CN101857540A - Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization - Google Patents
Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization Download PDFInfo
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Abstract
The invention discloses a method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from waste nylon-66 serving as a raw amerial through depolymerization, which is characterized by comprising the following steps of: depolymerizing the waste nylon-66 by using hydrochloric acid to obtain refined adipic acid and hexamethylenediamine hydrochloride; polymerizing the hexamethylenediamine hydrochloride and dicyandiamide (in a molar ratio of 1:1) at the temperature of between 170 and 190DEG C for 1 to 3 hours to obtain a white or pale yellow solid polyhexamethylene diguanidine chloride; and adding dicyandiamide and ammonium chloride powder in a molar ratio of 1:2 into a reactor, performing reaction at high temperature for 1 to 3 hours, slowly adding hexamethylenediamine hydrochloride powder, continuously reacting for 3 to 7 hours to obtain a white or pale yellow solid polyhexamethylene guanidine chloride. The method improves production efficiency, reduces production cost, and solves the problems of difficult separation of the product hexamethylenediamine due to depolymerization, low yield and poor benefit; and the technological process is environment-friendly, simple and convenient, and is suitable for industrial production.
Description
Technical field
The present invention relates to utilize the nylon-66 waste through depolymerization to produce the novel method of hexanodioic acid, hexamethylene-diamine hydrochloride and polyhexamethylene list (two) guanidinesalt hydrochlorate sterilizing agent, especially introduced the novel method of a kind of suitable suitability for industrialized production polyhexamethylene list (two) guanidinesalt hydrochlorate.
Background technology
Nylon-66 is the macromolecular material that is formed by hexanodioic acid and hexanediamine polycondensation, in the synthetic and course of processing, can produce unacceptable product and tankage at it.Simultaneously, various nylon 66 goods are difficult to handle after being used, and not only cause waste, and environment is polluted.Therefore, recycle the extensive concern that waste and old nylon-66 has caused society.How it is turned waste into wealth, brings into play the focus that its economic benefit that has and social benefit become research.Nylon reclaims main method at present has: melt pelletization regeneration; Chemical recovery; Energy recovery; Landfill disposal etc.Chemical recycling is adopted widely, and for example: Minte Nylon Industry Co., Ltd., Ningbo has applied for a kind ofly producing the Chinese patent of the technology of hexanodioic acid, hexanediamine with nylon-66 disaggregation, and the patent No. is CN1611477; Sky, Liaoning becomes chemical industry company limited to declare a kind of Chinese patent of production method of useless nylon recycling, and the patent No. is CN1569802.Also have some to utilize the nylon-66 of chemical recycling disaggregation of waste and old.Yet, when the depolymerization nylon-66 is produced hexanodioic acid and hexanediamine monomer, exist still that productive rate is low, separation difficulty, problem that purity is not high.
Guanidine class Application of disinfectants has had the history in more than 50 year, and what the initial stage used mainly is poly hexamethylene biguanide class sterilizing agent, as 1,6-pair (just-to the chlorobenzene biguanides) hexane (having another name called chlorhexidine, Tubulicid).In recent years, find that in the world polyhexamethylene list guanidine class sterilizing agent has higher fungicidal effectiveness, and fungicidal spectrum is wide, minimum inhibitory concentration (MIC) is low, speed of action is fast, the photo-thermal stable chemical performance, soluble in water, have no side effect, characteristics such as non-corrosiveness, toxicity are low, meet in the international community requirement to the sterilization and disinfection product, receive much attention, become sterilizing agent most popular on the current market, the trend that replaces the biguanides sterilizing agent is gradually arranged greatly.That has developed has two kinds of polyhexamethylene list guanidine phosphoric acid salt and polyhexamethylene list guanidinesalt hydrochlorates, and polyhexamethylene guanidine phosphoric acid salt is because the existence of phosphate radical, toxicity is bigger, eyes and skin mucosa had pungency, also can produce destroy simultaneously, thereby be careful, with good conditionsi in the world its use to environment.Polyhexamethylene list guanidinesalt hydrochlorate has become the nonpoisonous and tasteless sterilised products that is widely used.Had multiple process for producing method for Polyhaxemethylenguanidine Hydrochloride salt, for example the Polyhaxemethylenguanidine Hydrochloride salt sold of current market is that to adopt publication number be that the described preparation technology of CN02135317 produces; Publication number is that the patent of CN1390876A has been introduced a kind of preparation sterilant Polyhaxemethylenguanidine Hydrochloride salt and preparation method thereof; A kind of Polyhaxemethylenguanidine Hydrochloride salt and preparation method thereof has been invented by Tongling Biological High Polymer Technology Co., Ltd., and publication number is CN101245141A, and it is by Guanidinium hydrochloride and triethylenediamine and add initiator and at high temperature be polymerized; Publication number be CN101289536A patented invention by Guanidinium hydrochloride and 1, the method that Polyhaxemethylenguanidine Hydrochloride salt is produced in the polymerization under hot conditions of 6-two amido hexanes.
The above-mentioned method for preparing Polyhaxemethylenguanidine Hydrochloride salt respectively has relative merits because of preparation technology is different.The present invention is on existing patent of invention basis, success to the depolymerized product exploitation that makes the transition, the technology of recycling the nylon-66 waste is improved, utilized depolymerization product hexamethylene-diamine hydrochloride direct production sterilizing agent polyhexamethylene list (two) guanidinesalt hydrochlorate.Both overcome the shortcoming that yield is low, separation is difficult that the intimate diacid of depolymerization nylon-66 manufacture order, hexanediamine exist, solved the problem that productivity effect is poor, cost is high again.With the waste material nylon-66 is that industrialized producing technology that starting material prepare polyhexamethylene list (two) guanidinesalt hydrochlorate there is no in other documents or patent and reported.
Summary of the invention
Purpose of the present invention mainly is to provide a kind of at the existing problem of present nylon-66 recycling to produce hexanodioic acid with nylon-66 disaggregation, the method of hexamethylene-diamine hydrochloride and polyhexamethylene list (two) guanidinesalt hydrochlorate, it is on existing technical foundation, nylon-66 disaggregation is produced hexanodioic acid, the technological process of hexanediamine is improved, adopt hydrochloric acid to come the depolymerization nylon-66, and its depolymerization product hexamethylene-diamine hydrochloride is used to prepare polyhexamethylene list (two) guanidinesalt hydrochlorate, both solved and had the difficult separation of hexanediamine in the nylon-66 removal process, yield is low, problem of poor benefits has solved the problem of production sterilizing agent polyhexamethylene list (two) guanidinesalt hydrochlorate raw material sources again.
The technical scheme that the present invention is directed to above-mentioned technical problem employing is: a kind of method of producing hexanodioic acid, hexamethylene-diamine hydrochloride and polyhexamethylene list (two) guanidinesalt hydrochlorate with nylon-66 disaggregation, it is characterized in that including acidolysis workshop section, hexanodioic acid and separate and separate with recrystallization workshop section, hexamethylene-diamine hydrochloride and purifying workshop section, polyhexamethylene list (two) guanidinesalt hydrochlorate prepare workshop section, each workshop section's step is as described below:
(1), acidolysis workshop section, mass concentration 18-25% aqueous hydrochloric acid is added the top to be equipped with in the reactor of reflux exchanger and hydrogen chloride gas absorption unit, add nylon-66 while heating then, under the condition of normal pressure and 100-110 ℃, reacted 8～12 hours, obtain acid hydrolysis solution;
(2), hexanodioic acid separates and recrystallization workshop section, reactor is slowly vacuumized, treat that absolute pressure kept later on 20-30 minute less than 10KPa, acid hydrolysis solution in the step (1) is cooled to 30-40 ℃, separate to obtain thick adipic acid crystals with coarse filter, decolour again, recrystallization, oven dry obtain refining hexanodioic acid;
(3), hexamethylene-diamine hydrochloride separates and purifying workshop section, the 30-40% of the thick hexamethylene-diamine hydrochloride solution decompression evaporation concentration that obtains in the step (2) to cumulative volume, be cooled to 30-40 ℃, the industrial alcohol that adds 3-5 times of volume is separated out thick hexamethylene-diamine hydrochloride crystal, more after filtration, decolouring, recrystallization, drying obtain refining hexamethylene-diamine hydrochloride;
(4), polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section, the hexamethylene-diamine hydrochloride and the technical grade Dyhard RU 100 that obtain in the step (3) are roughly 1: 1 add-on input reactor according to mol ratio, nitrogen protection, stirred 10-30 minute, be warming up to 170-190 ℃, stirring reaction 3-7 hour, obtain hexamethylene and ammonium chloride mixt, slowly be pressed in the separating tank that fills industrial alcohol with the reaction solution of nitrogen while hot molten state, fully stir after-filtration, filter residue gets byproduct of reaction ammonium chloride behind the water recrystallization purifying, ethanol is removed in the underpressure distillation of hexamethylene ethanolic soln, obtained white or faint yellow solid hexamethylene; Calculate productive rate greater than 95% with hexamethylene-diamine hydrochloride.
(5), polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section, in reactor, drop into Dyhard RU 100 and the ammonium chloride powder that mol ratio was roughly 1: 2, nitrogen protection, stirred 10-30 minute, be warming up to 170-190 ℃, stirring reaction 1-3 hour, slowly add the hexamethylene-diamine hydrochloride powder (hexamethylene-diamine hydrochloride: the mol ratio of ammonium chloride 1: 1) that obtains in the step (3), continue reaction 3-7 hour, obtain polyhexamethylene list guanidinesalt hydrochlorate and ammonium chloride mixt, slowly be pressed in the separating tank that fills industrial alcohol with the reaction solution of nitrogen while hot molten state, fully stir after-filtration, filter residue gets byproduct of reaction ammonium chloride behind the water recrystallization purifying, with polyhexamethylene list guanidinesalt hydrochlorate ethanol filtrate, ethanol is removed in underpressure distillation, obtains white or faint yellow solid polyhexamethylene list guanidinesalt hydrochlorate; Calculate productive rate greater than 95% with hexamethylene-diamine hydrochloride.
Step (4) or step (5) can be to select to use.
(6), recycle step, with used ethanol reuse after the rectifying tower weight steams in the ethanol filtrate of step (3) and step (4) or the step (5), tower still residue refrigerated separation, evaporation dilute hydrochloric acid solution reuse step in the lump (1) in filtrate and step (2) and the step (3), the filter residue in filter residue and step (4) or the step (5) merge to be handled.
Evaporation concentration described in the step (3) is to the 30-40% of cumulative volume, preferred 35%; The industrial alcohol that adds 3-5 times of volume, preferred 4 times.
Gac is adopted in decolouring described in the step (3), and add-on is the 3-5% of thick hexamethylene-diamine hydrochloride crystal mass.
Temperature of reaction described in step (4) or the step (5) and reaction times determine that according to end-use the reaction times, molecular weight long more, the high more then polyhexamethylene of temperature of reaction list (two) guanidinesalt hydrochlorate was high more.
Tower still residue treatment process described in the step (6) need be after 5-7 production cycle, as offal treatment.
Involved equipment configurations such as reactor, mechanical stirring and pipeline in step (4) or the step (5) all need to adopt high temperature resistant non-metallic material and reaction system isolation such as enamel.
During adding hexamethylene-diamine hydrochloride powder described in the step (5), according to hexamethylene-diamine hydrochloride: the mol ratio that the ammonium chloride powder was roughly 1: 1 feeds intake, and agitation condition control down evenly added in 30 minutes.
Filter residue described in the step (5), the ammonium chloride reuse that obtains behind the water recrystallization purifying is to step (5).
Compare with technology with prior art, advantage of the present invention and effect are:
The present invention mainly be at present waste material nylon-66 disaggregation produce hexanodioic acid, hexanediamine productive rate lower, separate the problem of difficulty, productivity effect difference.On existing technical foundation, nylon-66 disaggregation is produced the technological process of hexanodioic acid, hexanediamine and improved, the exploitation that makes the transition of its depolymerized product.Adopt hydrochloric acid to come the depolymerization nylon-66, and its depolymerization product hexamethylene-diamine hydrochloride is directly used in preparation polyhexamethylene list (two) guanidinesalt hydrochlorate, both solved the problem of nylon-66 recycling, solve the problem of production sterilizing agent polyhexamethylene list (two) guanidinesalt hydrochlorate raw material sources again, improved comprehensive productivity effect and profit margin.The waste that produces in the production process is few, and pollution on the environment is little, has reduced production cost, has improved production efficiency, and production technique is suitable for suitability for industrialized production.In addition, prepared polyhexamethylene list (two) guanidinesalt hydrochlorate can be made into stable solid powdery, is convenient to transportation like this, uses, can be in field widespread uses such as weaving, daily use chemicals, water treatments.
Description of drawings
Fig. 1 correlated response process flow diagram;
Fig. 2 chemical reaction process synoptic diagram of being correlated with.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1
(1) depolymerization workshop section: the 30% industrial by-product hydrochloric acid that adds 1500Kg in the reactor of reflux exchanger and hydrogen chloride gas absorption unit is housed at the top, add 500Kg water, heating, add useless nylon-66 fragment 1000Kg while stirring, control reaction temperature is at 100-110 ℃, normal pressure, time 8h, reaction conversion ratio reaches more than 90%, obtains acid hydrolysis solution.Acid hydrolysis solution filters by coarse filter and is pressed into crystallizer, accelerate crystallisation by cooling speed by the top decompression of bleeding, froth breaking is collected in the liquid of carrying secretly in the pumping process screen filtration surge tank externally, feeds to be crystallized jar of temperature of recirculated cooling water and reduce to till 30-40 ℃ in chuck.After finishing, crystallization separates thick crystallization of adipic acid and thick hexamethylene-diamine hydrochloride solution with chamber filter press.
(2) the refining workshop section of hexanodioic acid: water temperature is heated to more than 90 ℃ in the still that will decolour, progressively add the thick hexanodioic acid solid that is equivalent to water yield weight ratio 50% this moment, wait to dissolve the back and add the gac that is equivalent to weight ratio 4%, stir decolouring, use plate filter isolating active charcoal and insoluble impurities, crystallisation by cooling, filtration, oven dry again obtains the pure product of the hexanodioic acid of purity more than 99.7%, 490Kg, yield 76%.
(3) the refining workshop section of hexamethylene-diamine hydrochloride: the liquid merging reduction vaporization of collecting in the thick hexamethylene-diamine hydrochloride solution that depolymerization operation (1) is obtained and the screen filtration surge tank is concentrated into 35% of cumulative volume, be cooled to 35 ℃, the industrial alcohol that adds 3-5 times of volume is separated out thick hexamethylene-diamine hydrochloride crystal, again after filtration, add the activated carbon decolorizing, recrystallization, the drying that are equivalent to weight ratio 4% and obtain refining hexamethylene-diamine hydrochloride, purity is greater than 99%, 610Kg, yield 73%.
(4) polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section; the hexamethylene-diamine hydrochloride and the technical grade Dyhard RU 100 that obtain in the hexamethylene-diamine hydrochloride refining step are dropped into reactor according to 1: 1 add-on of mol ratio; nitrogen protection; stir 30min; be warming up to 180 ℃; stirring reaction 5h; obtain hexamethylene and ammonium chloride mixt; slowly be pressed in the separating tank that fills industrial alcohol with the reaction solution of nitrogen while hot molten state; fully stir after-filtration; filter residue gets byproduct of reaction ammonium chloride behind the water recrystallization purifying; ethanol is removed in the underpressure distillation of hexamethylene ethanolic soln; obtain the white solid hexamethylene, yield is greater than 95%, with its crushing packing.
Depolymerization workshop section (1), the refining workshop section (2) of hexanodioic acid and the refining workshop section (3) of hexamethylene-diamine hydrochloride are with embodiment 1.
(4) polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section; the input mol ratio is 1: 2 Dyhard RU 100 and an ammonium chloride powder in reactor; nitrogen protection; stir 25min; be warming up to 180 ℃; stirring reaction 2h; slowly add the hexamethylene-diamine hydrochloride powder that obtains in the refining workshop section (3) of hexamethylene-diamine hydrochloride; continue reaction 5h; obtain polyhexamethylene list guanidinesalt hydrochlorate and ammonium chloride mixt; slowly be pressed in the separating tank that fills industrial alcohol with the reaction solution of nitrogen while hot, fully stir after-filtration, with polyhexamethylene list guanidinesalt hydrochlorate ethanol filtrate molten state; ethanol is removed in underpressure distillation; obtain light yellow solid polyhexamethylene list guanidinesalt hydrochlorate, yield is greater than 92%, with its crushing packing.
Embodiment 3
Depolymerization workshop section (1), the refining workshop section (2) of hexanodioic acid, the refining workshop section (3) of hexanediamine vitriol and polyhexamethylene list (two) guanidine sulfate prepare workshop section (4) with embodiment 2.
With the thick ammonium chloride white powder that obtains after the above-mentioned filtration, add 300Kg hot water (80 ± 5 ℃), stirring and dissolving is filtered, and till reduction vaporization was concentrated into and just has crystallization to separate out, cooling was filtered, and vacuum-drying gets 150Kg POV ammonium solid, and yield is more than 86%.According to the reaction equivalence ratio, suitably replenish fresh ammonium chloride, reuse to polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section (4).
This paper mol ratio substantially is meant that the permission mol ratio fluctuates 10% on equivalent reaction basis.
Claims (9)
1. method of producing hexanodioic acid, hexamethylene-diamine hydrochloride and polyhexamethylene list (two) guanidinesalt hydrochlorate with nylon-66 disaggregation, it is characterized in that it includes acidolysis workshop section, hexanodioic acid and separates and separate with recrystallization workshop section, hexamethylene-diamine hydrochloride and purifying workshop section and polyhexamethylene list (two) guanidinesalt hydrochlorate prepare workshop section, each workshop section's step is as described below:
(1), acidolysis workshop section, mass concentration 18-25% aqueous hydrochloric acid is added the top to be equipped with in the reactor of reflux exchanger and hydrogen chloride gas absorption unit, in heat-processed, add nylon-66 then, press the mass ratio 100: 40～60 of nylon and hydrogenchloride, under the condition of normal pressure and 100-110 ℃, reacted 8～12 hours, obtain acid hydrolysis solution;
(2), hexanodioic acid separates and recrystallization workshop section, reactor is vacuumized, treat that absolute pressure kept later on 20-30 minute less than 10KPa, acid hydrolysis solution in the step (1) is cooled to 30-40 ℃, separate to obtain thick adipic acid crystals with coarse filter, decolour again, recrystallization, oven dry obtain refining hexanodioic acid;
(3), hexamethylene-diamine hydrochloride separates and purifying workshop section, the 30-40% of the thick hexamethylene-diamine hydrochloride solution decompression evaporation concentration that obtains in the step (2) to cumulative volume, be cooled to 30-40 ℃, the industrial alcohol that adds 3-5 times of volume is separated out thick hexamethylene-diamine hydrochloride crystal, more after filtration, decolouring, recrystallization, drying obtain refining hexamethylene-diamine hydrochloride;
(4), polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section, the hexamethylene-diamine hydrochloride and the technical grade Dyhard RU 100 that obtain in the step (3) are roughly 1: 1 add-on input reactor according to mol ratio, nitrogen protection, stirred 10-30 minute, be warming up to 170-190 ℃, stirring reaction 3-7 hour, obtain hexamethylene and ammonium chloride mixt, reaction solution with molten state is pressed in the separating tank that fills industrial alcohol while hot, stir after-filtration, ethanol is removed in the underpressure distillation of hexamethylene ethanolic soln, obtained white or faint yellow solid hexamethylene;
(5), polyhexamethylene list (two) guanidinesalt hydrochlorate prepares workshop section, in reactor, drop into Dyhard RU 100 and the ammonium chloride powder that mol ratio was roughly 1: 2, nitrogen protection, stirred 10-30 minute, be warming up to 170-190 ℃, stirring reaction 1-3 hour, slowly add the hexamethylene-diamine hydrochloride powder that obtains in the step (3), continue reaction 3-7 hour, obtain polyhexamethylene list guanidinesalt hydrochlorate and ammonium chloride mixt, the reaction solution with molten state is pressed in the separating tank that fills industrial alcohol while hot, stir after-filtration, with polyhexamethylene list guanidinesalt hydrochlorate ethanol filtrate, ethanol is removed in underpressure distillation, obtains white or faint yellow solid polyhexamethylene list guanidinesalt hydrochlorate;
Step (4) or step (5) can be to select to use.
2. method according to claim 1, it is characterized in that workshop section's step also includes step (6) and recycles step, with used ethanol reuse after the rectifying tower weight steams in the ethanol filtrate of step (3) and step (4) or the step (5), tower still residue refrigerated separation, evaporation dilute hydrochloric acid solution reuse step in the lump (1) in filtrate and step (2) and the step (3), the filter residue in filter residue and step (4) or the step (5) merge to be handled.
3. method according to claim 2 is characterized in that the 30-40% of the evaporation concentration described in the step (3) to cumulative volume, preferred 35%; The industrial alcohol that adds 3-5 times of volume, preferred 4 times.
4. method according to claim 2 is characterized in that the decolouring employing gac described in the step (3), and add-on is the 3-5% of thick hexamethylene-diamine hydrochloride crystal mass.
5. method according to claim 2, it is characterized in that temperature of reaction described in step (4) or the step (5) and reaction times are definite according to end-use, the reaction times, molecular weight long more, the high more then polyhexamethylene of temperature of reaction list (two) guanidinesalt hydrochlorate was high more.
6. method according to claim 2 is characterized in that the tower still residue treatment process described in the step (6), need be after 5-7 production cycle, as offal treatment.
7. method according to claim 2 is characterized in that involved equipment configurations such as reactor, mechanical stirring and pipeline in step (4) or the step (5), all needs to adopt high temperature resistant non-metallic material and reaction system isolation such as enamel.
8. method according to claim 2, when it is characterized in that the adding hexamethylene-diamine hydrochloride powder described in the step (5), according to hexamethylene-diamine hydrochloride: the ammonium chloride powder is that 1: 1 mol ratio feeds intake, agitation condition control down evenly added in 30 minutes.
9. method according to claim 2 is characterized in that stirring in the step (5) after-filtration and obtains filter residue, gets byproduct of reaction ammonium chloride behind the water recrystallization purifying, and reuse is to step (5).
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| CN 200910097552 CN101857540B (en) | 2009-04-09 | 2009-04-09 | Method for producing adipic acid, hexamethylenediamine hydrochloride and polyhexamethylene (di)guanidine chloride from nylon-66 through depolymerization |
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| CN103145981A (en) * | 2011-12-07 | 2013-06-12 | 上海高聚生物科技有限公司 | Polyhexamethylene guanidine phosphate and synthetic method thereof |
| CN103396546A (en) * | 2013-08-01 | 2013-11-20 | 湖南利洁科技有限公司 | Method for preparing polyhexamethylene biguanidine hydrochloride by suspension polymerization |
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| ITRM20020529A1 (en) * | 2002-10-18 | 2004-04-19 | Franco Staino | STERILIZING POLYMERS, PROCESS OF THEIR PREPARATION AND USE. |
| CN1257880C (en) * | 2003-10-29 | 2006-05-31 | 宁波敏特尼龙工业有限公司 | Process for producing adipic acid and hexanediamine by depolymerization of nylon-66 |
| CN1273434C (en) * | 2004-05-13 | 2006-09-06 | 辽阳天成化工有限公司 | Production method with reclaimed waste nylon as material |
| CN101289536A (en) * | 2008-05-20 | 2008-10-22 | 方建文 | Method for preparing poly(hexamethylene) hydrochloride |
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| CN103145981A (en) * | 2011-12-07 | 2013-06-12 | 上海高聚生物科技有限公司 | Polyhexamethylene guanidine phosphate and synthetic method thereof |
| CN103396546A (en) * | 2013-08-01 | 2013-11-20 | 湖南利洁科技有限公司 | Method for preparing polyhexamethylene biguanidine hydrochloride by suspension polymerization |
| CN103396546B (en) * | 2013-08-01 | 2015-09-30 | 湖南利洁科技有限公司 | The method of hexamethylene is prepared in a kind of suspension polymerization |
| CN107868023A (en) * | 2016-09-22 | 2018-04-03 | 中国石油化学工业开发股份有限公司 | Biguanide phosphate synthesis method and antibacterial agent |
| CN107868023B (en) * | 2016-09-22 | 2020-05-08 | 中国石油化学工业开发股份有限公司 | Biguanide phosphate synthesis method and antibacterial agent |
| CN107056624A (en) * | 2017-04-19 | 2017-08-18 | 青岛科技大学 | A kind of alcoholysis recovery method of nylon 66 material |
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| CN108084434A (en) * | 2017-12-04 | 2018-05-29 | 辽宁科技大学 | A kind of method that polyhexamethylene list guanidine hydrochloride is prepared by spent acid lye |
| CN110746595A (en) * | 2019-11-01 | 2020-02-04 | 吉林师范大学 | Preparation method of poly (propylene glycol) guanidine hydrochloride |
| CN110746595B (en) * | 2019-11-01 | 2023-12-22 | 吉林师范大学 | Preparation method of poly (propylene glycol) guanidine hydrochloride |
| WO2022240822A1 (en) * | 2021-05-14 | 2022-11-17 | Research Triangle Institute | Depolymerization of polymers with ammonia and amines |
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