CN105482028A - Preparation method of polymer - Google Patents
Preparation method of polymer Download PDFInfo
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- CN105482028A CN105482028A CN201511003633.9A CN201511003633A CN105482028A CN 105482028 A CN105482028 A CN 105482028A CN 201511003633 A CN201511003633 A CN 201511003633A CN 105482028 A CN105482028 A CN 105482028A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
- A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/10—Aqueous solvent
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- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Pharmacology & Pharmacy (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
The invention provides a preparation method of a polymer. The preparation method comprises the following steps: 1) providing a reactant, wherein the reactant at least comprises a first compound, a second compound and a radical initiator; the first compound is shown in a formula I; the second compound is shown in a formula II; the first compound is provided in the form of a water solution or an ethanol water solution; the second compound is provided in the form of an ethanol solution; 2) mixing the reactant to obtain a mixture; 3) heating to carry out reaction; 4) after the reaction is completed, continuously heating to evaporate solvents and preparing the polymer through vacuum drying. The preparation method has the beneficial effects that a (meth)acryloyloxy ethyl trimethyl ammonium chloride water solution sold on the market is directly utilized as the reactant to undergo reaction and a solid is unnecessary to be extracted from the water solution and dissolved in organic solvents and surfactants are unnecessary to be used, thus greatly reducing the production cost; the reaction product is more applicable as a functional carrier of medicines.
Description
Technical field
The invention belongs to the functional polymer chemical technology fields such as pharmaceutical excipient, be specifically related to quaternary ammonium group (methyl) acrylate copolymer novel preparation method.
Background technology
Quaternary ammonium group (methyl) acrylate copolymer is the functional vector of medicine etc., can realize the slow controlled release of medicine, makeup and agricultural chemicals, is also used as static inhibitor, water conditioner, concrete anti-mud agent etc.
Due to quaternary ammonium group (methyl) acrylic ester solids such as methacryloxyethyl trimethyl ammonium chloride (or being called the trimethylammonio ethyl ester of methacrylic acid chlorination) and acryloyloxyethyl trimethyl ammonium chlorides (or being called the trimethylammonio ethyl ester of vinylformic acid chlorination), be dissolved in the acrylic monomer such as acrylate, methacrylic ester hardly, therefore be difficult to carry out conventional free radical mass polymerization.Usually, adopt the organic solvents such as dehydrated alcohol that the quaternary ammonium group methacrylic esters such as the trimethylammonio ethyl ester of methacrylic acid chlorination are mixed with solution, again with treat that the oil-soluble acrylic ester monomer of copolymerization mixes and form solution system, cause radical polymerization by oil-soluble initiator and prepare ammonio methacrylate multipolymer; Or, quaternary ammonium group methacrylic ester is made into the aqueous solution, under the effect of tensio-active agent with treat that the oil-soluble acrylic ester monomer of copolymerization mixes and form emulsion system, cause radical polymerization by oil soluble or water miscible initiator and prepare ammonio methacrylate multipolymer.
Publication number is CN101314052A, publication date is on December 3rd, 2008, name is called that the Chinese patent application of " a kind of transdermal drug administration carrier system and preparation method thereof " discloses a kind of acrylic based binders composition, described acrylic based binders polymerization single polymerization monomer used comprises a small amount of trimethylammonio ethyl ester of methacrylic acid chlorination, polymerization process used comprises solution polymerization, letex polymerization or graft polymerization, solvent for use comprises ethanol and Virahol, or acetone, ethyl acetate etc., be solvent with vinyl acetic monomer in the solution polymerization example implemented.
(the syntheses and properties of methacryloxyethyl trimethyl ammonium chloride and methylmethacrylate copolymer such as Li Mingxian, University Of Hebei's journal (natural science edition) 2002,22 (1): 36-39) chloroform and alcohol mixed solvent (1: 1 is adopted, V/V) methacryloxyethyl trimethyl ammonium chloride and methyl methacrylate copolymer is carried out, monomer mass mark 45% (m/V), be warming up to 60 DEG C, add initiator A IBN (consumption is monomer mass 1%), react 6h under constant temperature, monomer conversion can reach 97%.Product need through dissolve with ethanol-acetone precipitation separation and purification.Relate to separation and the recovery of mixed solvent simultaneously.But this system is not suitable for preparation and the production of pharmaceutical carrier because of the introducing of chloroform.
Although solution polymerization then with to the chain tra nsfer of solvent and speed slow and the deficiency of dry powdery or granular resin should not be made, heat radiation is easily, even structure, quality product be guaranteed.Be CN103102445A at publication number, publication date is on May 15th, 2013, name is called in the Chinese patent application of " a kind of pH independent form gathers first acrylate and preparation method thereof ", ethyl propenoate, methyl methacrylate and methacrylic acid chlorination dimethylamino ethyl ester are dissolved in dehydrated alcohol (being equivalent to 60 ~ 80% of monomer total amount), cause with azo-bis-iso-dimethyl, carry out solution polymerization.Wherein, the mass ratio of ethyl propenoate, methyl methacrylate, methacrylic acid chlorination dimethylamino ethyl ester and ethanol, azo-bis-iso-dimethyl is l:1.688-2.012:0.202-0.598:1.369-2.568:0.0256-0.0365.Concrete steps are: (1) gets ethyl propenoate, methyl methacrylate, methacrylic acid chlorination dimethylamino ethyl ester and azo-bis-iso-dimethyl by described weight proportion and ethanol drops in reactor, maintain 2-4 hour when being warming up to 55 ± 3 DEG C, complete first paragraph polymerization; Be warming up to 70 ± 3 DEG C again, continue reaction 2-3 hour, until be polymerized; (2) intensification 80-85 DEG C concentrates, and when to steam ethanol be the 45-55% of input amount, stops concentrated, discharging while hot, shaping, then dries, broken, i.e. finished product.
Publication number is CN101475662A, and publication date is on July 8th, 2009, the Chinese patent application introduction that name is called " preparation method of the medicinal poly-first acryloyl ammonium ester of a kind of low film formation temperature, medium perviousness " be " solution-mass polymerization " technique.Wherein, ethyl propenoate/butyl acrylate/methyl methacrylate/trimethylammonio ethyl ester of methacrylic acid chlorination (mol ratio) is (0.25-1.5): (0.5-1.5): (1-2): (0.10-0.19); In earlier stage be to mix with ethyl propenoate, methyl methacrylate with dissolve with ethanol solid monomer methacrylic acid chlorination dimethylamino ethyl ester and initiator azobisisobutyronitrile (AIBN) (being equivalent to 5 ~ 15% of monomer total amount) to carry out solution polymerization, with " make it heat radiation easily, prevent polymerization autoacceleration, implode, Branching and cross-linking "; React the desolvation that heats up mid-term, reaction progressively enters the body casting polymerization in later stage.
In above-described prior art, when synthesizing quaternary ammonium group (methyl) acrylate copolymer, solid quaternary ammonium group (methyl) acrylic ester monomer used could be mixed into solution system with oil soluble acrylic ester monomer after all needing first solubilizing agent to dissolve.Quaternary ammonium group (methyl) acrylate copolymer is insoluble to (methyl) acrylate because of monomer (methyl) acryloyloxyethyl trimethyl ammonium chloride, and its synthesis adopts mass polymerization system or adopts anhydrous organic solvent to form solution polymerization system.(methyl) acryloyloxyethyl trimethyl ammonium chloride monomer very easily moisture absorption, to accumulating, pack and open that to weigh the dehumidification requirements of environment high, be difficult to precise, thus market sale mostly be 75 ~ 80% (methyl) acryloyloxyethyl trimethyl aqueous ammonium chloride solution.
Therefore, those skilled in the art be devoted to exploitation one be suitable in water environment, utilize quaternary ammonium group (methyl) acrylate and acrylate to carry out the method for copolymerization.
Summary of the invention
Because the above-mentioned defect of prior art, the invention provides a kind of new method for producing polymer, the technical problem that solve realizes utilizing quaternary ammonium group (methyl) acrylate and acrylate carry out copolyreaction and form multipolymer in water environment.
For solving the problem, the technical scheme that the present invention takes is: a kind of preparation method of polymkeric substance, comprises the steps:
1) provide reactant, described reactant comprises at least the first compound, the second compound and radical initiator, and the first compound is as shown in the formula shown in I, and the second compound is as shown in the formula shown in II; Wherein, described first compound provides with the form of the aqueous solution or aqueous ethanolic solution; Described second compound provides with the form of ethanolic soln;
Wherein, R1 is H or methyl; R2 is H or methyl; R3 is the alkyl of C1 ~ C4;
2) reactant is mixed to get mixture;
3) heating is reacted;
4), after having reacted, continue heating evaporation solvent, obtain described polymkeric substance through vacuum-drying.
Preferably, in described mixture, the mass ratio of described first compound, the second compound, radical initiator, ethanol, water is: 0.05 ~ 0.5:1.98 ~ 2.02:0.01 ~ 0.05:3 ~ 6:0.15 ~ 0.6.
Preferably, in described mixture, the mass ratio of described first compound, the second compound, radical initiator, ethanol, water is: 0.45:2:0.03:4.5:0.15.
Preferably, described reactant also comprises the 3rd compound, and the 3rd compound is such as formula shown in II, and described 3rd compound provides with the form of ethanolic soln.More preferably, in described mixture, the mass ratio of described first compound, the second compound, the 3rd compound, radical initiator, ethanol, water is: 0.05 ~ 0.5:1.98 ~ 2.02:0.98 ~ 1.02:0.01 ~ 0.05:3 ~ 6:0.15 ~ 0.6.More preferably, in described mixture, the mass ratio of described first compound, the second compound, the 3rd compound, radical initiator, ethanol, water is: 0.45:2:1:0.03:4.5:0.15.
Preferably, described radical initiator is Diisopropyl azodicarboxylate.
Preferably, in step 3) in, the temperature of described reaction is 50 ~ 85 DEG C, and the reaction times is 6 ~ 12h.More preferably, step 3) concrete operations be: react 1h after being warming up to 55 ± 5 DEG C, then react 3 ~ 6h, back flow reaction 2 ~ 5h after then rising to 80 ~ 85 DEG C after rising to 70 ± 5 DEG C.
Preferably, in step 4) in, the equipment that vacuum-drying adopts is wiped film evaporator or belt vacuum moisture eliminator.
Applicant of the present invention is surprised to find that when utilizing existing method to carry out and relating to the copolyreaction of (methyl) acryloyloxyethyl trimethyl ammonium chloride and acrylate, although (methyl) acryloyloxyethyl trimethyl ammonium chloride is dissolved in acrylate hardly, need by organic solvents such as dehydrated alcohols, or by tensio-active agent effect with treat that the oil-soluble acrylic ester monomer of copolymerization mixes and form emulsion system, if but during crylic acid ester mixture directly by the aqueous solution of (methyl) acryloyloxyethyl trimethyl ammonium chloride and dissolve with ethanol, by dissolving each other of water and ethanol, also the good reaction system of mixedness can be formed.
Beneficial effect of the present invention is: directly utilize (methyl) acryloyloxyethyl trimethyl aqueous ammonium chloride solution of market sale to react as reactant, organic solvent need not be dissolved into again from extraction with aqueous solution solid, do not need by tensio-active agent yet, greatly reduce production cost, reaction product is more suitable for the functional vector of medicine.
Below the technique effect of design of the present invention, concrete structure and generation is described further, to understand object of the present invention, characteristic sum effect fully.
Embodiment
Embodiment one
1, reactant prepares
(1) first compound
First compound is (methyl) acryloyloxyethyl trimethyl ammonium chloride, buy (methyl) acryloyloxyethyl trimethyl aqueous ammonium chloride solution that mass percent is 75%, take 600g, wherein containing (methyl) acryloyloxyethyl trimethyl ammonium chloride 450g.
(2) second compounds and the 3rd compound
Second compound is methyl methacrylate, and the 3rd compound is ethyl propenoate, takes methyl methacrylate 2kg, takes and ethyl propenoate 1kg, is dissolved in 2.5kg ethanol.
(3) radical initiator
Radical initiator is Diisopropyl azodicarboxylate, takes Diisopropyl azodicarboxylate 30g, is dissolved in 0.5kg ethanol.
2, react
Under agitation successively the first compound, the second compound and the 3rd compound, radical initiator are dropped into reactor, after being warming up to 55 ± 5 DEG C, react 1h, then react 3 ~ 6h, back flow reaction 2 ~ 5h after then rising to 80 ~ 85 DEG C after rising to 70 ± 5 DEG C.
3, product obtains
After polyreaction terminates, steam 50 ~ 90% of ethanol otal investment, then, adopt wiped film evaporator in 90 ~ 120 DEG C of vacuum-drying 1 ~ 5h, obtain the multipolymer that product is the first compound, the second compound and the 3rd compound, altogether 3.18kg.
Embodiment two
1, reactant prepares
(1) first compound
First compound is acryloyloxyethyl trimethyl ammonium chloride, buys the acryloyloxyethyl trimethyl aqueous ammonium chloride solution that mass percent is 75%, takes 600g, wherein containing acryloyloxyethyl trimethyl ammonium chloride 450g.
(2) second compounds and the 3rd compound
Second compound is methyl methacrylate, and the 3rd compound is butyl acrylate, takes methyl methacrylate 2kg, takes and butyl acrylate 1kg, is dissolved in 4kg ethanol.
(3) radical initiator
Radical initiator is Diisopropyl azodicarboxylate, takes Diisopropyl azodicarboxylate 50g, is dissolved in 1kg ethanol.
2, react
Under agitation successively the first compound, the second compound and the 3rd compound, radical initiator are dropped into reactor, after being warming up to 55 ± 5 DEG C, react 1h, then react 3 ~ 6h after rising to 70 ± 5 DEG C, then rise to 80 ~ 85 DEG C of back flow reaction 2 ~ 5h.
3, product obtains
After polyreaction terminates, steam 50 ~ 90% of ethanol otal investment, then, adopt belt vacuum moisture eliminator in 90 ~ 120 DEG C of vacuum-drying 1 ~ 5h, with exhaust screw extruding pelletization and recycling design, obtain the multipolymer that product is the first compound, the second compound and the 3rd compound, altogether 3.21kg.
Embodiment three
1, reactant prepares
(1) first compound
First compound is (methyl) acryloyloxyethyl trimethyl ammonium chloride, buy (methyl) acryloyloxyethyl trimethyl aqueous ammonium chloride solution that mass percent is 75%, take 600g, wherein containing (methyl) acryloyloxyethyl trimethyl ammonium chloride 450g.
(2) second compounds and the 3rd compound
Second compound is methyl methacrylate, and the 3rd compound is ethyl propenoate, takes methyl methacrylate 2kg, takes and ethyl propenoate 1kg, is dissolved in 4kg ethanol.
(3) radical initiator
Radical initiator is Diisopropyl azodicarboxylate, takes Diisopropyl azodicarboxylate 10g, is dissolved in 1kg ethanol.
2, react
Under agitation successively the first compound, the second compound and the 3rd compound, radical initiator are dropped into reactor, after being warming up to 55 ± 5 DEG C, react 1h, then rise to 70 ± 5 DEG C of reactions rear 3 ~ 6h, back flow reaction 2 ~ 5h after then rising to 80 ~ 85 DEG C.
3, product obtains
After polyreaction terminates, steam 50 ~ 90% of ethanol otal investment, then, adopt belt vacuum moisture eliminator in 90 ~ 120 DEG C of vacuum-drying 1 ~ 5h, with exhaust screw extruding pelletization and recycling design, obtain the multipolymer that product is the first compound, the second compound and the 3rd compound, altogether 3.12kg.
Embodiment four
1, reactant prepares
(1) first compound
First compound is acryloyloxyethyl trimethyl ammonium chloride, buys the acryloyloxyethyl trimethyl aqueous ammonium chloride solution that mass percent is 75%, takes 600g, wherein containing acryloyloxyethyl trimethyl ammonium chloride 450g.
(2) second compounds
Second compound is methyl methacrylate, takes methyl methacrylate 2kg, is dissolved in 2.5kg ethanol.
(3) radical initiator
Radical initiator is Diisopropyl azodicarboxylate, takes Diisopropyl azodicarboxylate 50g, is dissolved in 0.5kg ethanol.
2, react
Under agitation successively the first compound, the second compound, radical initiator are dropped into reactor, after being warming up to 55 ± 5 DEG C, react 1h, then react 3 ~ 6h, back flow reaction 2 ~ 5h after then rising to 80 ~ 85 DEG C after rising to 70 ± 5 DEG C.
3, product obtains
After polyreaction terminates, steam 50 ~ 90% of ethanol otal investment, then, adopt wiped film evaporator in 90 ~ 120 DEG C of vacuum-drying 1 ~ 5h, obtain the multipolymer that product is the first compound and the second compound, altogether 2.08kg.
More than describe preferred embodiment of the present invention in detail.Should be appreciated that those of ordinary skill in the art just design according to the present invention can make many modifications and variations without the need to creative work.Therefore, all technician in the art, all should by the determined protection domain of claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. a preparation method for polymkeric substance, is characterized in that, comprises the steps:
1) provide reactant, described reactant comprises at least the first compound, the second compound and radical initiator, and the first compound is as shown in the formula shown in I, and the second compound is as shown in the formula shown in II; Wherein, described first compound provides with the form of the aqueous solution or aqueous ethanolic solution; Described second compound provides with the form of ethanolic soln;
Wherein, R1 is H or methyl; R2 is H or methyl; R3 is the alkyl of C1 ~ C4;
2) reactant is mixed to get mixture;
3) heating is reacted;
4), after having reacted, continue heating evaporation solvent, obtain described polymkeric substance through vacuum-drying.
2. preparation method according to claim 1, it is characterized in that, in described mixture, the mass ratio of described first compound, the second compound, radical initiator, ethanol, water is: 0.05 ~ 0.5:1.98 ~ 2.02:0.01 ~ 0.05:3 ~ 6:0.15 ~ 0.6.
3. preparation method according to claim 1, is characterized in that, in described mixture, the mass ratio of described first compound, the second compound, radical initiator, ethanol, water is: 0.45:2:0.03:4.5:0.15.
4. preparation method according to claim 1, is characterized in that, described reactant also comprises the 3rd compound, and the 3rd compound is such as formula shown in II, and described 3rd compound provides with the form of ethanolic soln.
5. preparation method according to claim 4, it is characterized in that, in described mixture, the mass ratio of described first compound, the second compound, the 3rd compound, radical initiator, ethanol, water is: 0.05 ~ 0.5:1.98 ~ 2.02:0.98 ~ 1.02:0.01 ~ 0.05:3 ~ 6:0.15 ~ 0.6.
6. preparation method according to claim 4, is characterized in that, in described mixture, the mass ratio of described first compound, the second compound, the 3rd compound, radical initiator, ethanol, water is: 0.45:2:1:0.03:4.5:0.15.
7. preparation method according to claim 1, is characterized in that, described radical initiator is Diisopropyl azodicarboxylate.
8. preparation method according to claim 1, is characterized in that, in step 3) in, the temperature of described reaction is 50 ~ 85 DEG C, and the reaction times is 6 ~ 12h.
9. preparation method according to claim 8, is characterized in that, step 3) concrete operations be: react 1h after being warming up to 55 ± 5 DEG C, then after rising to 70 ± 5 DEG C react 3 ~ 6h, back flow reaction 2 ~ 5h after then rising to 80 ~ 85 DEG C.
10. preparation method according to claim 1, is characterized in that, in step 4) in, the equipment that vacuum-drying adopts is wiped film evaporator or belt vacuum moisture eliminator.
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| CN201511003633.9A CN105482028A (en) | 2015-12-26 | 2015-12-26 | Preparation method of polymer |
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| CN201511003633.9A CN105482028A (en) | 2015-12-26 | 2015-12-26 | Preparation method of polymer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040070A (en) * | 2019-12-25 | 2020-04-21 | 悦康药业集团安徽天然制药有限公司 | Preparation method of ammonium polymethacrylate |
Citations (2)
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| CN1328069A (en) * | 2001-07-02 | 2001-12-26 | 山东轻工业学院 | Process for preparing coating material as coating film of gastric disintegrable water medicine |
| CN1918203A (en) * | 2004-02-09 | 2007-02-21 | 三菱化学株式会社 | Water-soluble resin, cosmetic hair preparation containing the same, and silicone oil adsorption aid |
-
2015
- 2015-12-26 CN CN201511003633.9A patent/CN105482028A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328069A (en) * | 2001-07-02 | 2001-12-26 | 山东轻工业学院 | Process for preparing coating material as coating film of gastric disintegrable water medicine |
| CN1918203A (en) * | 2004-02-09 | 2007-02-21 | 三菱化学株式会社 | Water-soluble resin, cosmetic hair preparation containing the same, and silicone oil adsorption aid |
Non-Patent Citations (2)
| Title |
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| 全国工业表面活性剂生产技术协作组，全国工业表面活性剂中心编: "《2000工业表面活性剂技术经济文集》", 30 October 2000 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111040070A (en) * | 2019-12-25 | 2020-04-21 | 悦康药业集团安徽天然制药有限公司 | Preparation method of ammonium polymethacrylate |
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