CN110577639A - Pentamethyleneguanidine salt and preparation method and application thereof - Google Patents
Pentamethyleneguanidine salt and preparation method and application thereof Download PDFInfo
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- CN110577639A CN110577639A CN201910736548.5A CN201910736548A CN110577639A CN 110577639 A CN110577639 A CN 110577639A CN 201910736548 A CN201910736548 A CN 201910736548A CN 110577639 A CN110577639 A CN 110577639A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
- A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
- A01N47/44—Guanidine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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Abstract
the invention discloses a polypentamethyleneguanidine salt and a preparation method thereof, wherein the structural formula of the polypentamethyleneguanidine salt is shown in the specificationwherein the polymerization degree n is 40-120, and X is HCl or H3PO4、H2SO4or HO-CO-CH2‑CH3the preparation method comprises the following steps: 1) sequentially adding 1, 5-pentanediamine and an initiator into a reaction vessel, sealing the reaction vessel, stirring and heating to 95-105 ℃; 2) maintaining the reaction temperature and homogenizingQuickly adding guanidine salt, and stirring for 30 min; 3) stirring and reacting according to a temperature rise program; 4) adding a stopping agent, stopping heating, stirring for 30min, and cooling to room temperature to obtain a polymer melt; 5) transferring the polymer melt into a hydrolysis tank, adding deionized water for hydrolysis to obtain an aqueous solution of a crude product of the polypentamethyleneguanidine salt; 6) purifying, concentrating and drying to obtain the solid of the polypentamethyleneguanidine salt. The polypentamethyleneguanidine salt and the preparation method thereof adopt cheap and easily available raw materials to produce the bactericide which has the same bactericidal effect with the polyhexamethyleneguanidine hydrochloride, and have simple process and low production cost.
Description
Technical Field
the invention relates to the field of high molecular polymers, in particular to a polypentamethyleneguanidine salt and a preparation method and application thereof.
Background
the currently widely used novel guanidine polymer antibacterial agent, namely polyhexamethylene guanidine hydrochloride, has the advantages of broad sterilization spectrum, mild performance, high safety, colorless and odorless aqueous solution, no drug resistance of bacteria to the aqueous solution and the like, and is widely applied to the fields of daily chemicals, chemical additives, industrial sterilization and corrosion prevention, spinning, papermaking, tanning, agricultural planting and the like. The existing polyhexamethylene guanidine hydrochloride synthesis mode is single, and is usually synthesized by taking hexamethylene diamine as a main raw material, but the hexamethylene diamine in the market is single in source at present, and is produced and distributed by a plurality of overseas large-scale enterprises, the imported hexamethylene diamine is expensive, so that the cost of the polyhexamethylene guanidine hydrochloride is relatively high, the development and the application of the polyhexamethylene guanidine hydrochloride are limited, and in addition, once the supply of the hexamethylene diamine is limited by the overseas companies, domestic related production units face the difficulty that the production cannot be carried out. In 2018, the supply of the hexamethylene diamine raw material is limited, the price is doubled, and even the trouble that no raw material can be bought is faced, so that the domestic polyhexamethylene guanidine hydrochloride manufacturers suffer from the suffering.
Therefore, the problem that the technical personnel in the field need to solve is to provide a guanidine polymer antibacterial agent for replacing polyhexamethylene guanidine hydrochloride and a preparation method thereof by using cheap and easily available raw materials to produce the bactericide with the sterilizing effect consistent with that of the polyhexamethylene guanidine hydrochloride.
Disclosure of Invention
The invention provides a polyhexamethylene guanidine hydrochloride, a preparation method and application thereof, and aims to solve the problems that the production cost of the polyhexamethylene guanidine hydrochloride is high and the supply of the hexamethylene diamine is limited in the prior art.
the polypentamethyleneguanidine salt and the preparation method thereof provided by the invention adopt cheap and easily available raw materials to produce the bactericide which has the same bactericidal effect with the polyhexamethyleneguanidine hydrochloride, and have simple process and low production cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
The first aspect of the invention provides a polypentamethyleneguanidine salt, which has a structure shown in a formula I:
Wherein the polymerization degree n is 40-120, and X is HCl or H3PO4、H2SO4Or HO-CO-CH2-CH3。
The second aspect of the invention provides a preparation method of a polypentamethyleneguanidine salt, which comprises the following specific steps:
(1) Sequentially adding 1, 5-pentanediamine and an initiator into a reaction container, sealing the reaction container, stirring for 20min, and heating to 95-105 ℃;
(2) Maintaining the reaction temperature, adding guanidine salt at a constant speed within 30min, and continuously stirring for 30 min;
(3) Stirring and reacting according to a temperature rise program;
(4) Adding a stopping agent, stopping heating, continuously stirring for 30min, stopping reaction, and cooling to room temperature to obtain a polymer melt;
(5) transferring the polymer melt prepared in the reaction container to a hydrolysis tank, adding deionized water for hydrolysis, and obtaining an aqueous solution of a crude product of the polypentamethyleneguanidine salt;
(6) and purifying the aqueous solution of the crude product of the poly-pentamethylene guanidine salt by using an ion exchange membrane separator, and concentrating and drying the purified solution to obtain the poly-pentamethylene guanidine salt.
Further, in the step (1), the initiator is succinaldehyde or glutaraldehyde.
Further, in the step (2), the guanidine salt is guanidine hydrochloride, guanidine phosphate, guanidine sulfate or guanidine propionate.
Further, in the step (3), the temperature-programmed reaction sequentially comprises: stirring and reacting at 115-125 ℃ for 50-70 min, and stirring and reacting at 135-145 ℃ for 80-120 min.
further, in the step (4), the stopping agent is butanediol or pentanediol.
Further, in the steps (1) to (4), the molar ratio of the 1, 5-pentanediamine, the guanidine salt, the initiator and the stopping agent is 1 (0.95-1.05) to (0.01-0.012): (0.01-0.012).
further, in the step (5), the mass concentration of the aqueous solution of the crude product of the polypentamethyleneguanidine salt is 10-40%.
Further, in the step (6), the purity of the prepared solid of the polypentamethyleneguanidine salt is more than 99%.
further, the polypentamethyleneguanidine salt prepared by the method can be used as an antibacterial agent.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
(1) the pentanediamine is used for replacing the hexanediamine to produce the polymer guanidine salt, so that the cost is lower, and the selling price of the polypentamethyleneguanidine salt can be accepted by more industries and application ranges;
(2) The pentanediamine raw material is more stable and easily obtained, and has been produced by a plurality of large-scale enterprises in China, and the raw material can not be limited by foreign companies, so that the stability of the raw material source and the price can be ensured;
(3) The pentamethylene guanidine is produced by using the pentamethylene diamine, the temperature rise program and the production process are simpler, the synthesis time is shorter, and the unit productivity can be further improved;
(4) The poly (pentamethylene guanidine) has better effect of killing microorganisms;
(5) compared with polyhexamethylene guanidine hydrochloride, the compound has a very strong killing and inhibiting effect on aquatic harmful algae, is suitable for application ranges of aquaculture, water quality regulation, landscape water and the like, and can effectively fill the weak application item of the polyhexamethylene guanidine hydrochloride.
Drawings
FIG. 1 is a schematic representation of the structural formula of the monomeric units of polypentamethyleneguanidine hydrochloride of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of polypentamethyleneguanidine hydrochloride according to the present invention.
Detailed Description
the present invention will be described in detail and specifically with reference to the following examples to facilitate better understanding of the present invention, but the following examples do not limit the scope of the present invention.
Example 1
The preparation method of the polypentamethyleneguanidine hydrochloride sequentially comprises the following steps:
(1) adding 102.18 kg of 1, 5-pentanediamine and 1.03 kg of butanedialdehyde into a reaction vessel in sequence, sealing the reaction vessel, stirring for 20min to uniformly mix, and heating to 95-105 ℃;
(2) maintaining the reaction temperature, adding 95.53 kg of guanidine hydrochloride at a constant speed within 30min, and continuously stirring for 30min to ensure uniform stirring;
(3) Stirring and reacting at 115-125 ℃ for 50min, heating, and stirring and reacting at 135-145 ℃ for 80 min;
(4) Adding 1.04 kg of pentanediol into the reaction vessel, stopping heating, continuing to stir for 30min, stopping reaction, and cooling to room temperature to obtain a polymer melt;
(5) Transferring the polymer melt into a hydrolysis tank, adding deionized water for hydrolysis, and preparing an aqueous solution of a crude product of the polypentamethyleneguanidine hydrochloride;
(6) and purifying the aqueous solution of the crude product of the poly-pentamethylene guanidine hydrochloride by using an ion exchange membrane separator, and concentrating and drying the purified solution to obtain solid poly-pentamethylene guanidine hydrochloride, namely 158.60 kg of poly-pentamethylene guanidine hydrochloride with the purity of more than 99%.
the poly (pentamethylene guanidine hydrochloride) of the invention is analyzed by nuclear magnetic resonance, as shown in figure 1 and figure 2, the poly (pentamethylene guanidine hydrochloride) has six different kinds of H, which are respectively marked as a, b, c, D, e and f according to the types of H, because H (D and e) directly connected with N on guanidine and H (f) directly connected with Cl in HCl are active protons, when deuterium substituted water (D)2O) as a solvent, no peak was observed in the nmr hydrogen spectrum. Therefore, the spectrum only has three peaks corresponding to three kinds of H, namely a (at 3.2), b (at 1.6) and c (at 1.3), and a water peak (at 4.8) caused by the deuterated water solvent.
Example 2
the preparation method of the polypentamethyleneguanidine hydrochloride sequentially comprises the following steps:
(1) Adding 300.0 kg of 1, 5-pentanediamine and 3.03 kg of butanedialdehyde into a reaction vessel in sequence, sealing the reaction vessel, stirring for 20min to mix uniformly, and heating to 95-105 ℃;
(2) maintaining the reaction temperature, adding 274.87 kg of guanidine hydrochloride at a constant speed within 30min, and continuing stirring for 30min to ensure uniform stirring;
(3) Stirring and reacting at 115-125 ℃ for 65min, then heating, and stirring and reacting at 135-145 ℃ for 120 min;
(4) Adding 3.18 kg of butanediol into the reaction vessel, stopping heating, continuing stirring for 30min, stopping reaction, and cooling to room temperature to obtain a polymer melt;
(5) transferring the polymer melt into a hydrolysis tank, adding deionized water for hydrolysis, and preparing an aqueous solution of a crude product of the polypentamethyleneguanidine salt;
(6) And purifying the aqueous solution of the crude product of the poly-pentamethylene guanidine hydrochloride by using an ion exchange membrane separator, and concentrating and drying the purified solution to obtain solid poly-pentamethylene guanidine hydrochloride, namely 472.83 kg of poly-pentamethylene guanidine hydrochloride with the purity of more than 99%.
example 3
the preparation method of the poly (pentamethylene guanidine propionate) comprises the following steps in sequence:
(1) adding 102.18 kg of 1, 5-pentanediamine and 1.00 kg of glutaraldehyde into a reaction vessel in sequence, sealing the reaction vessel, stirring for 20min to uniformly mix, and heating to 95-105 ℃;
(2) Maintaining the reaction temperature, adding 131.13 kg of guanidine propionate at a constant speed within 30min, and continuing stirring for 30min to ensure uniform stirring;
(3) stirring and reacting at 115-125 ℃ for 50min, heating, and stirring and reacting at 135-145 ℃ for 80 min;
(4) Adding 0.90 kg of butanediol into the reaction vessel, stopping heating, continuing stirring for 30min, stopping reaction, and cooling to room temperature to obtain a polymer melt;
(5) Transferring the polymer melt into a hydrolysis tank, adding deionized water for hydrolysis, and preparing an aqueous solution of a crude product of the poly (pentamethylene guanidine propionate);
(6) And (3) purifying the aqueous solution of the crude product of the poly (pentamethylene guanidine propionate) by using an ion exchange membrane separator, and concentrating and drying the purified solution to obtain solid poly (pentamethylene guanidine propionate), namely 190.34 kg of poly (pentamethylene guanidine propionate) with the purity of more than 99%.
comparative test
the polypentamethyleneguanidine salt prepared according to the present invention was compared with polyhexamethyleneguanidine hydrochloride.
the polypentamethyleneguanidine salt is selected from: taking 100.0g of the solid of the polypentamethyleneguanidine hydrochloride prepared in the first example;
the polyhexamethylene guanidine hydrochloride is selected from: 100.0g of solid polyhexamethyleneguanidine hydrochloride produced by Shanghai high-polymer Biotech Co., Ltd.
Firstly, a microorganism killing test: respectively adopting 0.05% (w/w) concentration of poly-pentamethylene guanidine hydrochloride and 0.05% (w/w) concentration of poly-hexamethylene guanidine hydrochloride to act on escherichia coli, staphylococcus aureus and candida albicans for 2 min; the test results show that the sterilization rate of the polypentamethyleneguanidine hydrochloride of the present invention is higher, as shown in table 1.
TABLE 1 quantitative sterilization test of suspensions
| Sample (I) | Polypentamethyleneguanidine hydrochloride | Polyhexamethylene guanidine hydrochloride |
| Killing rate of colibacillus | 99.9％ | 96.8％ |
| kill rate of staphylococcus aureus | 99.9％ | 98.3％ |
| Candida albicans killing rate | 98.2％ | 92.6％ |
Secondly, killing and inhibiting test of harmful aquatic algae: the inhibition effect of 2ppm concentration of poly-pentamethylene guanidine hydrochloride and 2ppm concentration of poly-hexamethylene guanidine hydrochloride on microcystis aeruginosa is respectively adopted, and the test result shows that: after the polyhexamethylene guanidine hydrochloride is treated for 48 hours, the algae cells are active and normal, and no inhibition effect is generated; and about 66.67% of algae cells lose the activity after 24 hours and about 86.67% of algae cells lose the activity after 48 hours, so that the inhibition is obvious.
the embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications and substitutions to those skilled in the art are also within the scope of the present invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (10)
1. A polypentamethyleneguanidine salt having the formula (i):
wherein the polymerization degree n is 40-120, and X is HCl or H3PO4、H2SO4Or HO-CO-CH2-CH3。
2. A method for preparing the polypentamethyleneguanidine salt according to claim 1, comprising the steps of:
(1) sequentially adding 1, 5-pentanediamine and an initiator into a reaction container, sealing the reaction container, stirring for 20min, and heating to 95-105 ℃;
(2) maintaining the reaction temperature, adding guanidine salt at a constant speed within 30min, and continuously stirring for 30 min;
(3) Stirring and reacting according to a temperature rise program;
(4) Adding a stopping agent, stopping heating, continuously stirring for 30min, stopping reaction, and cooling to room temperature to obtain a polymer melt;
(5) Transferring the polymer melt prepared in the reaction container to a hydrolysis tank, adding deionized water for hydrolysis, and obtaining an aqueous solution of a crude product of the polypentamethyleneguanidine salt;
(6) and purifying the aqueous solution of the crude product of the poly-pentamethylene guanidine salt by using an ion exchange membrane separator, and concentrating and drying the purified solution to obtain the poly-pentamethylene guanidine salt.
3. The method of preparing polypentamethyleneguanidine salt according to claim 2, wherein the initiator is succinaldehyde or glutaraldehyde in step (1).
4. The method for preparing a polypentamethyleneguanidine salt according to claim 2, wherein in the step (2), the guanidine salt is guanidine hydrochloride, guanidine phosphate, guanidine sulfate or guanidine propionate.
5. the method for preparing polypentamethyleneguanidine salt according to claim 2, wherein in the step (3), the temperature-programmed reaction sequentially comprises: stirring and reacting at 115-125 ℃ for 50-70 min, and stirring and reacting at 135-145 ℃ for 80-120 min.
6. The method of preparing polypentamethyleneguanidine salt according to claim 2, wherein the stopping agent is butanediol or pentanediol in the step (4).
7. the method for preparing polypentamethyleneguanidine salt according to claim 2, wherein in the steps (1) to (4), the molar ratio of the 1, 5-pentanediamine, the guanidine salt, the initiator and the terminator is 1 (0.95-1.05) to (0.01-0.012): (0.01-0.012).
8. the method for preparing the polypentamethyleneguanidine salt according to claim 2, wherein in the step (5), the mass concentration of the aqueous solution of the crude polypentamethyleneguanidine salt is 10-40%.
9. The method of preparing polypentamethyleneguanidine salt according to claim 2, wherein the purity of the solid polypentamethyleneguanidine salt prepared in the step (6) is more than 99%.
10. Use of a polypentamethyleneguanidine salt prepared according to any one of claims 2 to 9 in an antibacterial agent.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961343A (en) * | 2021-02-19 | 2021-06-15 | 上海凯赛生物技术股份有限公司 | Pentanediamine guanidine phosphate oligomer, preparation method thereof and antibacterial polymer prepared from pentanediamine guanidine phosphate oligomer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1350022A (en) * | 2000-10-19 | 2002-05-22 | 上海塑杰科技有限公司 | Polyamine-guanidine salt polymer and its prepn |
| WO2005016994A1 (en) * | 2003-08-18 | 2005-02-24 | Sk Chemicals Co., Ltd. | Method for preparing polyalkylenebiguanidine salt |
| CN109400819A (en) * | 2018-10-25 | 2019-03-01 | 中建西部建设西南有限公司 | A kind of collection viscosity reduction antibacterial amphoteric polycarboxylic acid series high efficiency water reducing agent and preparation method thereof |
| CN109503832A (en) * | 2018-10-18 | 2019-03-22 | 上海高聚生物科技有限公司 | A kind of polycyclic oxygen propyl group hexyl guanidine hydrochloride and preparation method thereof |
-
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- 2019-08-09 CN CN201910736548.5A patent/CN110577639A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1350022A (en) * | 2000-10-19 | 2002-05-22 | 上海塑杰科技有限公司 | Polyamine-guanidine salt polymer and its prepn |
| WO2005016994A1 (en) * | 2003-08-18 | 2005-02-24 | Sk Chemicals Co., Ltd. | Method for preparing polyalkylenebiguanidine salt |
| CN109503832A (en) * | 2018-10-18 | 2019-03-22 | 上海高聚生物科技有限公司 | A kind of polycyclic oxygen propyl group hexyl guanidine hydrochloride and preparation method thereof |
| CN109400819A (en) * | 2018-10-25 | 2019-03-01 | 中建西部建设西南有限公司 | A kind of collection viscosity reduction antibacterial amphoteric polycarboxylic acid series high efficiency water reducing agent and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961343A (en) * | 2021-02-19 | 2021-06-15 | 上海凯赛生物技术股份有限公司 | Pentanediamine guanidine phosphate oligomer, preparation method thereof and antibacterial polymer prepared from pentanediamine guanidine phosphate oligomer |
| CN112961343B (en) * | 2021-02-19 | 2023-08-29 | 上海凯赛生物技术股份有限公司 | Pentanediamine guanidine phosphate oligomer, preparation method thereof and antibacterial polymer prepared from oligomer |
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