CN103396546A - Method for preparing polyhexamethylene biguanidine hydrochloride by suspension polymerization - Google Patents
Method for preparing polyhexamethylene biguanidine hydrochloride by suspension polymerization Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000010557 suspension polymerization reaction Methods 0.000 title claims abstract description 9
- -1 polyhexamethylene Polymers 0.000 title abstract description 9
- AKGZDINYLOSBTE-UHFFFAOYSA-N [(e)-n'-(diaminomethylideneamino)carbamimidoyl]azanium;chloride Chemical compound Cl.NC(=N)NN=C(N)N AKGZDINYLOSBTE-UHFFFAOYSA-N 0.000 title abstract 3
- 239000007864 aqueous solution Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000009835 boiling Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- 238000004821 distillation Methods 0.000 claims description 23
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 15
- LDFVINFJZGUOAZ-UHFFFAOYSA-N hexane-1,6-diamine;hydrochloride Chemical compound [Cl-].NCCCCCC[NH3+] LDFVINFJZGUOAZ-UHFFFAOYSA-N 0.000 claims description 13
- BTPGOPSJRHWTFO-UHFFFAOYSA-N NC(=N)N.CC=1C(=O)CC(CC1C)(C)C Chemical compound NC(=N)N.CC=1C(=O)CC(CC1C)(C)C BTPGOPSJRHWTFO-UHFFFAOYSA-N 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 10
- 239000012044 organic layer Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000004061 bleaching Methods 0.000 claims description 3
- 239000007844 bleaching agent Substances 0.000 claims description 3
- 238000003809 water extraction Methods 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- 230000003068 static effect Effects 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 21
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 abstract description 10
- 238000003756 stirring Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000008282 halocarbons Chemical class 0.000 abstract 2
- YXZZOMVBHPCKMM-UHFFFAOYSA-N 2-[6-[[amino-(cyanoamino)methylidene]amino]hexyl]-1-cyanoguanidine Chemical compound N#CNC(N)=NCCCCCCN=C(N)NC#N YXZZOMVBHPCKMM-UHFFFAOYSA-N 0.000 abstract 1
- XMVQMBLTFKAIOX-UHFFFAOYSA-N 6-azaniumylhexylazanium;dichloride Chemical compound [Cl-].[Cl-].[NH3+]CCCCCC[NH3+] XMVQMBLTFKAIOX-UHFFFAOYSA-N 0.000 abstract 1
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 238000011084 recovery Methods 0.000 description 18
- 238000001816 cooling Methods 0.000 description 16
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 15
- 229940117389 dichlorobenzene Drugs 0.000 description 15
- 229920002413 Polyhexanide Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 5
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical compound O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- IXBPPZBJIFNGJJ-UHFFFAOYSA-N sodium;cyanoiminomethylideneazanide Chemical compound [Na+].N#C[N-]C#N IXBPPZBJIFNGJJ-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003799 water insoluble solvent Substances 0.000 description 1
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- Polyamides (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for preparing polyhexamethylene biguanidine hydrochloride by suspension polymerization. According to the method, hexamethylenediamine dihydrochloride and 1,6-bis(cyano-guanidino)hexane are subjected to suspension polymerization by using a water insoluble organic solvent halogenated hydrocarbon with high density, high boiling point and strong polarity as a dispersing agent. A mass ratio of the halogenated hydrocarbon to reactants is 0.3-6 : 1. The method overcomes the disadvantages that residual polyethylene glycol in a product aqueous solution is difficult to remove in a conventional solvent polymerization by using polyethylene glycol 400 as a solvent; molecular weight is relatively low and residual n-hexanol in the product aqueous solution can not be removed completely by using n-hexanol as a solvent; and that viscosity becomes large and stirring is difficult at a late stage of reaction in melt polymerization. Therefore, the method is a relatively good method for industrialized production of polyhexamethylene biguanidine hydrochloride.
Description
Technical field
The invention belongs to organic chemistry filed, be specifically related to a kind of method of organic high molecular polymer preparation.
Background technology
Hexamethylene (PHMB) is a kind of 21 century broad spectrum antimicrobicide the most safely and efficiently that is acknowledged as, colorless and odorless, and Mlc is low, the wide spectrum low toxicity, speed of action is fast, and foam volume is low, and can after forming for a long time antibacterial of one deck positively charged ion at article surface, and can not cause and generate antibiotic bacterium characteristic, be widely used at present medicine equipment, PE, household, fabric, food, milk, and the nursing series product etc.The sterilization effect of PHMB and the size of its molecular weight have relation.Molecular weight is larger, and sterilization effect is better, and the time of effect is longer.At present, most enterprises fixes on 2500 left and right with the molecular weight of PHMB.
The people such as East are at Polymer, and 1997,15,3973-3984 has reported the route of synthetic PHMB.Different according to starting raw material, synthetic route has three: route one is take hexamethylene-diamine hydrochloride (HmDA.2HCl) and Dyhard RU 100 (DCDA) as raw material; Route two is take hexamethylene-diamine hydrochloride and dicyanamide sodium (SDC) as raw material; Route three: with hexamethylene-diamine hydrochloride and 1,6-dicyanogen methyl isophorone guanidine radicals hexane (HmBCG), be raw material.And every route can be divided into solution polymerization process and melt phase polycondensation.The crude product that obtains after polymerization, also must precipitate ammonium chloride (or sodium-chlor) and oligopolymer to remove generation in saturated nacl aqueous solution.But route one can not be used in precipitation polymers in saturated nacl aqueous solution to be come except the ammonium chloride and the oligopolymer that generate in dereaction.Must adopt him method to purify, thereby this route later separation cost is very high.The melt phase polycondensation process of route two is as follows: the SDC of equivalent and HmDA.2HCl are mixed, and reaction is 15 hours under 160-170 ℃, obtains frangible solid.The molecular weight of product that this method obtains is lower, and the PHMB productive rate that obtains after the saturated nacl aqueous solution precipitation only has 73.1%.The solution polymerization process process of route two is as follows: the SDC of equivalent and HmDA.2HCl are heated to 160-170 ℃ in glycol ether (DEG), reacted 15 hours, cooling after, add acetone to make product sclerosis, solid collected by filtration, solid obtained product in three days 70-80 ℃ of lower vacuum-drying.The solvent glycol ether that this method is used and water dissolves each other and boiling point is higher, be difficult for except clean; Aftertreatment adds volatile acetone, has increased cost; The productive rate that obtains after the saturated nacl aqueous solution precipitation has 54.7%.Route three melt phase polycondensation processes are as follows: the HmBCG of equivalent and HmDA.2HCl are mixed, and nitrogen protection, reacted 12 hours at 165-175 ℃ under oil bath.Solid starts fusing in the 1-2 that starts hour, and viscosity constantly increases.Cool to room temperature after reaction finishes, obtain the easy crushed solid of water absorbability.The PHMB productive rate that obtains after the saturated nacl aqueous solution precipitation is 99.1%.The process of route three solution polymerization process is as follows: the HmBCG of equivalent and HmDA.2HCl and n-formyl sarcolysine base pyrrolidone (NMP) mix in reaction flask; nitrogen protection; under mechanical stirring; 145-155 ℃ was reacted 14 hours; after the reaction end is cooling, solvent is toppled over, add acetone to make products solidifying; separate solid, obtained product with solid in 2 days 60 ℃ of lower vacuum-dryings.The PHMB productive rate that obtains after the saturated nacl aqueous solution precipitation only has 68.7%.In sum, the scorification of route three is best.
Except East report, domestic also some patent report PHMB synthetic.
The people such as the Li Hailong of University Of Ningbo report take hexamethylene-diamine hydrochloride (HmDA.2HCl) and Dyhard RU 100 (DCDA) as raw material with the synthetic PHMB of scorification in patent CN200910097552.8; its process is as follows: equimolar DCDA and HmDA.2HCl are mixed; nitrogen protection; stirred 30 minutes; be warming up to 170-190 ℃; stirred 3-7 hour; obtain the mixture of PHMB and ammonium chloride; melts is joined in the reactor that fills ethanol while hot; agitation and filtration is fallen ammonium chloride, and the filtrate evaporate to dryness obtains PHMB.The PHMB that is synthesized by this method is glass solid, and product purity is not high, and viscosity is smaller, and molecular weight ratio is lower.In fact this method is exactly the route 1 of East.
Li Yang, Li Fugang is in " fine chemical material and centre ", 2011,2, reported the solvent method of method one in 27-29 one literary composition, its process is as follows: take a certain amount of DCDA and HmDA.2HCl, its mol ratio is 1:1.1, add a certain amount of propyl carbinol, be heated with stirring to 130 degree in the situation that reflux, after stoichiometric number hour, solvent steamed, be warming up to 170 ℃, constant temperature 12 hours.Lower boiling propyl carbinol is that the solvent effect is not fine, and the product that obtains is also that purity is not high, and propyl carbinol is difficult for except clean, and product viscosity is little, and molecular weight is low.
In sum, the best synthetic method of PHMB of report is with melt polymerization under the HmBCG of equivalent and HmDA.2HCl high temperature at present.
But in HmBCG and the polymerization of HmDA.2HCl melt polymerization, reaction system viscosity is very large, is unfavorable for stirring, and easily burns agitator motor.
Summary of the invention
For the weak point that this area exists, the object of the invention is to provide a kind of suspension polymerization and prepares the method for hexamethylene.
The concrete technical scheme that realizes the object of the invention is:
Adopting high boiling point, high-density, strong polarity, water-insoluble polyhalohydrocarbon is dispersion agent, with hexamethylene-diamine hydrochloride and the at high temperature suspension polymerization of 1,6-dicyanogen methyl isophorone guanidine radicals hexane.Reaction formula is suc as formula (1).
Formula (1)
After polymerization is completed, add the water dissolution polymkeric substance, at room temperature separate the polyhalohydrocarbon solvent, with azeotropic distn, remove polyhalohydrocarbon solvent residual in the aqueous solution, then add bleaching agent bleaching, can obtain molecular weight greater than 2500 hexamethylene.
Described high boiling point, high-density, strong polarity, its density of water-insoluble polyhalohydrocarbon more than 1.3 grams per milliliters, boiling point is more than 160 ℃.
The mass ratio of polyhalohydrocarbon and reaction mass is 0.3:1-6:1.
Aftertreatment after polymerization is as follows:
A. polymerization complete after, add pure water that hexamethylene is dissolved, the quiet organic layer that separates, organic layer water extraction one time, combining water layer is the hexamethylene aqueous solution;
B. the water layer that merges carries out component distillation, and azeotropic steams the residual polyhalohydrocarbon in the hexamethylene aqueous solution, until distillate no longer contains organism;
C. add bleaching agent bleaching in the remaining aqueous solution of distillation, after decolouring, add as required pure water and make the hexamethylene in the aqueous solution reach the concentration that needs.
The organic solvent (polyhalohydrocarbon) that the organic solvent that d. will separate (polyhalohydrocarbon) and component distillation reclaim merges, and drying is heavily steamed, and namely is recycled.Polyhalohydrocarbon
Beneficial effect of the present invention is:
It is dispersion agent that the present invention selects high boiling point, high-density, strong polarity, water-insoluble solvent polyhalohydrocarbon, raw material is mixed, at high temperature suspension polymerization.Overcome in prior art solvent polymerization method method the shortcoming that when poly(oxyethylene glycol) 400 is solvent, residual polyoxyethylene glycol is difficult for removing; When having overcome n-hexyl alcohol and being solvent, molecular weight is lower, and in product water solution, residual n-hexyl alcohol is difficult for except clean shortcoming; Overcome reaction later stage viscosity in the melt phase polycondensation and become the large shortcoming that stirs difficulty.Therefore, the present invention is a kind of more excellent method of suitable suitability for industrialized production hexamethylene.
Embodiment
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.
Embodiment 1:
With 8kg1,6-dicyanogen methyl isophorone guanidine radicals hexane, 6.05kg hexamethylene-diamine hydrochloride and 10.8L dichlorobenzene mix in 50 liters of reactors, under nitrogen protection, slowly are warming up to 150 ℃.In 1-2 hour that starts, solid starts fusing, is suspended in solvent, and reaction starts, and rear viscosity slowly becomes greatly, continues reaction 18 hours, stopped reaction.Add appropriate boiling water, dope is dissolved, cooling, layering, separate organic layer.Water layer carries out component distillation to remove the organic solvent that remains in the aqueous solution, steams to till distillating organic solvent-free.The gac that adds aqueous solution weight 5% toward distillation in the remaining aqueous solution, reflux decolour 1.5 hours, cooling, filter, obtain the transparent hexamethylene aqueous solution.Mend appropriate water it is made into 20% solution.
The aqueous sample that takes a morsel evaporated under reduced pressure, obtain solid sample, and yield is 98.5%, and molecular weight is 2600.
The dichlorobenzene of the dichlorobenzene of separatory recovery and component distillation recovery is merged, and with distilling after the Calcium Chloride Powder Anhydrous drying, the dichlorobenzene that is recycled, the dichlorobenzene of recovery are used for polyreaction again.
Embodiment 2:
With 8kg1,6-dicyanogen methyl isophorone guanidine radicals hexane, 6.05kg hexamethylene-diamine hydrochloride and 10.8L trichlorobenzene mix in 50 liters of reactors, and nitrogen protection slowly is warming up to 200 ℃.In 1 hour that starts, solid starts fusing, is suspended on solvent, and reaction starts, and rear viscosity slowly becomes greatly, continues reaction 4 hours, stopped reaction.Add appropriate boiling water, dope is dissolved, cooling, layering, separate organic layer.Water layer carries out component distillation to remove the organic solvent that remains in the aqueous solution, steams to till distillating organic solvent-free.The gac that adds aqueous solution weight 5% toward distillation in the remaining aqueous solution, reflux decolour 1.5 hours, cooling, filter, obtain transparent hexamethylene aqueous solution solution.Mend appropriate water it is made into 20% solution.
The aqueous sample that takes a morsel evaporated under reduced pressure, obtain solid sample, and yield is 98.7%, and molecular weight is 2500.
The trichlorobenzene of the trichlorobenzene of separatory recovery and component distillation recovery is merged, and with distilling after the Calcium Chloride Powder Anhydrous drying, the trichlorobenzene that is recycled, the trichlorobenzene of recovery are used for polyreaction again.
Embodiment 3
With 8kg1,6-dicyanogen methyl isophorone guanidine radicals hexane, 6.05kg hexamethylene-diamine hydrochloride and 22.2L dibromobenzene mix in reactor, and nitrogen protection slowly is warming up to 200 ℃.In 1 hour that starts, solid starts fusing, is suspended on solvent, and reaction starts, and rear viscosity slowly becomes greatly, continues reaction 4 hours, stopped reaction.Add appropriate hot water, dope is dissolved, cooling, layering, separate organic layer.Water layer carries out component distillation to remove the organic solvent that remains in the aqueous solution, steams to till distillating organic solvent-free.The gac that adds aqueous solution weight 5% toward distillation in the remaining aqueous solution, reflux decolour 1.5 hours, cooling, filter, obtain transparent hexamethylene aqueous solution solution.Mend appropriate water it is made into 20% solution.
The aqueous sample that takes a morsel evaporated under reduced pressure, obtain solid sample, and yield is 98.9%, and molecular weight is 2650.
The dibromobenzene of the dibromobenzene of separatory recovery and component distillation recovery is merged, and with distilling after the Calcium Chloride Powder Anhydrous drying, the dibromobenzene that is recycled, the dibromobenzene of recovery are used for polyreaction again.
Embodiment 4
With 8kg1,6-dicyanogen methyl isophorone guanidine radicals hexane, 6.05kg hexamethylene-diamine hydrochloride and 33.3L dichlorobenzene mix in reactor, and nitrogen protection slowly is warming up to 150 ℃.In 1-2 hour that starts, solid starts fusing, is suspended on solvent, and reaction starts, and rear viscosity slowly becomes greatly, continues reaction 18 hours, stopped reaction.Add appropriate hot water, dope is dissolved, cooling, layering, separate organic phase.Water layer carries out component distillation to remove the organic solvent that remains in the aqueous solution, steams to till distillating organic solvent-free.The gac that adds aqueous solution weight 5% toward distillation in the remaining aqueous solution, reflux decolour 1.5 hours, cooling, filter, obtain transparent hexamethylene aqueous solution solution.Mend appropriate water it is made into 20% solution.
The aqueous sample that takes a morsel evaporated under reduced pressure, obtain solid sample, and yield is 99.2%, and molecular weight is 2700.
The dichlorobenzene of the dichlorobenzene of separatory recovery and component distillation recovery is merged, and with distilling after the Calcium Chloride Powder Anhydrous drying, the dichlorobenzene that is recycled, the dichlorobenzene of recovery are used for polyreaction again.
Embodiment 5
With 8kg1,6-dicyanogen methyl isophorone guanidine radicals hexane, 6.05kg hexamethylene-diamine hydrochloride and 5.4L dichlorobenzene mix in reactor, and nitrogen protection slowly is warming up to 152 ℃.In 1-2 hour that starts, solid starts fusing, is suspended on solvent, and reaction starts, and rear viscosity slowly becomes greatly, continues reaction 18 hours, stopped reaction.Add appropriate boiling water, dope is dissolved, cooling, layering, separate organic phase.Water layer carries out component distillation to remove the organic solvent that remains in the aqueous solution, steams to till distillating organic solvent-free.The gac that adds aqueous solution weight 5% toward distillation in the remaining aqueous solution, reflux decolour 1.5 hours, cooling, filter, obtain transparent hexamethylene aqueous solution solution.Mend appropriate water it is made into 20% solution.
The aqueous sample that takes a morsel evaporated under reduced pressure, obtain solid sample, and yield is 98.4%, and molecular weight is 2700.
The dichlorobenzene of the dichlorobenzene of separatory recovery and component distillation recovery is merged, and with distilling after the Calcium Chloride Powder Anhydrous drying, the dichlorobenzene that is recycled, the dichlorobenzene of recovery are used for polyreaction again.
Embodiment 6
With 8kg1,6-dicyanogen methyl isophorone guanidine radicals hexane, 6.05kg hexamethylene-diamine hydrochloride and 20.8L clorafin 70 mix in reactor, and nitrogen protection slowly is warming up to 152 ℃.In 1-2 hour that starts, solid starts fusing, is suspended on solvent, and reaction starts, and rear viscosity slowly becomes greatly, continues reaction 22 hours, stopped reaction.Add appropriate hot water, dope is dissolved, cooling, layering, separate organic phase.Water layer carries out component distillation to remove the organic solvent that remains in the aqueous solution, steams to till distillating organic solvent-free.The gac that adds aqueous solution weight 5% toward distillation in the remaining aqueous solution, reflux decolour 1.5 hours, cooling, filter, obtain transparent hexamethylene aqueous solution solution.Mend appropriate water it is made into 20% solution.
The aqueous sample that takes a morsel evaporated under reduced pressure, obtain solid sample, and yield is 98.4%, and molecular weight is 2700.
The clorafin 70 of the clorafin 70 of separatory recovery and component distillation recovery is merged, and with distilling after the Calcium Chloride Powder Anhydrous drying, the clorafin 70 that is recycled, the clorafin 70 of recovery are used for polyreaction again.
Comparative Examples
With 8kg1,6-dicyanogen methyl isophorone guanidine radicals hexane, 6.05kg hexamethylene-diamine hydrochloride and 10.8L poly(oxyethylene glycol) 400 are mixed in 50 liters of reactors, under nitrogen protection, slowly are warming up to 150 ℃.In 1-2 hour that starts, solid starts fusing, is suspended in solvent, and reaction starts, and rear viscosity slowly becomes greatly, continues reaction 18 hours, stopped reaction.Add appropriate boiling water, dope is dissolved, cooling.The gac that adds aqueous solution quality 5%, decolouring is 1.5 hours under reflux state, and is cooling, filters, and obtains clear solution.Add water and be made into 20% solution.
The sample evaporated under reduced pressure that takes a morsel, obtain solid sample, and molecular weight is 2200, and because the boiling point of poly(oxyethylene glycol) 400 is higher, and poly(oxyethylene glycol) 400 and water dissolves each other, so cause the poly(oxyethylene glycol) 400 in product to be not easy to remove.Because a large amount of ethylene glycol 400 is arranged in product, can't calculated yield.Same method, the selection n-hexyl alcohol is solvent, but its boiling point is slightly lower than the temperature of polymerization, and the molecular weight of the product that obtains is 2000.
Although, above used general explanation, embodiment and test, the present invention is described in detail, on basis of the present invention, can make some modifications or improvement to it, and this will be apparent to those skilled in the art.Therefore, these modifications or improvements, all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (5)
1. a suspension polymerization prepares the method for hexamethylene, it is characterized in that, take density more than 1.3 grams per milliliters, boiling point at the insoluble organic solvent of strong polar water more than 160 ℃ as dispersion agent, with hexamethylene-diamine hydrochloride and the suspension polymerization of 1,6-dicyanogen methyl isophorone guanidine radicals hexane.
2. the method for preparing hexamethylene according to claim 1, is characterized in that, the insoluble organic solvent of described water is polyhalohydrocarbon.
3. the method for preparing hexamethylene according to claim 2, is characterized in that, the mass ratio of described polyhalohydrocarbon and reaction mass is 0.3:1-6:1.
4. a method for preparing hexamethylene, is characterized in that, the last handling process of described method comprises the following steps:
A. polymerization complete after, add pure water that product is dissolved, static layering, separate organic layer, organic layer water extraction one time, combining water layer;
B. water layer carries out component distillation, and azeotropic steams the residual polyhalohydrocarbon in product water solution, until distillate no longer contains organism;
C. add bleaching agent bleaching in the remaining aqueous solution in distil container, remove discoloring agent;
D. add water in the discolored aqueous solution, make the hexamethylene aqueous solution of desired concn;
The organic layer that the organic layer that e. will separate and component distillation reclaim merges, and drying is heavily steamed and reclaimed, the insoluble organic solvent of recycle-water;
F. the insoluble organic solvent of water that reclaims is as the dispersion agent of next melt polymerization.
5. the method for preparing hexamethylene according to claim 4, is characterized in that, the discoloring agent that uses is gac or hydrogen peroxide.
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