CN101007869B - Anion slurry polymerization method for preparing caprolactam homopolymer and copolymer - Google Patents
Anion slurry polymerization method for preparing caprolactam homopolymer and copolymer Download PDFInfo
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- CN101007869B CN101007869B CN 200610003223 CN200610003223A CN101007869B CN 101007869 B CN101007869 B CN 101007869B CN 200610003223 CN200610003223 CN 200610003223 CN 200610003223 A CN200610003223 A CN 200610003223A CN 101007869 B CN101007869 B CN 101007869B
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Abstract
The invention relates to a method for preparing aminocaprolactam homopolymer and copolymer. It takes aminocaprolactam as monomer, takes aliphatic hydrocarbon as dispersing agent, takes alkali or base metal as catalyst, takes acyl chloride, format agent or isocyanate as catalyst promoter to carry out slurry polymerization process for anion and copolymerization with polyether, and gets powder nylon 6 homopolymer and copolymer low-melting point thermosol at low temperature below 160 Deg. C and in a short time. The invention is characterized in that it possesses feature of easy controllable stability for molecular weight and liner molecular construction, it is easy to ass residual catalyst deactivator to make product possess good property for spinning and second-time shaping at the end of reaction or after reaction.
Description
Invention field
The present invention relates to a kind ofly prepare the method for caprolactam homopolymer and multipolymer, the caprolactam homopolymer that obtains thus and multipolymer and uses thereof by the anion slurry polymerization technology.
Background of invention
The synthetic of polycaprolactam (nylon 6) mainly contains the hydrolysis polymerization technique of hexanolactam and extrudes the anionic polymerization that (RIM) is representative with monomer casting (MC nylon), reaction at present.
The hydrolysis technology is to be monomer with the hexanolactam, is ring opening agent with the less water, carries out 20-28 hour polyreaction in the VK polymerizing pipe under 250-280 ℃, and the temperature of reaction is than higher, and the time is long.Because this technology belongs to the balance reversible reaction, always contains monomer and the oligopolymer of 3-10% in the product, thereby needs the water hot extraction, facility investment and running cost have further been increased.This method can only the production relative viscosity be the polymkeric substance below 3.0, for demands such as high strength fiber peacekeeping films, must carry out solid state polymerization about 10 hours under near fusing point (220 ℃) in inert atmosphere to section, has further increased production cost.
The method of anionoid polymerization has the outstanding advantage that speed of response is fast, temperature is low, molecular weight of product is high.At present, the hexanolactam anionoid polymerization of exploitation both at home and abroad mainly contains monomer moulding casting nylon (MC nylon) and (RIM) technology is extruded in reaction, but sophisticated monomer casting technology (MC nylon) only is suitable for materials processings such as massive casting, can not make conventional thermoplastic resin section and process flexibly, use dumb.It is to try hard to technology that the low temperature of anionoid polymerization, high speed advantage and flexible processing advantage that thermoplasticity is cut into slices are combined that (RIM) technology is extruded in reaction, but, there is the deficiency of two aspects in this method: at first, because anionic polymerisation is very violent, the molecular weight of reaction product is difficult to stable control; Secondly, because this reaction belongs to living polymerization, behind the reaction terminating, the active centre still remains in the product section, and when post forming processing was heated, the active centre can produce side chain and crosslinked by trigger molecule, and what be unfavorable for processing normally carries out.The reaction extrusion molding does not still have the passivation measure of effective active centre, makes the post forming processing of making section limited.
Summary of the invention
The novel method that the purpose of this invention is to provide a kind of preparation caprolactam homopolymer (nylon 6), this method is utilized the characteristics that anionoid polymerization speed is fast, temperature of reaction is low, utilize the slurry polymerization characteristics gentler than body anionic polymerization, thereby can prepare the Powdered linear nylon 6 that is easy to inactivate activity center and residual catalyst, make this polymkeric substance be easier to carry out post forming processing.
Another object of the present invention provides a kind of novel method for preparing caprolactam copolymer, and the characteristics that this method utilizes hexanolactam to be easier to carry out with the alcoholic extract hydroxyl group oligopolymer copolymerization in anionoid polymerization than in the hydrolysis polymerization prepare modification of nylon low melting point hot melt adhesive.
These and other purposes of the present invention, feature and advantage will become more clear after reading this specification sheets.
Detailed Description Of The Invention
One aspect of the present invention provides a kind of method for preparing caprolactam homopolymer by the anion slurry polymerization technology, this method is monomer with the hexanolactam, with alkali or basic metal is catalyzer, with acyl chlorides, Grignard reagent or isocyanic ester is promotor, with the aliphatic hydrocarbon is that dispersion agent carries out anion slurry polymerization, product through filtering separation and drying, makes Powdered or granulated polymer after acid or acid anhydrides carry out Passivation Treatment to the active centre.For the acid of carrying out passivation or acid anhydrides, can not add in the polymeric later stage yet, but make Powdered or granulated polymer after adding following stabilizers before or add following stabilizers in directly be mixed in the polymer powder, when the second-heating moulding, play the passivation of residual catalyst.This polymer powder is easy to be dissolved in and carries out secondary processing in the organic or inorganic solvent, also can be after adding various stablizers such as oxidation inhibitor and modified additive, and directly melt-processed or granulation through melt-spinning with extrude, makes well behaved fiber and plastics.
The present invention provides a kind of method for preparing caprolactam copolymer by the anion slurry polymerization technology on the other hand, this method is monomer with the hexanolactam, with the polyethers is properties-correcting agent, with alkali or basic metal is catalyzer, with acyl chlorides, Grignard reagent or isocyanic ester is promotor, with the aliphatic hydrocarbon is that dispersion agent carries out the copolymerization of negatively charged ion slurry, makes fusing point and be 120-170 ℃ Powdered or particulate state low melting point hot melt adhesive.This hot melt adhesive can be used for the heat bonding of textiles, and has good bonding intensity.
Specifically describe preparation method of the present invention below.
The equal polymerization of hexanolactam
Caprolactam monomer put into reactor and be heated to 70-120 ℃ temperature, vacuumize and remove micro-moisture to the water capacity that monomer absorbs and be lower than 0.02wt%, adding based on monomer weight then is 1.0 * 10
-3-8.0 * 10
-3The alkali of % or base metal catalysts, under 90-120 ℃, continue to vacuumize, water to the water capacity of getting rid of the reaction generation is lower than 0.015wt%, adding is the promotors such as acyl chlorides, Grignard reagent or isocyanic ester of 1.2-4.8mol% based on monomeric molar weight, add inertia aliphatic hydrocarbon dispersion agent simultaneously, add-on is the 4-30wt% of monomer weight.Under agitation be heated to temperature and reach 140-160 ℃, reaction system becomes muddiness by clear, produces a large amount of granulated polymers in 10-20 minute, and (this moment, monomer conversion was about 35-45% when being difficult to stir when the polymerization system thickness, stop heating and stirring, product is discharged.Through precipitation and filtering separation, filter cake is through 80 ℃ of water washings, and carries out vacuum-drying in 90 ℃, obtains the white powder of diameter 5-150 μ m.
Adding based on polymer weight in above-mentioned polymer powder is the active centre passivator of 0.1-1.0wt%, after mixing, melt extrude or spinning in 250 ℃ with screw extrusion press, make the continuous filament yarn of single wire fracture intensity 3cN/dtex-9cN/dtex; The polymer phase that the melt-processable of polymkeric substance and hydrolysis method make is same, and the tensile strength through melt extruding the standard testing batten of making reaches 900kg/cm
2
The inventive method can adopt semicontinuous mode to carry out, and turn back to polymerization reactor with the filtrate after the filtering separation this moment, together reacts with freshly prepd reactive monomer and the promotor of adding, and continues to generate new polymer powder.
The inventive method can also adopt intermittent mode to carry out, and the adding of active centre passivator this moment also can be behind reaction terminating, carries out before the material discharging.As the acid of pKa value between 3-7 is added system, continue stirring and get final product discharging after 15-30 minute.
In the methods of the invention, used catalyzer is identical with the type of monomer moulding casting nylon and reactive extrusion technology with promotor, but in order at utmost to reduce crosslinked and generation side chain, has selected more gentle catalyzer, promotor and the reaction conditions of reaction for use.The effect of catalyzer is to make the lactan activation, generates the lactan negatively charged ion, i.e. reactive monomer.Shown in the following reaction formula:
M in the formula and B-M
+Represent catalyzer alkali metal lithium, sodium, potassium, caesium and its compound respectively, but for reaction is relaxed, the compound of employing sodium such as sodium hydride and sodium hydroxide are more useful.In the methods of the invention, alkali or alkali-metal consumption are 1.0 * 10 based on monomer hexanolactam weight
-3-8.0 * 10
-3%, preferred 1.5 * 10
-3-6.0 * 10
-3%, more preferably 1.8 * 10
-3-4.0 * 10
-3%.
The effect of promotor is to make the above-mentioned reactive monomer of caprolactam monomer and generation carry out polymerization, fast reaction speed, as being the reaction of promotor with the acyl chlorides:
Promotor also can be used isocyanates except that acyl chlorides such as Acetyl Chloride 98Min., as aromatics or aliphatic isocyanate, and tolylene diisocyanate especially, hexamethylene diisocyanate etc.Can also adopt grignard reagent, for example the N-ethanoyl lactan of making by grignard reagent.In the methods of the invention, the consumption of promotor is 1.2-4.8mol% based on the molar weight of monomer hexanolactam, preferred 1.3-4.5mol%, more preferably 1.5-3.0mol%.
The effect of dispersion agent is that reaction monomers is dispersed into countless little liquid pearls, or the concentration that is dissolved in the dispersion agent, and then makes with making monomer segment monomer and reactive monomer reduces, and the speed of response of anionoid polymerization also suitably reduces, reaction process is thawed, make molecular weight of product be easy to stable control.Dispersion agent also helps opens the polymer dispersed that generates, and becomes small-particle or fine powder, and this helps carrying out subsequently the Passivation Treatment in active centre.In addition, dispersion agent also helps heat transfer, makes temperature and heat reach uniform distribution, prevents crosslinked and generation side chain.Dispersion agent adopts the inertia aliphatic hydrocarbon, and as the hexanaphthene through purifying, kerosene, diesel oil etc., these hydro carbons do not influence normal polymerization, relative low price, and nontoxic pollution-free is easy to reclaim and purifies.In the methods of the invention, the consumption of dispersion agent is 4-30wt% based on monomer hexanolactam weight.
Because anionoid polymerization belongs to living polymerization, after polyreaction stops, active centre (also claiming catalyst residues) is just temporarily frozen, under the comparatively high temps that the post forming of polymkeric substance is processed, these active centre can be brought back to life, and cause a series of side reaction, produce crosslinked and side chain, make poor processability, and have influence on the use properties of the finished product, shown in preceding two formulas of following reaction formula:
M represents catalyzer in the formula, and HX represents acid, and promptly the macromolecular chain of polymerisate under the organic bases effect of catalyst residues the reaction as III.IV takes place, and its product instability is pressed IIIV.V chain rupture is taken place, and polymerisate is degraded.For this reason, need polymerisate is carried out the Passivation Treatment in active centre.Passivator usable acid and acid anhydrides are as the 3rd formula of above-mentioned reaction formula, the H in the acid
+Ion can react with the catalyst residues on the active centre, and polymer molecule is tended towards stability.Acidity generally is controlled at the pKa value between 3-7, if acidity is too high, the acidolysis reaction of polymkeric substance can take place simultaneously, and acidity is too low then can not effectively remove catalyst residues.The inventive method employing pKa is 4.74 acetate and Tetra hydro Phthalic anhydride.
Hexanolactam and polyethers copolymerization prepare the low melting point hot melt adhesive
The first half operation of this method is identical with the equal polymerization of hexanolactam, and difference is will add polyethers second monomer in the later stage, because the introducing of pure terminal hydroxy group, the consumption of promotor also needs corresponding increase, and polymerization temperature needs suitably to improve.Concrete enforcement is as follows:
Caprolactam monomer put into reactor and be heated to 70-120 ℃ temperature, vacuum dehumidifies to water capacity and is lower than 0.02wt%, and adding based on monomer weight then is 1.0 * 10
-3-8.0 * 10
-3The alkali of % or base metal catalysts, react under vacuum condition in 90-120 ℃ of continuation, water to the water capacity of getting rid of the reaction generation is lower than 0.015wt%, adding is acyl chlorides or isocyanic ester or the Grignard reagent promotor of 1.5-6.0mol% based on monomeric molar weight, add simultaneously based on monomer weight is the polyoxyethylene glycol PEG (molecular weight is 800-1500) or poly-1 of 2.0-10.0wt%, 4-butyleneglycol PBG (molecular weight is 800-1500), for avoiding bringing into moisture, need polyethers is carried out the vacuum dehumidification treatments, its moisture percentage also should be lower than 0.015wt%, under agitation adding based on hexanolactam weight simultaneously is the aliphatic hydrocarbon dispersion agent of 4-30wt%, and under agitation be heated to temperature and reach 115-180 ℃, reaction system becomes muddiness by clear, produces a large amount of granulated polymers in 15-30 minute, when the system thickness extremely is difficult for stirring, stop heating and stir discharging, filtration, 80 ℃ of water washings, 90 ℃ of vacuum-dryings obtain the pale yellow powder of particle diameter 5-150 μ m.
The fusing point of gained copolymer powder changes with the molecular weight and the addition of polyethers between 120-180 ℃.Therefore, the multipolymer that obtains thus can be used as the low melting point hot melt adhesive.
Compare with the hexanolactam hydrolysis polymerization technique of widespread use, the inventive method has the advantages that temperature of reaction is low, polymerization velocity is fast.Compare with reactive extrusion technology with hexanolactam anionic monomer cast poymerization technology, the inventive method has molecular weight product and is easy to control, the characteristics of post forming machining control, performance and the Heat stability is good of polymkeric substance.
Embodiment
The invention will be further described below by embodiment, should be noted that these embodiment only are used for the present invention is illustrated, and should not be construed limitation of the present invention.
Embodiment 1: nylon 6 homopolymer synthetic
The 10kg caprolactam monomer is joined 50 liters of reactors, be heated to 70-120 ℃ temperature, vacuumize and remove micro-moisture to the water capacity that monomer absorbs and be lower than 0.02wt%, add 0.2 * 10
-2The sodium hydroxide catalyst of wt%, under 90-120 ℃, continue to vacuumize, water to the water capacity of getting rid of the reaction generation is lower than 0.015wt%, adds cocatalyst toluene diisocyanate and the 2.5 liters of dispersion agent kerosene (technical pure, boiling spread 160-220 ℃) of 1.63mol%.Through 155 ℃ of reactions 30 minutes, the acquisition monomer conversion is 45% nylon 6 slurries, the acetate (based on the 1.0wt% of hexanolactam consumption) that under this temperature of reaction, adds pKa=4.74, stir and residual catalyst and residual activity center carried out Passivation Treatment in 20 minutes, discharging then, filtration, washing, oven dry make dry powder PA6, after tested, melting point polymer is 210 ℃, and it is M that viscosimetry records molecular weight
W=13890.Add 0.5% oxidation inhibitor 168/1010 in every gram dry powder, carry out melt-spinning in 250 ℃, have good spinning properties, the linear density that makes fiber is 6.7dtex, and breaking tenacity 4.5cN/dtex, extension at break are 11.5%.
Embodiment 2: the preparation of low melting point hot melt adhesive
The 10kg caprolactam monomer is added 50 liters of reactors, be heated to 70-120 ℃ temperature, vacuumize and remove micro-moisture to the water capacity that monomer absorbs and be lower than 0.02wt%, add 0.2 * 10
-2The sodium hydroxide catalyst of wt%, under 90-120 ℃, continued to vacuumize 30 minutes, water to the water capacity of getting rid of the reaction generation is lower than 0.015wt%, add the 2.0mol% cocatalyst toluene diisocyanate, add molecular weight simultaneously and be 1000 polyoxyethylene glycol PEG (hexanolactam weight 6%), under agitation add 2.5 liters of dispersion agent kerosene (technical pures, boiling spread 180-220 ℃), be warming up to 115-170 ℃ of stirring reaction 20-30 minute, obtaining monomer conversion is the PA6/PEG copolymer pulp of 40-45%, after the discharging after filtration, washing, oven dry, obtain powdery PA6/PEG multipolymer, after tested, its fusing point is 120 ℃, and molecular weight is 10000-13000.With this powder evenly be coated in two-layer pure cotton fabric between, in 170 ℃ of hot pressing 25 seconds on ironing machine, obtain the bonds well performance, through peeling off test, the warp-wise stripping strength is greater than fabric breaking strength (147.7N/5cm), and the broadwise breaking tenacity is 54.6 (N/5cm).
The fusing point of multipolymer changes with the variation of PEG add-on, and following relation is specifically arranged:
| PEG content (wt%) | 0 | 3 | 4 | 5 | 6 | 8 |
| The multipolymer fusing point (℃) | 210 | 174 | 150 | 140 | 120 | 164 |
Claims (9)
1. method for preparing caprolactam copolymer, comprise with the hexanolactam being monomer, with the polyethers is properties-correcting agent, with alkali or basic metal is catalyzer, with acyl chlorides or isocyanic ester is promotor, is that dispersion agent carries out the copolymerization of negatively charged ion slurry with the aliphatic hydrocarbon, makes fusing point and be 120-170 ℃ Powdered or particulate state low melting point hot melt adhesive, wherein use based on monomer weight and be the polyoxyethylene glycol PEG of 800-1500 or poly-1,4-butyleneglycol PBG as the molecular weight of 4.0-10.0wt% as polyethers.
2. according to the process of claim 1 wherein that used alkali or basic metal are lithium, sodium, potassium, caesium or its compound, and its consumption is 1.0 * 10 based on monomer hexanolactam weight
-3-8.0 * 10
-3%.
3. according to the method for claim 2, wherein alkali or alkali-metal consumption are 1.5 * 10 based on monomer hexanolactam weight
-3-6.0 * 10
-3%.
4. according to the method for claim 3, wherein alkali or alkali-metal consumption are 1.8 * 10 based on monomer hexanolactam weight
-3-4.0 * 10
-3%.
5. according to each method among the claim 2-4, wherein used alkali or basic metal are the compound of sodium.
6. according to the method for claim 5, wherein the compound of used sodium is sodium hydride and sodium hydroxide.
7. according to the process of claim 1 wherein that the acyl chlorides as promotor is an Acetyl Chloride 98Min., be aromatics or aliphatic isocyanate as the isocyanic ester of promotor, and the consumption of described promotor is 1.5-6.0mol% based on the molar weight of monomer hexanolactam.
8. according to the method for claim 7, wherein the isocyanic ester as promotor is tolylene diisocyanate or hexamethylene diisocyanate.
9. according to the process of claim 1 wherein that the aliphatic hydrocarbon as dispersion agent is the liquid inertia aliphatic hydrocarbon that is selected from hexanaphthene, kerosene, diesel oil, and its consumption is 4-30wt% based on monomer hexanolactam weight.
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| CN101735451B (en) * | 2009-12-11 | 2012-09-19 | 东华大学 | Method for producing polyamide thermoplastic elastomer |
| MY180633A (en) * | 2011-07-05 | 2020-12-03 | Basf Se | Solid particles, containing lactam, activator, and catalyst, method for producing said solid particles, and use of said solid particles |
| CN104630925B (en) * | 2015-02-05 | 2017-04-05 | 江苏科技大学 | A kind of reactive extrursion preparation method of polyamide micro nanometer fiber |
| CN110066372A (en) * | 2019-04-23 | 2019-07-30 | 常熟市江南粘合剂有限公司 | A kind of polyisocyanate nylon co-catalyst |
| CN112646171A (en) * | 2019-10-11 | 2021-04-13 | 江苏金陵网业有限公司 | Compound proportioning method of trampoline protective net material |
| CN111925520B (en) * | 2020-07-30 | 2022-09-06 | 恒天纤维集团有限公司 | Method for preparing polybutyrolactam by slurry polymerization of anion ring opening |
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