example 3. Product
receive in the form of hydrochloride salt
with the release of 240 g
Example. A series of samples are made, changing the composition of the amines used as crosslinking agents.
or functional units of both type and concentration. These aggregated compositions are listed in Table 1.
EXAMPLE 8. The same apparatus and the same starting mixture (EMA and xylene) are used as in Example 1. Aggregation, analogous to example 1, is achieved in one of two ways: a) heating the EMAA sludge to 200 vol. / min with the addition of 10.89 g of MIBPA and 1.5 ml of water, further stirring for 1 hour, increasing the temperature to reflux (and removing all the water from the condensation reaction using a Dean-Stark trap by heating under reflux (final temperature AZE.); b) heating the sludge EMKA at 200 rpm to 125 s with the addition of MIBPA and water directly This is an increase in temperature to reflux (136 ° C) with the continuation of reflux to the total amount of water from the condensation reaction by azeotropic distillation at the final temperature. At the end of method a) or b) the temperature of the contents of the flask is reduced to 125 ° C, then adding 153.3 g of DMAPA and 4.5 MP of water. The slurry is heated to 133c before refluxing, continuing until the water is completely removed from condensation by azeotropic distillation to a final temperature of 139140 ° C.
Trust, sludge filter in hot form (above). The filtration time at this stage is 30-60 minutes, in contrast to a time less than 5 minutes for the aggregated material obtained in examples 1-7. The filtered product is processed either as free amine or hydrochloride salt by the methods described in Example 1. Again - during processing - the filtration time is high (from 30 minutes to 2 hours), in contrast to the duration of the aggregated products according to examples 17, was 5 10 min. non-aggregated products obtained from this and the methods given below dry out poorly and require crushing or processing by a ball mill
before passing through a 100 &amp; s screen, in contrast to the aggregated products of Examples 1-7, which do not require crushing or processing in a ball mill before passing through a sieve (SU mesh) after drying.
Example 9. In this example, the same equipment and the same starting mixture (EMA and xylene) are used as in Example 8. The slurry is heated to 90JJ 95c, then 10.89 g are added.
(tt, 075 mol) MIBPA and stirred at 95 ° C for 1 h. After that, 7.66 g (o, O75 mol of DMAPA is added and the mixture is stirred for 1 h. The slurry is heated under reflux (134 s) water from
the condensation reactions are completely removed by azeotropic distillation to a final temperature of 139 C.- After this, the sludge is cooled to, 87.05 g of oxyethylamine is added, stirring
 slurry for 1 h at 95c. The temperature of the sponge is increased to 134 ° C, and the entire amount of water from the condensation reaction is completely removed by azeotropic distillation to a final temperature of 139-140 ° C. The target slurry is filtered hot for 30 minutes and processed as free amine by the method of Example 1, dried, intensively crushed in a ball mill and passed through a sieve.
0 (100 mesh). The amounts allocated after 12 runs vary from 219 to 244 g, depending on the processing efficiency of the ball mill, before passing through the sieve.
J EXAMPLE 10 The process is carried out according to Example 8, except that the water from the reaction is not removed after the addition of MIBPA, but left in the sludge until DMAPA is added. After that, all the water from
Both of the amine reactions are removed in one step of azeotropic distillation to a final slurry temperature of 140 ° C. The product is processed as a free amine.
5 Example. The process is carried out according to the example, except that the water from the reaction is not removed by adding MPPA after aggregation, and only after adding DMAPA, removing it
0 completely (from both amine reactions) at one stage of azeotropic distillation. The target sludge is filtered hot in less than 5 minutes, then the product is processed as
„Free amine by example.
PRI mme R 2. Consider the effect of time and mixing rate during aggregation, taking into account the filtration rate of hot target sludges.
60 Conduct a series of comparable runs, following the example process, changing the duration of the aggregation process and the mixing speed. All products are processed as free amines in example 1. The results are shown in table. 2 and compared therein with non-aggregated products prepared according to Example 8. Example 13. In order to more accurately determine the requirements for temperature and solvent for aggregation, a series of experiments are carried out using EMKA as a crude product in a number of solvents and different temperatures and mixing speeds. It was found that a change in the stirring speed in the range of 150-400 rpm affects only the size of the resulting aggregated product. A large role is played by the type of solvent and the temperature range of the aggregation process. In this example, a 1 L flask is used, in which 700 ml of solvent and 50 g of EMKA are charged. At different times and at different temperatures, 20 ml aliquots of the sludge are taken and placed in test tubes. Upon cooling, the tubes are shaken, measuring the time it takes for the polymer to fall out of the solvent. The results are shown in Table. 3. EXAMPLE 14 An indicator of the size of particles in a dispersion, whether aggregated or not, is the swelling index, expressed as the amount of water or other dispersant in grains absorbed under equilibrium conditions per gram of polymer derivative. A sample of the appropriate sizes is dispersed in excess dispersant, pH adjustment to 4 or other. Dispersions are allowed to reach equilibrium conditions for 1 hour, then the centrifugal is then for half an hour at 75 ° C in a pre-weighed centrifuge flask. Unreacted material is drained to determine the weight of the centrifuged swollen gel. All data were obtained using 0.04 M brine as a dispersant at pH 4.0. Thus, the value of the swelling index is equal to the weight of 0.04 M brine absorbed by 1 g of polymer. It is known that the swelling is inversely proportional to the density of cross-linked insoluble cross-linking resins. In a number of cases, with an increase in the addition to the derivative amount of MIBPA, the expected decrease in swelling is observed, all other parameters of the ogiots are equal. However, for an aggregated material according to the invention, it has been found that the swelling of an aggregated product at any constant MIIT concentration and equal cross-link density can be changed without difficulty and it is very different from non-aggregated derivatives if the amount of water added during the preparation of the aggregated polyelectrolyte is changed and modify the steps of removing water from the reaction. In tab. Figure 4 shows a series of aggregated and non-aggregated polymers containing LBBPA and DMAPA, according to Examples 1, 8DO and 11, but with different amounts of wool added either with MIBPA or DMAPA. All polymers contain 5 mol.% MIBPA and 90. Mol ...% DMAPA. Table
5 5
7 9
7 9 5 5
H {
81 77
Ca
C A and citrate
85 85
C A
6 4 6 b 6 6 4 4-5 С А
four
85 83 79 79 75 87 89 C A C A C A C A C A C A HC1
He KS ile ndimi n (SCHDA) Free amine (CA)
Xylene (t-kip. 139)
Continued table. one
Table 2:
Table3
More than 10 10 6-7 b 4 3 2.5-3
Xylene
Toluene (t. Kip.lift)
Benzene (t. Kip.)
Dioxane (t. Kip.)
Monochlorobenzene (m. Bale}
p-Dichlorbe n 3 ol (t. Kip.)
o-Dichlorbe n 3 ol
Ethylbenzene (t. Kip.)
. Continuation of the table. 3 "Oshkdenie experience stop after
MIBPA without water; DMAP without water
O19.54
O210.05
O1- 9.44
O2- 8.91
MIBPa without water; DMAP with 1.0 ml of water
1,0110,71
1,0211,23
1.01 - 8.85
1.02 - 8.99
MIBPAS 1.5mwater; DMAPA WITH 4.5 ML WATER
6,0112,98
6.0213.00
6.01- 8.88
6.02- 9.43

权利要求:
Claims (1)
[1]
Invention Formula
The method of obtaining polyelectrolytes containing amino-imide groups by treating a polymer based on ethylene and maleic acid or its anhydride with alkyl amino-alkylamines,
Continued table. 3
which shkil is lower m, replacing most of the acid
60 groups for amine-imide and cross-linking of the polymer, characterized in that, in order to improve the filterability of the polyelectrolyte and its drying, as well as to improve and simplify the adsorption
65 albumin chained product, a polymer of a fixed period of time. Table 4
17795490,. 18
preheated in inert sources of information that
an organic solvent or VNHprints into account in the examination of the mixture at 115-160C for 15-1. US patent 3554985,
60 min. 260-785, published, 1971 (prototype)

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同族专利:

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公开号 | 公开日

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EP0000977A1|1979-03-07|

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RO85538B|1984-11-30|

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ES471955A1|1979-10-16|

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CA1129145A|1982-08-03|

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US4118554A|1978-10-03|

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AU520096B2|1982-01-14|

---

JPS6330325B2|1988-06-17|

---

BR7804723A|1979-04-03|

---

JPS5460392A|1979-05-15|

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EP0000977B1|1981-09-02|

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IT1097313B|1985-08-31|

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HU180881B|1983-05-30|

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IL55193A|1981-06-29|

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IL55193D0|1978-09-29|

---

DE2861005D1|1981-11-26|

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AU3824178A|1980-01-24|

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ATA531878A|1981-06-15|

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PT68335B|1994-02-25|

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PT68335A|1978-08-01|

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AT365612B|1982-02-10|

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RO85538A|1984-10-31|

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IT7826004D0|1978-07-21|

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US3655509A|1969-05-29|1972-04-11|Monsanto Co|Process for the separation of virus from non-viral proteins|US4411795A|1980-03-10|1983-10-25|Baxter Travenol Laboratories, Inc.|Particle adsorption|

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US6740633B2|2000-05-09|2004-05-25|Basf Aktiengesellschaft|Polyelectrolyte complexes and a method for production thereof|

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WO2001085819A2|2000-05-09|2001-11-15|Basf Aktiengesellschaft|Polyelectrolyte complexes and a method for production thereof|

法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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US05/818,919|US4118554A|1977-07-25|1977-07-25|Aggregated polyelectrolytes|

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