CN104130395B - The addition transferred in pipeline of the copper into nylon synthesis - Google Patents

The addition transferred in pipeline of the copper into nylon synthesis Download PDF

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Publication number
CN104130395B
CN104130395B CN201410141646.1A CN201410141646A CN104130395B CN 104130395 B CN104130395 B CN 104130395B CN 201410141646 A CN201410141646 A CN 201410141646A CN 104130395 B CN104130395 B CN 104130395B
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copper
polyamide
conduit
flash vessel
weight
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CN104130395A (en
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托马斯·A·米茨卡
约翰·P·普安萨蒂
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Invista Textiles UK Ltd
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Invista Textiles UK Ltd
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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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

A kind of system for polyamide, the system comprises：Main paradigmatic system, the main paradigmatic system are configured to one or more raw material being converted into polyamide products；The conduit in the main paradigmatic system downstream, the conduit are configured to transfer the polyamide products；With the feeding line for including the output into the conduit, wherein the feeding line is configured to feed cupric composition into conduit.Forming the method for daiamid composition includes polymerizeing one or more raw material in main paradigmatic system to form polyamide products, the polyamide products from the main paradigmatic system are transferred in the catheter, and cupric composition is fed into the conduit in the main paradigmatic system downstream.

Description

The addition transferred in pipeline of the copper into nylon synthesis
Cross reference to related applications
This application claims the benefit of priority for the U.S. Provisional Patent Application No. 61/817,917 that on May 1st, 2013 submits, The disclosure of which is incorporated herein by reference in their entirety.
Technical field
This application involves the systems for forming the method for daiamid composition and being used to prepare polyamide.
Background technology
Polyamide has for example high durability of useful property and intensity, this causes them can be in a variety of environment It uses.Polyamide such as nylon, aromatic polyamides and poly- (aspartic acid) sodium are commonly used in, for example, carpet, airbag, mechanical part, Dress ornament, rope and stocking.Nylon 6,6 is a kind of most-often used polyamide.The long chain and compact texture of nylon 6,6 make It obtains it and is qualified as advanced nylon fiber, show high mechanical properties, rigidity and thermal stability.
Polyamide is commercially synthesized in extensive manufacturing equipment.Polyamide can by by diamines and dicarboxylic acids, sometimes with The form of the ammonium carboxylate salt of two compounds polymerize in solvent such as water and obtains.For example, nylon 6,6 can be by making six methylenes Base diammonium adipate undergoes condensation reaction, is synthesized with forming amido bond and discharging water.In such as evaporator, reactor, flash distillation In a series of components of device and finisher, can by heat apply to reaction mixture, and water can gradually be removed with Driving balance is towards polyamide (such as nylon 6,6), until polymer chain reaches required molecular weight ranges.Afterwards, can incite somebody to action The polyamide of melting is extruded as pellet, can spin as fiber or be processed into other shapes.
Can by additive the different phase of technique add in reaction mixture so as to improve or improve polyamide certain Characteristic needed for a little.For example, one or more antioxidants can be added in what is be broken at any time to polyamide to reduce polyamide Possibility, particularly under the high temperature conditions.One example of the antioxidant being usually added into is copper-containing compound, such as copper halide (CuI, CuBr) or copper acetate.Typically, copper-containing compound is had been added in source of saline solution, extremely carboxylic acid ammonium is included for example, adding in The container of salt.
Addition of the copper-containing compound to source of saline solution may cause one or more of copper metal downstream equipment unit operation It is plated out on a inside, such as in evaporator, reactor, flash vessel and finisher.Plating out for copper metal may interfere with every Equipment is run and is likely to reduced the bulk life time of equipment, for example, equipment is before repairing, replacing or otherwise safeguarding The time quantum that can be run in technical specification.Maintenance with copper-plated equipment may be difficult, expensive and take 's.Some copper metals plated out may also become to be moved out of and may be entrained in polymerizing polyamide logistics, wherein being moved The copper metal gone out may interfere with the operation of technique, such as by the flowing that blocks or otherwise interfere polyamide polymer or Person's copper metal may be unfavourably incorporated in final polyamide products.The addition of copper-containing compound is also possible to cause adding in The equipment in point downstream of copper-containing compound or the corrosion of pipe.
Copper-containing compound may also cause polyamide polymer in source of saline solution or in the addition of other upstream positions Gelation.The gelation of polyamide may interfere the flowing of polyamide when polyamide flows through process equipment, and may Reduce the quality of final polyamide products.
As described herein, embodiment of the present invention can provide the solution of these problems.
The content of the invention
The present disclosure describes polyamide is prepared, such as the system and method for nylon 6,6.The system and method for the disclosure can wrap It includes and feeds cupric composition into the transmission pipeline in the main paradigmatic system downstream of polyamide manufacturing process.For example, the disclosure System and method can include the charging transferred in pipeline of the cupric composition to evaporator, reactor and flash vessel downstream.It passes Passing pipeline can also be in the downstream of finisher.Addition of the cupric composition in paradigmatic system downstream can plate out to avoid copper metal Onto the equipment of paradigmatic system, such as in reactor or flash vessel, and the possibility of the gelation of polyamide stream can also be reduced Property.
The present disclosure describes a kind of systems for being used to prepare polyamide.The system can include：Paradigmatic system, the polymerization System configuration is that one or more raw material are converted into polyamide products；The conduit in paradigmatic system downstream, the conduit configuration To transfer polyamide products；And include the feeding line of the output into the conduit, wherein the feeding line is configured to Cupric composition is fed into conduit.
The present disclosure describes a kind of methods for forming daiamid composition.This method can be included one or more former materials Material polymerize to form polyamide products in paradigmatic system, transfers the polyamide products from paradigmatic system in the catheter and incites somebody to action Cupric composition is fed into the conduit in paradigmatic system downstream.
These and other examples and feature of the system and method for the present invention will be described in more detail below middle part and illustrate.This general introduction Purpose be that the general introduction of subject of the present invention is provided, be not intended to provide exclusiveness or exhaustive explanation.Including following detailed description with The further information of system and method on the present invention is provided.
Description of the drawings
Fig. 1 is for manufacturing the schematic flow diagram of the example system of nylon 6,6.
Fig. 2 is for cupric composition to be fed to showing for the feed system in the conduit of the example system provided into Fig. 1 It is intended to.
Specific embodiment
Disclosure description is a kind of for manufacturing polyamide, such as the method and system of nylon 6,6.System described herein and side Method can include for reduce or eliminate copper facing or gelation possibility cupric composition is added in the device of polyamide, System and method.
It should be explained using the boundary not only included as scope with flexible way with the value of range format expression and clearly described Numerical value, and including all independent numerical value or subrange included in the range of this, as by each numerical value and subrange Clearly statement is the same.For example, the scope of " about 0.1% to about 5% " or " about 0.1% to 5% " should be construed to not only include About 0.1% to about 5%, and including the individual value (for example, 1%, 2%, 3% and 4%) in pointed scope and sub- model It encloses (for example, 0.1% to 0.5%, 1.1% to 2.2%, 3.3% to 4.4%).Unless otherwise noted, statement " about X to Y " has The meaning identical with " about X to about Y ".Equally, unless otherwise noted, state that " about X, Y or about Z " has and " about X, about Y or about Z " Identical meaning.
Herein, unless context clearly dictates otherwise, using term "one", " one kind " or " described " to be to include One or more than one.Unless otherwise noted, the "or" of nonexcludability is referred to using term "or".In addition, it is to be appreciated that Purpose that words or terms that are using herein and in addition not defining are merely to illustrate is and not restrictive.Any paragraph mark The use of topic is intended to the understanding of help file and is not interpreted to limit；It can be special with the relevant information of paragraph heading Paragraph inside or outside occur.In addition, all publications, patent and the patent document quoted herein by quote with Entire contents individually through reference with reference to here, as combined.This paper be so incorporated by reference those text In the case that usage is inconsistent between offering, with reference to citation in usage should be considered as supplement herein；It is right In irreconcilable contradiction, usage herein is subject to.
Manufacturing method described herein can be carried out main without departing from the present invention with order described herein or random order The principle of topic, except when explicitly pointing out time or operation order.In addition, the specific part of this method can be carried out at the same time, remove Claim language non-clearly points out that they are dividually carried out.For example, narration carries out X and the claim of narration progress Y can Simultaneously to be carried out in single operation, and obtained technique will fall literal scope in technique claimed It is interior.
As used herein term " about " can allow certain variable pitch in value or range, for example, described Value or the scope limitation 10% in, in 5% or in 1%.
As used herein term " substantially " refers to major part or mainly, be such as at least about 50%, 60%, 70%th, 80%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, 99.9%, 99.99% or at least about More than 99.999%.
As it is used herein, term " dicarboxylic acids " broadly refers to C4-C18Alpha, omega-dicarboxylic acid.The term includes C4-C10 Alpha, omega-dicarboxylic acid and C4-C8Alpha, omega-dicarboxylic acid.C4-C18The example for the dicarboxylic acids that alpha, omega-dicarboxylic acid includes includes, but unlimited In, succinic acid (butanedioic), glutaric acid (pentane diacid),
Adipic acid (hexane diacid), pimelic acid (heptane diacid), suberic acid (octane diacid), azelaic acid (nonane diacid) and Decanedioic acid (decane diacid).In some embodiments, C4-C18α, ω-carboxylic acid are adipic acid, pimelic acid or suberic acid.Again In other embodiments, C4-C18Alpha, omega-dicarboxylic acid is adipic acid.
As it is used herein, term " diamines " broadly refers to C4-C18α, ω-diamines.The term includes C4-C10α, ω-diamines and C4-C8α, ω-diamines.By C4-C18α, the example for the diamines that ω-diamines includes include, but are not limited to, and butane- Isosorbide-5-Nitrae-diamines, pentane -1,5- diamines and hexane -1,6- diamines, also referred to as hexamethylene diamine.In some embodiments, C4- C18α, ω-one amine are hexamethylene diamines.
In some instances, it is contemplated herein that the use that adipic acid is combined with hexamethylene diamine.
As it is used herein, term " polyamide " broadly refers to polyamide such as nylon 6, nylon 7, nylon 11, nylon 12nd, nylon 6,6, nylon 6,9；Nylon 6,10, nylon 6,12 or their copolymer.
As it is used herein, term " polymer " " copolymer can be included.
As it is used herein, term " relative viscosity " refers to the solution and molten of the measurement at 25 DEG C in capillary viscometer The ratio of agent viscosity.Such as it is the basis of the test program by the ASTM D789-06 relative viscosities measured and is that polyamide exists 8.4 weight % solution in 90% formic acid (90 weight % formic acid and 10 weight % water) 25 DEG C viscosity (in terms of centipoise) with 90% formic acid is from the ratio in 25 DEG C of viscosity (in terms of centipoise).Relative viscosity may be used as viscosity and further molecule The replacement measurement of amount.
As it is used herein, refer to can be with the liquid of dissolved solid, liquid or gas for term " solvent ".The non-limit of solvent Property example processed is siloxanes, organic compound, water, alcohol, ionic liquid and supercritical fluid.
It is used to prepare the system of polyamide
Fig. 1 is for manufacturing polyamide, and particularly for manufacturing the flow chart of the instance system 10 of nylon 6,6.System System 10 can include reservoir 12, accommodate the water-soluble of liquid or the substantially dicarboxylic acids of liquid phase, diamines and solvent (for example, water) Liquid.Dicarboxylic acids and diamines can form ammonium carboxylate salt.In an example, the feelings of the manufacture of nylon 6,6 are configured in system 10 Under condition, reservoir 12 can include hexa-methylene diammonium adipate, can be dissolved in water in reservoir 12.Reservoir 12 can be with To mix or store the aqueous solution of ammonium carboxylate salt.
In this example, dicarboxylic acids and diamines can be added in substantially equimolar ratio to reservoir 12.Obtained carboxylic Acid ammonium salt solution can have about 7.5, the pH of such as from about 7.4 to about 7.6.The ammonium carboxylate salt of each molecule can include a molecule Diamines and a molecule dicarboxylic acids.Aqueous solution can be preheated before reservoir 12 is introduced to, such as with preheater, Huo Zheke Aqueous solution is such as used heater in reservoir 12 or with vapor, the vapor such as formed in another part of system 10 adds Heat.
The solution of dicarboxylic acids and diamines can will be included, for example, ammonium carboxylate salt aqueous solution, passes from reservoir 12 via conduit 16 It is handed to evaporator 14.Evaporator 14 be configurable to by the water of the part from aqueous solution basically liquid phase with vapor stream 18 form is converted into substantially gas phase.In instances, evaporator 14 is by aqueous solution by being heated to about 100 DEG C to about 230 DEG C, Such as from about 100 DEG C to about 150 DEG C, for example, about 110 DEG C, about 120 DEG C, about 130 DEG C, about 140 DEG C, about 150 DEG C, about 160 DEG C, about 170 DEG C, about 180 DEG C, about 190 DEG C, about 200 DEG C, about 210 DEG C, the temperature of about 220 DEG C or about 230 DEG C form vapor stream 18.Evaporation Device 14 can increase the concentration of ammonium carboxylate salts.In instances, leave reservoir 12 and feed to the carboxylic acid ammonium in evaporator 14 The concentration of salting liquid is that about 40 weight % to about 80 weight % salt or about 52 weight % are to about 65 weight % salt in water, in water About 63 weight % salt.Evaporator 14 can increase the concentration of ammonium carboxylate salts, such as the about 72 weight % salt into water.
Via evaporation remove water can cause in the evaporator 14 dicarboxylic acids at least part of present in solution and It reacts to form the Polvamide prepolymer that can include the polymer chain of relatively short dicarboxylic acids and diamines diamine portion.Change speech It, removal water can start the condensation reaction between dicarboxylic acids and diamines, to form the first order that can be final polyamide chains Oligomer.As noted above, evaporator 14 can be with concentrated aqueous solution, for example, solution by that will leave evaporator 14 Water concentration reduces, and is such as reduced to about 5 weight % to the water concentration of the water of about 50 weight %, for example, about 25 weight % to about 35 weights Measure % water, such as from about 25 weight %, about 26 weight %, about 27 weight %, about 28 weight %, about 29 weight %, about 30 weight %, About 31 weight %, about 32 weight %, about 33 weight %, the water of about 34 weight % or about 35 weight %.
Vapor stream 18 can be allowed to escape to air or vapor stream 18 to condense and feed and be back to reservoir 12 (not shown).Condensed steam can also be purified, such as via filtering or other purification process.It can also be steamed using condensed water Gas as generate can in terms of the others of system 10 in the water source of vapor that uses, as discussed below.Water steams Air-flow 18 itself is also used as the otherwise vapor for system 10, and such as will be located at, at reservoir 12 or it is basic On downstream immediately aqueous solution preheating.
Can will include water, unreacted dicarboxylic acids and diamines, for example, in the form of unreacted ammonium carboxylate salt and, If it does, the reaction mixture of Polvamide prepolymer is transferred to reactor 20 from evaporator 14 via conduit 22.In reactor In 20, other water from reaction mixture is removed and unreacted dicarboxylic acids and diamines can react with each other or and polyamides Amine prepolymer react, or both be carried out at the same time, to form the first polyamide polymer.Temperature in reactor 20 can be further The temperature in evaporator 14 is increased to over to remove other water.In instances, the temperature in reactor 20 can be about 150 DEG C To about 300 DEG C, such as from about 200 DEG C to about 250 DEG C, for example, about 220 DEG C to about 230 DEG C, such as from about 228 DEG C, for example, about 150 DEG C, about 160 DEG C, about 170 DEG C, about 180 DEG C, about 190 DEG C, about 200 DEG C, about 210 DEG C, about 215 DEG C, about 220 DEG C, about 225 DEG C, about 230 DEG C, about 235 DEG C, about 240 DEG C, about 245 DEG C, about 250 DEG C, about 260 DEG C, about 270 DEG C, about 280 DEG C, about 290 DEG C or about 300 DEG C.It leaves anti- Answer the first polyamide polymer of device 20 and the solution of unreacted dicarboxylic acids and diamines that there can be the water of about 1 weight % to about The water concentration of the water of 20 weight %, the such as from about water of 5 weight % to about 15 weight % water, for example, about 1 weight %, about 2 weight %, About 3 weight %, about 4 weight %, about 5 weight %, about 6 weight %, about 7 weight %, about 8 weight %, about 8.5 weight %, about 9 weights Measure the water of the weight % of %, about 9.5,10,11,12,13,14,15,16,17,18,19 or 20 weight %.
Reactor 20 can be equipped with being in fluid communication with reactor 20, the rectifying column that is such as in fluid communication via conduit 26 24.Rectifying column 24 can be with, and then, it is in fluid communication with floss hole pipeline 28.
Can by the first polyamide polymer formed in reactor 20 together with unreacted dicarboxylic acids and diamines from Reactor 20 is transferred to flash vessel 30 via conduit 32.In flash vessel 30, the first polyamide polymer and unreacted dicarboxyl The substantive rise of the temperature of the reaction mixture of acid and diamines, is such as increased to about 150 DEG C to about 400 DEG C, for example, about 250 DEG C to about 350 DEG C, such as from about 260 DEG C to about 300 DEG C, such as from about 280 DEG C, for example, about 200 DEG C or about 210 DEG C, about 220 DEG C, about 230 DEG C, about 240 DEG C, about 250 DEG C, about 260 DEG C, about 265 DEG C, about 270 DEG C, about 275 DEG C, about 280 DEG C, about 285 DEG C, about 290 DEG C, about 295 DEG C, about 300 DEG C, about 305 DEG C, about 310 DEG C, about 320 DEG C, about 330 DEG C, the temperature of about 340 DEG C or about 350 DEG C.In flash vessel 30 Inlet, the pressure of reaction mixture is relatively high, such as from about 1.7 megapascal (MPa) (about 245 pounds/square inch of absolute pressures (psia)) to about 2.1MPa (305psia), for example, about 1.9MPa (about 275psia) to about 2MPa (about 290psia).Pressure can To be gradually lowered as reaction mixture is advanced through flash vessel 30, so that in the exit of flash vessel 30, pressure is opposite It is low, in some cases close to vacuum, such as with about 6 kPas (kPa) (about 0.9psia) to about 50kPa (about 7.2psia), The absolute pressure of such as from about 25kPa (about 3.7psia) to about 45kPa (about 6.5psia).High temperature in flash vessel 30 gradually drops Low pressure is applied on reaction mixture with reaction mixture by flash vessel 30, by other water from reaction mixture It is removed in the form of flashing the vapor left.It is left as vapor is flashed from reaction mixture, the first polyamide polymer Further polymerization can be undergone to form the second polyamide polymer.At the port of export of flash vessel 30, vaporous water can be formed The two-phase mixture of steam and the second polyamide polymer and the liquid mixture of unreacted dicarboxylic acids and diamines.It can be by water Steam is discharged from flash vessel 30, such as by the discharge orifice (not shown) in flash vessel 30 or with leaving sudden strain of a muscle via delivery channel 34 The product stream of steaming device 30 is together.Leave the second polyamide polymer of flash vessel 30 and the solution of unreacted dicarboxylic acids and diamines Can with about 0.1 weight % water to about 5 weight % water water concentration, such as from about the water of 0.5 weight % is to about 2 weight %'s Water, for example, about 0.1 weight %, about 0.2 weight %, about 0.4 weight %, about 0.5 weight %, about 0.6 weight %, about 0.8 weight Measure %, about 0.9 weight %, about 1 weight %, about 1.1 weight %, about 1.2 weight %, about 1.4 weight %, about 1.5 weight %, about The water of 1.6 weight %, about 1.8 weight % or about 2 weight %.Leave the second polyamide polymer of flash vessel 30 and unreacted The solution of dicarboxylic acids and diamines can have about 5 to about 30, the relative viscosity of such as from about 9 to about 20.
Flash vessel 30 can include at least one relatively long pipe, and winding passes through flash vessel 30, also referred to as flash vessel 30 Pipe.The pipe can deliver the entrance of reaction mixture from flash vessel 30 to outlet.The pipe can be cut in inlet with small Area such as minor diameter originates, and can along the length expansion of pipe, until it has the sectional area of opposite bigger in exit, For example, relatively large diameter.Sectional area increasing from entrance to outlet can reduce pressure from the entrance of flash vessel 30 to outlet, As described above.
The condensation that catalyst can be added in to reaction mixture to peomote formation polyamide described herein is anti- It should.In instances, can by catalyst at evaporator 14 (for example, into entrance in evaporator 14 in), in reactor At 20 (for example, into entrance in reactor 20 in) or at flash vessel 30 (for example, into the entrance in flash vessel 30 In) add in reaction mixture.Although catalyst can be added in, catalyst is not for polymerizing polyamide reaction occurs It is necessary.In an example, catalyst can include at least one in sodium hypophosphite, manganese hypophosphite and phenyl phosphinic acid.
The second polyamide polymer that can will be formed in flash vessel 30, unreacted dicarboxylic acids and diamines via Conduit 34 is transferred to finisher 36 from flash vessel 30.Finisher 36 can remove other water so that the second polyamide gathers Object experience is closed further to polymerize to form the final polyamide polymer with final required molecular weight or molecular weight ranges. Selected final required molecular weight or molecular weight ranges can depend on the final required property of polyamide products.Aftercondensated Water in device 36 can be removed by applying high temperature and vacuum pressure to the reaction mixture in finisher 36.Pass through control Apply to residence time in finisher 36 of vacuum pressure and reaction mixture of finisher 36, can control most The final scope of the molecular weight of whole polyamide polymer.Temperature in finisher 36 can be about 150 DEG C to about 400 DEG C, Such as from about 250 DEG C to about 350 DEG C, for example, about 260 DEG C to about 300 DEG C, such as from about 284 DEG C or about 285 DEG C, for example, about 210 DEG C, about 220 DEG C, about 230 DEG C, about 240 DEG C, about 250 DEG C, about 260 DEG C, about 265 DEG C, about 270 DEG C, about 275 DEG C, about 280 DEG C, about 285 DEG C, about 290 DEG C, about 295 DEG C, about 300 DEG C, about 305 DEG C, about 310 DEG C, about 320 DEG C, about 330 DEG C, about 340 DEG C or about 350 DEG C.At one In example, the pressure in finisher 36 can be it is similar or identical with the pressure in the exit of flash vessel 30, such as from about 5kPa (about 0.7psia) to about 50kPa (about 7.2psia), such as from about 10kPa (1.4psia) to about 20kPa (about 2.9psia).From Open finisher 36 final polyamide polymer can have about 0.0001 weight % to the water of about 2 weight % water it is dense Degree, the water of the water of for example, about 0.001 weight % to about 1 weight %, such as from about 0.01 weight % to about 1 weight %, for example, about 0.0001 weight %, about 0.001 weight %, about 0.01 weight %, about 0.05 weight %, about 0.1 weight %, about 0.2 weight %, About 0.3 weight %, about 0.4 weight %, about 0.5 weight %, about 0.6 weight %, about 0.7 weight %, about 0.8 weight %, about 0.9 Weight %, about 1 weight %, about 1.2 weight %, about 1.4 weight %, about 1.5 weight %, about 1.6 weight %, about 1.8 weight % Or about 2 weight % water.Leave finisher 36 final polyamide polymer can with about 30 to about 100 it is relatively viscous Degree.
Final polyamide polymer can leave finisher 36 by transferring pipeline 40.Transferring pipeline 40 can feed Into final process system 42, wherein final polyamide polymer can pass through further mechanical treatment, such as spin, squeeze out Be granulated one or more of.For example, final polyamide polymer can be passed through the die head with multiple small capillaries It squeezes out, continuously to prepare multiple polyamide strands.Strands can be cut into polyamide pellet in comminutor.
Reactor 20 and flash vessel 30 can be referred to herein as " main paradigmatic system ", because the major part of dicarboxylic acids and diamines It is aggregated in reactor 20 and flash vessel 30 and occurs.Although system 10 can include the other equipment wherein polymerizeing, as after Condensation kettle 36, the others equipment are not considered as the part of " main paradigmatic system " for the purpose of this disclosure.
The other example description of general technology is in U.S. Patent number 2,130,948, U.S. Patent number 2,361,717, U.S. State's patent No. 2,689,839, U.S. Patent number 3,113,843, U.S. Patent number 3,361,537, U.S. Patent number 3,717, 330th, U.S. Patent number 3,900,450 and U.S. Patent number 4,134,736 in, disclosures of which is incorporated by reference, such as It is provided equally again with entire content herein.
Additive can be added in polyamide polymer to provide or improve multiple spies of obtained polyamide products Sign.For example, pigment can be added in control the color of polyamide products, such as titanium dioxide (Ti02) it may be used as white pigment. End-capping reagent, such as acetic acid can be added in the end of technique, for example, to terminate polymerization.End-capping reagent can also be added in reservoir Salt in 12.If using catalyst, inactivating agent, such as sodium acid carbonate can be added in the end of technique so that catalyst Inactivation.
A kind of additive that can add in increase the bulk life time of polyamide products is antioxidant.Antioxidant adds Agent can prevent, reduces or postpone polyamide and be attributed to one or more degradations in heat, light and oxygen.In polyamide In manufacture, such as the common antioxidant stabilization additive used in the manufacture of nylon 6,6 is copper-containing compound, such as copper Salt or copper complex.
Copper-containing compound can be added in the arbitrary number of level of technique, and the salting liquid being typically added in reservoir 12, To reactor 20 or into the reaction mixture flowing in flash vessel 30.In the instance system 10 of the disclosure, it can will contain The downstream largely polymerizeing that copper compound occurs in the main paradigmatic system of system 10, for example, in the downstream of flash vessel 30 or It is added in the downstream of reactor 20 but in the upstream of flash vessel 30, as described in more detail.In the case process of Fig. 1 In, the first cupric composition 50 can be added in via the first feeding line 52 to leading between flash vessel 30 and finisher 36 Pipe 34 can add in the second cupric composition 54 in 36 downstream of finisher and processing via the second feeding line 56 Transmission pipeline 40 of 42 upstream of system, or both is carried out at the same time.
It can add in the example of the copper-containing compound of system 10 and include, but are not limited to, mantoquita and copper complex.Mantoquita Example include copper (I) salt (for example, cuprous salt) and copper (II) salt (for example, cupric salt), can be halogenation mantoquita shape Formula, such as cupric iodide (I) (CuI), copper bromide (I) (CuBr), copper bromide (II) (CuBr2) or copper chloride (II) (CuCl2).Also may be used To use other mantoquitas, such as copper acetate (II) (Cu (OC (O) CH3)2)。
Copper-containing compound can with can support, improve or supplement copper-containing compound stabilisation or antioxidant effect one Kind or various other additive is helped to be added in combination.Herein by copper-containing compound and one or more this groups for helping additive It is collectively referred to as " cupric composition ", and sometimes referred to as " antioxidant bag " or " antioxidant blends "." cupric combines term The copper-containing compound and one or more that object " can refer to mix or be combined before adding in polyamide polymer The composition of additive is helped, said composition is included in point identical in substantially the same time or system 10 and adds in polyamide The copper-containing compound and one or more of polymer help composition final in additive or final polyamide products to include containing It copper compound and optionally includes one or more and helps additive.Can include together with copper-containing compound to support, improve or The example for helping additive of supplement copper-containing compound includes, but are not limited to, one or more sylvite such as potassium bromide (KBr) and iodine Change potassium (KI).
However, copper-containing compound, which is added in polyamide such as nylon 6,6, may cause problem.For example, copper-containing compound is Know in the equipment in polyamide manufacturing process or pipe and plated out as copper metal.The copper plated out may interfere with process equipment, such as anti- Answer the operation of device 20, rectifying column 24, flash vessel 30 or finisher 36.The copper plated is also possible to the particular component for causing technique Time between safeguarding or shutting down, " maintenance of life " for being referred to herein as the special order of equipment shorten.For example, sudden strain of a muscle described above Steaming device such as flash vessel 30 can have the specified maintenance of life of 24 to 36 months, but plating out in copper metal to the pipe of flash vessel can Maintenance of life can be reduced to 6 to 12 months.Be attributed to the maintenance of life for the shortening that copper plates out may cause more shut down and Higher safeguard spends.
Shorter maintenance of life is attributed to, plating out for copper may cause long-term shut down and cannot manufacture final polyamide production Object.It is alternatively possible to second or backup of equipment are installed with stopping operation or safeguarding in the first of equipment or main part Process operation is kept in journey.For example, if copper is plated out on flash vessel, then system may need the second flash vessel so that can The system is converted to second new flash vessel from first copper-plated flash vessel.Possibility is needed for the second flash vessel It is expensive.For example, each flash vessel may be expensive, and system will also need to other pipe, valve and control system portion Part between two flash vessels so as to convert, so that can for only adding total additional capital needs of other flash vessel Can be about four times of flash vessel cost.If it is expected that copper is in arbitrary other equipment, as between reactor, finisher or equipment Arbitrary pipe in plate out, it may be necessary to the similar increase in the total fund cost of system.
In addition to shutting down with the cost of the second optional equipment, the maintenance comprising copper-plated equipment is also possible to be more to choose It is war property and more expensive.It is plated out on flash vessel with copper, exemplified by such as plating out on the inner surface of flash vessel pipe, can incited somebody to action again Pipe takes out from flash vessel, and can remove copper chemistry.The technique that copper is removed from pipe may be expensive, time-consuming, and And other safety measure may be needed.A kind of method of copper is removed from flash vessel pipe can be included with nitric acid (HNO3) cleaning Pipe, copper that can be gradually with being plated in above are reacted and removed it.However, security may be needed using the work of nitric acid Prevention is exposed to nitric acid to avoid improper.In addition, it carefully configures anyway or using nitric acid, is all likely difficult to or impossible Prevent nitric acid from removing rather than only removing copper facing by at least sub-fraction of the material of pipe such as stainless steel.Therefore, nitrate method may The bulk life time of pipe is substantially reduced, for example, the normal entire life from about 25 years was reduced to the entire life of about 10 to 12 years.Cause This, plating out for copper may cause higher cost, challenging maintenance program, and may need equipment it is more frequent more It changes, this is attributed to the service life that maintenance program itself reduces equipment.
Copper plates out the concentration for being likely to reduced copper-containing compound in polyamide products.This reduction in copper concentration may be led The system for causing low antioxidant effect or may needing a greater amount of copper-containing compounds to obtain with not plated out including copper is identical Required antioxidant effect.
The copper plated out may also come off during polyamide manufacturing process, and the copper metal to come off may cause to gather The obstruction of amide polymer product or stopping.Copper in final polyamide products may be decreased the quality of polyamide, such as pass through One or more physical properties are negatively influenced, such as intensity or durability or the discoloration by causing polyamide products.
Copper-containing compound is also possible to the gelation for causing the polyamide polymer in the technique.It is believed that copper-containing compound can To interact with polyamide polymer or react the formation or accumulation that cause gel, such as via the degradation of polyamide.Containing After addition of the copper compound in flash vessel or in finisher, the gelation of polyamide polymer may can especially go out Existing, this is attributed to the condition (for example, temperature and pressure) of these parts of equipment and is attributed to polyamide polymer when it is being dodged Reach high viscosity during higher molecular weight in steaming device and finisher.Gelation may interfere with the manufacture of polyamide, such as logical Cross the conduit in occluding device or system.
Copper-containing compound is also possible to cause etching problem, this either from copper-containing compound itself or with can be with cupric What compound included forming cupric composition together helps additive to combine, as described above.If for example, use copper bromide (I) (CuBr) or copper bromide (II) (CuBr2) be used as copper-containing compound or contain if being used together another kind with potassium bromide (KBr) Copper compound, cupric composition may become being corrosive very much.CuBr、CuBr2Or copper-containing compound and KBr combination it is believed that Form hydrobromic acid (HBr), possible corrosion pipeline, the pipe of flash vessel and other equipment.To prevent this corrosion, will contact Copper-containing compound and may cause the equipment of arbitrary additive of corrosion that may need by special resistant material, as titanium or its He is more peculiar, and metal alloy is made.However, these special materials may greatly increase the cost of system.
The inventor of embodiment of the present invention has found, (such as passes through when copper-containing compound is added in 30 upstream of flash vessel Start to add in copper-containing compound into reservoir 12 or to substantially just in the conduit 32 of 30 upstream of flash vessel in technique) When, many problems related with copper-containing compound described above occur.For example, copper metal is plated out when it is in flash vessel 30 The problem of may be special during generation because the pipe of flash vessel 30 may to copper under 30 service condition of flash vessel plating out especially It is sensitive.As described above, the influence that copper plates out to flash vessel 30 is also likely to be particularly expensive, showing needs other flash vessel 30th, the maintenance of life of reduction, the entire life of reduction and increased maintenance.
The gelation as caused by copper-containing compound may be under the treatment conditions (for example, temperature and pressure) of flash vessel 30 more It is susceptible to so that if copper-containing compound added in the upstream of flash vessel 30, gelation may be easier to occur.Flash vessel The small cross-sectional area of 30 inner tube is also likely to be especially sensitive to blocking when there is gelation.
In the instance system 10 of the disclosure, the polyamide that can be added in copper-containing compound to main paradigmatic system downstream gathers Object is closed, for example, the polyamide polymer in 30 downstream of reactor 20 and flash vessel.System 10 can be configured so that cupric chemical combination Object is added in after the water of major part is removed to polyamide polymer, such as so that the polyamides at copper-containing compound addition point The percentage of water is the less than about water of 20 weight % in amine polymer, for example, less than about 15,14,13,12,11,10,9,8,7,6, 5th, the water of the water of the water of the water of 4 or 3 weight %, less than about 2 weight %, less than about 1.5 weight %, less than about 1.4 weight % is few In the water of about 1.3 weight %, less than about 1.2 weight % water, the less than about water of the water of 1.1 weight % or less than about 1 weight %. System 10 is also configured as so that adding in copper-containing compound to the point of the specific relative viscosity of polyamide polymer acquisition, example Such as, at least about 2, such as at least about 2.5, for example, at least about 5, such as at least about 6, at least about 7, at least about 8, at least about 9, at least about 10th, at least about 11, at least about 12, at least about 13, at least about 14, at least about 15, at least about 16, at least about 17, at least about 18, extremely Few about 19, at least about 20, at least about 25, at least about 30, at least about 35, at least about 40, at least about 45, at least about 50, at least about 55th, at least about 60, at least about 65, at least about 70, at least about 75, at least about 80, at least about 85, at least about 90, at least about 95 or At least about 100.System 10 is also configured as specifying molecular weight so that copper-containing compound is added in polyamide polymer to obtain Point.
For example, copper-containing compound can be added in the conduit 34 and aftercondensated between flash vessel 30 and finisher 36 The one or both transferred in pipeline 40 in 36 downstream of device.Fig. 1 show can be used for by the first cupric composition 50 feed to First feeding line 52 of the conduit 34 between flash vessel 30 and finisher 36 and it can be used for the second cupric composition The second feeding line 56 of pipeline 40 is extremely transferred in 54 chargings.In some instances, system can include 52 He of the first feeding line One or both in second feeding line 56.
In some instances, the system only with the first feeding line 52 between flash vessel 30 and finisher 36 may It is needed, for example, the service condition dependent on system.In other examples, only have and be connected to 36 downstream of finisher Transmission pipeline 40 in the system of the second feeding line 56 may be desired, such as so that it is as late as possible in the process Add in copper-containing compound to avoid copper facing, gelation and/or corrosion appearance (for example, because transfer pipeline 40 in condition compared with Them are not easily leaded to occur) or the amount for the system 10 for being exposed to these problems is minimized (for example, allowing to only in a part Transmission pipeline and processing system 42 in experience safeguard, redundant equipment and other problems described above).
Although by added in the downstream of flash vessel 30 copper-containing compound can to avoid or minimize with copper-containing compound Add in the problem of related, copper-containing compound is added in the second polyamide polymer flowed from flash vessel 30 by conduit 34 or Addition is still difficult by transferring the final polyamide polymer that pipeline 40 flows extremely from finisher 36.These polyamides The molecular weight of amine polymer may be relatively high, this generally means that the material for flowing through conduit 34 or transmission pipeline 40 may be The fluid of high viscosity.In the case where nylon 66 manufactures, the second polyamide polymer for flowing through conduit 34 can have About 5 to about 9, and in some cases, 20 or about 30 relative viscosity is up to about, and flow through and transfer pipeline 40 most Whole polyamide polymer can have about 30 to about 50, and be up to about 100 relative viscosity in some cases.
These relatively high viscosity may to be particularly difficult to ensure copper-containing compound and any institute in polyamide polymer The suitable mixing for helping additive needed.In copper-containing compound and help additive not substantially completely and substantially mixed uniformly In the case of, required antioxidant effect may not exist in all positions in final polyamide products.In other words, polyamide Some positions in product may be still to being attributed to heat, light or oxygen oxidative degradation be sensitive, this may cause by polyamides The defects of polyamide article that amine product is formed or failure.Copper-containing compound and help additive in the second polyamide polymer and most Mixing in whole polyamide polymer, may be in charging to the mixing in the first polyamide polymer in flash vessel 30 with it Compare, it may be possible to significantly it is more difficult, for example, because the first polyamide polymer can have with the second polyamide polymer and Final polyamide polymer is compared to significantly lower molecular weight and relative viscosity.Especially, copper-containing compound is mixed to leading May be difficulty in final polyamide polymer in the second polyamide polymer in pipe 34 or in transmission pipeline 40, because For copper-containing compound can be bound in liquid or slurry mixture, but the liquid of copper-containing compound or slurry mixture are by allusion quotation There is the viscosity dramatically different with the first polyamide polymer or final polyamide polymer type.Mixing has dramatically different Two fluids of viscosity may be especially difficult.
In order to avoid it is related to addition of the copper-containing compound in 30 upstream of flash vessel the problem of, it is and enough also for providing Mixing so that cupric composition substantially consistent ground and equably mixes in entire polyamide polymer, system 10 can be with Including one or more mixers to mix cupric composition into polyamide polymer.For example, system 10 can include using In mixing to the first mixer 70A in the second polyamide polymer in conduit 34 or be used for the first cupric composition 50 By the second cupric composition 54 mix to transfer pipeline 40 in final polyamide polymer in the second mixer 70B or Person's system 10 can include both the first mixer 70A and the second mixer 70B.Each mixer 70A, 70B can incite somebody to action corresponding Cupric composition 50,54 mix to conduit 34 or transfer pipeline 40 in corresponding polyamide polymer in.
Copper additives can be added in via following form into stream：It adds in pure copper additives or is added via comprising copper Agent and the mixture of carrier material, it is the carrier material such as solvent (for example, water or organic solvent), 6,6 carrier of prefabricated nylon, another A kind of polymer support adds the part or combination thereof of the shunting product stream of additive.In point including product stream In the embodiment of stream, shunting can be the product stream or less of about 0.000,001 weight %, the 0.000 of product stream, 01 weight Measure %, 0.000,1,0.001,0.01,0.1,1,2,3,4,5,10,15,20,30,40 or about 50 weight %.Contain copper additives The material of addition to product stream can have following copper additives concentration：About 0.000,001 weight % to about 100 weight %, Or about 0.000,001 weight % or less or about 0.000,005 weight %, 0.000,01,0.000,05,0.000,1, 0.000,5、0.001、0.005、0.01、0.05、0.1、0.5、1、1.5、2、3、4、5、10、15、20、25、30、35、40、45、 50th, 55,60,65,70,75,80,85,90,95,96,97,98 or about 99 weight % or more.Additive or including the additive Mixture can with any appropriate flow velocity, such as from about 0.000,001L/ minutes or lower or about 0.000,005L/ minutes, 0.000,01、0.000,05、0.000,1、0.000,5、0.001、0.005、0.01、0.05、0.1、0.5、1、1.5、2、3、4、 5th, 10,15,20,25,50,75,100,125,150,175,200,250,300,400,500,750,1,000,2,500,5, 000th, 10,000,50,000 or about 100,000L/ minutes or higher, it adds in product stream.Additive or additive are added in it The temperature of the product stream of mixture can be any appropriate temperature, such as from about 100 DEG C -350 DEG C or about 100 DEG C or lower or about 110℃、120、130、140、150、160、170、180、190、200、210、220、230、240、250、260、270、280、 290th, 300,310,320,330,340 DEG C or about 350 DEG C or higher.Additive or mixture comprising additive can be appointed Suitable temperature of anticipating is added in product stream, such as temperature close with the temperature of product stream or temperature such as higher than the temperature of product stream Spend (for example, to prevent from condensing), such as from about 100 DEG C -350 DEG C or about 100 DEG C or lower or about 110 DEG C, 120,130,140, 150、160、170、180、190、200、210、220、230、240、250、260、270、280、290、300、310、320、330、 340 DEG C or about 350 DEG C or higher；Gather it is optionally possible to injection zone similarly be heated to prevent or minimize in product stream Close the condensation of object material.The concentration of copper additives can be any appropriate concentration in product stream after the addition of additive, Such as from about 0.000,001 weight % or lower or about 0.000,005 weight %, 0.000,01,0.000,05,0.000,1, 0.000,5th, 0.001,0.005,0.01,0.05,0.1,0.5,1,1.5,2,3,4 or about 5 weight % or lower.
Fig. 2, which is shown, can be used for mixing cupric composition 72 to the example in the conduit 74 of delivery polyamide polymer 76 The schematic diagram of mixer 70C.Example blender 70C may be used as first and second mixer 70A, 70B in the system 10 of Fig. 1 In any one.Therefore, cupric composition 72 can represent the first cupric composition 50 or the second cupric composition in Fig. 1 54, and conduit 74 can be conduit 34 between flash vessel 30 and finisher 36 or can be 36 downstream of finisher Transmission pipeline 40.In the embodiment with multiple mixers, each mixer can add in appointing in additive total amount It anticipates suitable ratio.For example, arbitrary mixer, such as any one in first or second mixer, can add in about 1 weight %'s Total additive, 2,3,4,5,10,15,20,25,30,35,40,45,50,55,60,65,70,75,80,85,90,95,96,97, Total additive of 98 or about 99 weight %, remaining part are added in via one or more other mixers.
In an example, cupric composition 72 can include the particle of copper-containing compound and polymer support, such as polymerize The solids of object carrier.It can also include other compounds in cupric composition 72, help additive, example as described above Such as in the form of the particle for helping additive.
The particle of copper-containing compound can include the particle of one or more copper-containing compounds described above, such as mantoquita Such as cupric iodide (I), copper bromide (I), copper bromide (II), copper acetate (II) or copper chloride (II).Polymer support can include can To melt and the polymer that is mixed with the polyamide polymer 76 in conduit 74, as described below.Polymer support can be with It is compatible with the final use needed for polyamide polymer 76, so that including for a small amount of polymer supports will be substantially not negative Influence the required physical property of final polyamide products.In some instances, polymer support include polyamide in order to provide with The substantially tight fit of polyamide polymer 76.For example, in the case where polyamide polymer 76 includes nylon 66, polymerization Object carrier can include nylon 6,6 or nylon 6.Polymer support can further include other kinds of polymer (for example, addition polymers Such as plastics, acrylic compounds, polyester), to be polymer support compatible with polyamide products (for example, nylon 6,6) and not for condition Negatively affect the mechanically or physically property needed for polyamide products.
In an example, polymer support can also be the form for the particle that may be mixed together, as with dry Mixture and copper-containing compound particle and may be required arbitrary additive is helped to mix.The particle of copper-containing compound and polymer supported Body can also be pre-formed for pellet or fritter with the predetermined ratio of copper-containing compound and polymer support.
The mixture of cupric composition 72 or pellet can be maintained at and be configured to charging (such as warp into feed screw 80 By feed well 82) hopper 78 in.Feed screw 80 can include tommy bar 84, can move cupric composition 72 logical Cross feed screw 80.Feed screw 80 can be heated to the temperature for being enough molten polymer carrier, generate cupric chemical combination The mixture of object and molten polymer carrier.In an example, mixture can include being dissolved in molten polymer carrier Copper-containing compound.In another example, mixture can include the copper-containing compound for remaining substantially solid form, example Such as, the particle as copper-containing compound, the wherein mixture form molten polymer carrier and substantially solid copper-containing compound Slurries.Mixture can further include a part of copper-containing compound being dissolved in molten polymer carrier and remain solid grain The combination of a part of copper-containing compound (it forms slurries with molten polymer carrier) of son.
In an example, feed screw 80 can be heated using heater (not shown), the heater can be with Partially or completely around at least a portion of feed screw 80.It is, for example, possible to use vapor chuck or other heat are handed over Feed screw 80 to be heated to the temperature for being enough molten polymer carrier by parallel operation.
Can by copper-containing compound, any help the mixture of additive and molten polymer carrier from feed screw 80 It is passed via that can feed substantially liquid mixture to the feeding line 86 in the molten polyamide polymer 76 in conduit 74 It is handed to conduit 74.Feeding line 86 can include pump 88, can be with the mixing of pressurizing melting polymer support and copper-containing compound Object so that it can enter polyamide polymer 76 stream and substantially mixed with polyamide polymer 76, such as mixed via turbulent flow It closes so that copper-containing compound and arbitrarily help additive that will essentially homogeneously be mixed in polyamide polymer 76.Conduit 74 can To include mixer, such as static mixer, by copper-containing compound and it is arbitrary help additive with polyamide polymer 76 equably Mixing.
Embodiment
Embodiments of the present invention can be by reference to the following instance that provides by way of example and by more preferable geographical Solution.The invention is not restricted to examples given herein.
For the general-purpose system of embodiment
In continuous 6,6 manufacturing process of nylon, adipic acid and hexamethylene diamine are blended in water with substantially equimolar ratio In, to form the aqueous mixture containing 6,6 salt of nylon and with about 50 weight % water.By saline solution with about 105L/ points Clock is transferred to evaporator.Saline solution is heated to about 125-135 DEG C (130 DEG C) and the salt of water from heating is water-soluble by evaporator Liquid removes so that water concentration is about 30 weight %.The salt mixture of evaporation was transferred to tubular reactor with about 75L/ minutes. The temperature of the salt mixture of evaporation is increased to about 218-250 DEG C (235 DEG C) by reactor, so as to allow reactor by water from heating The salt mixture of evaporation further remove so that water concentration reaches about 10 weight %, and salt is further polymerize.It will be anti- The mixture answered was transferred to flash vessel with about 60L/ minutes.The mixture of reaction is heated to about 270-290 DEG C by flash vessel (280 DEG C) from the mixture of reaction further to remove water so that water concentration reaches about 0.5 weight %, and causes reaction Mixture further polymerize.The mixture of flash distillation with about 13 relative viscosity was transferred to aftercondensated with about 54L/ minutes Device makes polyblend be subjected to vacuum further to remove water so that water concentration reaches about 0.1 weight % and relative viscosity reaches To about 60, so that polyamide obtains suitable final polymerization scope, the polyblend for afterwards crossing aftercondensated is with about It is transferred within 54L/ minutes the comminutor for generating the extruder of nylon strands via multi-thread material die head and strands being cut into pellet.
For determining the conventional method of gel fraction.Each gel fraction described in embodiment is determined by taking by two methods The average value of gel fraction determine.In first method, while reaction mixture is still heat, by liquid reaction mixture It is discharged from system, system is cooled down, dismantled, and visual inspection is to estimate the volume of gel therein.In the second approach, exist While reaction mixture is still heat, liquid reaction mixture is discharged from system, cooling fills water, and discharges water.From The system bulk for not having gel subtracts the volume from the water that system is discharged to determine the volume of the gel in system.In order to determine to set The specific part of equipment or specific position downstream are only by the specific parts of standby one or more or the gel fraction in specific position downstream System is filled with water.In two methods, the density of gel is it is estimated that be 0.9g/cm3。
Comparative example 1a- copper acetates are in the addition of flash vessel upstream
By 6,6 and 5 weight % copper acetates (II) of nylon (Cu (OC (O) CH3)2, also referred to as copper acetate) mixture add in Between polymer reactor and flash vessel, the nylon polymer blends of reactor downstream and flash vessel upstream.Mixture is being added About 235 DEG C are preheated to before entering, and is added in about 2.1L/h.
The addition of flash vessel upstream copper acetate cause a part of copper atom as copper metal flash vessel, finisher and with It is plated out in its transmission pipeline connected.After the operation of about 12 weeks, the layers of copper of about 0.1mm plates out setting in the downstream of addition It is standby upper.The copper metal that a part plates out becomes sometimes from flash vessel or finisher removal, and and nylon polymer blends It carries together, causes unfavorable copper metal thin slice in final polyamide products, reduce product qualities.Copper plates in flash vessel The synthesis speed gone out causes to shut down and clean flash vessel after the run time of about 8 months, this attribution at least partly The copper foil of significant quantity in product qualities are by final product and reduce.It is used to clean and safeguard offline when flash vessel is removed When, the copper plated out is removed via the program for using nitric acid so that copper metal to be removed from flash vessel pipe, this is time-consuming and holds high Expensive.Because relatively short service intervals and for the complicated cleaning procedure needed for flash vessel, the system two sudden strains of a muscle in parallel Steaming device replaces an operation, so that a flash vessel always remains on, this requires the capital investment of bigger in systems.
Temperature and pressure (280 DEG C and 2MPa) in flash vessel causes copper acetate to react and deteriorated with nylon.Deterioration Nylon cause the increased gelation in downstream (increased gel generate within about 2Kg/ weeks, with not having copper acetate to add before flash vessel The corresponding systematic comparison entered), it is accumulated in flash vessel, in the transmission pipeline and valve between flash vessel and finisher, after In condensation kettle and in the transmission pipeline in finisher downstream.Increased gel generates the overall quality for reducing final product.
Plating out for copper metal is also reduced into the acetic acid copper concentration in the final nylon polymer product of extruder, so as to Reduce the antioxidant of copper additives in the product that aftercondensated is crossed and the amount of stabilizer effect.Into the nylon polymerization of extruder In object mixture the concentration of copper acetate be attributed to the copper acetate of about 0.001 weight % as copper metal in systems plate out and Reduce about 33%.It is about 0.002 weight % into the acetic acid copper concentration in the final nylon polymer product of extruder.
Comparative example 1b- cupric iodides are in the addition of flash vessel upstream
The mixture of 6,6 and 5 weight % cupric iodides of nylon is added between polymer reactor and flash vessel, under reactor Trip and the nylon polymer blends of flash vessel upstream.Mixture is preheated to about 235 DEG C before addition, and with about 2.1L/h it adds in.
The addition of the cupric iodide of flash vessel upstream causes a part of copper atom as copper metal in flash vessel, finisher It is plated out in transmission pipeline connected to it.After operation about 12 weeks, the layers of copper of about 0.1mm is plated out in the equipment for adding in downstream On.The copper metal plated out of a part becomes to remove from flash vessel or finisher sometimes, and and nylon polymer blends It carries together, causes unfavorable copper metal thin slice in final polyamide products, reduce product qualities.Copper plates in flash vessel Going out the rate to be formed causes shutting down after the run time of about 8 months and cleans flash vessel, is at least partly due to Reduction on product qualities, this is attributed to the copper foil of significant quantity in final product.When flash vessel is changed, by what is plated out Copper is removed via the program for using nitric acid so that copper metal to be dissolved from flash vessel pipe, this is time-consuming and expensive.It is because right Relatively fast replacement and more complicated maintenance program are needed in flash vessel, which replaces a fortune with two flash vessels in parallel Row, so that a flash vessel always remains on, this requires the capital investment of bigger in system.
Temperature and pressure (280 DEG C and 2MPa) in flash vessel causes cupric iodide to react and deteriorated with nylon.Deterioration Nylon cause the increased gelation in downstream (such as with do not have before flash vessel cupric iodide add in corresponding systematic comparison, about Increased gel generates within 2Kg/ weeks), it is accumulated in flash vessel, in the transmission pipeline and valve between flash vessel and finisher, In finisher and in the transmission pipeline in finisher downstream.Increased gel generates the whole product for reducing final product Matter.
Plating out for copper metal is also reduced into the iodate copper concentration in the final nylon polymer product of extruder, so as to Reduce the antioxidant of copper additives and the amount of stabilizer effect in the product that aftercondensated is crossed.Into the nylon polymer of extruder The concentration of cupric iodide in mixture be attributed to the cupric iodide of about 0.001 weight % as copper metal in systems plate out and Reduce about 33%.It is about 0.002 weight % into the iodate copper concentration in the final nylon polymer product of extruder.
Comparative example 1c- copper bromides (II) are in the addition of flash vessel upstream
By the mixture of 6,6 and 5 weight % copper bromides (II) of nylon add between polymer reactor and flash vessel, reaction Device downstream and the nylon polymer blends of flash vessel upstream.Mixture is preheated to about 235 DEG C before addition, and with about 2.1L/h it adds in.
The addition of flash vessel upstream copper bromide (II) causes a part of copper atom as copper metal in flash vessel, aftercondensated It is plated out in device and transmission pipeline connected to it.After operation about 12 weeks, the layers of copper of about 0.1mm is on the equipment in downstream is added in It plates out.The copper metal plated out of a part becomes sometimes from flash vessel or finisher removal, and is mixed with nylon polymer Object is carried together, is caused unfavorable copper metal thin slice in final polyamide products, is reduced product qualities.In flash vessel The middle copper-plated rate of formation causes the flash vessel that shuts down and clean after the run time of about 8 months, this at least partly returns Because on product qualities in final product the copper foil of significant quantity reduction.It is used to clean offline when flash vessel is removed And maintenance, the copper plated out is removed via the program for using nitric acid so that copper metal is dissolved from flash vessel pipe, this be it is time-consuming and And expensive.Because relatively short service intervals and complicated cleaning procedure for flash vessel needs, system parallel connection Two flash vessels replace an operation, so that a flash vessel always remains on, this requires the cost of bigger in system to throw Money.
Temperature and pressure (280 DEG C and 2MPa) in flash vessel causes copper bromide (II) to react with nylon and deteriorate nylon. The nylon of deterioration causes the increased gelation in downstream, and (increased gel generates within about 2Kg/ weeks, with the bromine not before flash vessel Change the corresponding systematic comparison that copper (II) adds in), it is accumulated in flash vessel, the transmission pipeline between flash vessel and finisher In valve, in finisher and in the transmission pipeline in finisher downstream.Increased gel, which generates, reduces final product Overall quality.
Plating out for copper metal also reduces into copper bromide (II) concentration in the final nylon polymer product of extruder, So as to reduce the antioxidant of copper additives and the amount of stabilizer effect in the product that aftercondensated crosses.Into the nylon polymerization of extruder The concentration of copper bromide (II) is attributed to the copper bromide (II) of about 0.001 weight % as copper metal in systems in object mixture Plate out and reduce about 33%.It is about into copper bromide (II) concentration in the final nylon polymer product of extruder 0.002 weight %.
Addition of the embodiment 2- acetic acid copper additives between flash vessel and finisher
By the mixture of 6,6 and 5 weight % copper acetates (II) of nylon add between polymer reactor and flash vessel, flash distillation Device downstream and the nylon polymer blends transferred in pipeline of finisher upstream.Mixture is preheated to about before addition 280 DEG C, and added in about 2.1L/h.
Copper acetate avoid flash vessel to the addition of pipeline after the flash vessel in copper facing.Because copper is not in flash vessel It plates out, flash vessel has the run time of about 36 months.Longer run time is attributed to, which is used only single flash distillation Device is built, and the downtime of single flash vessel is tolerable.The cleaning procedure of flash vessel need not be used for copper-plated The processing of removal.Lower pressure condition causes plating out for less copper metal compared with comparative example 1a in finisher, has The copper acetate of about 0.000,01 weight % plates out within the system, provide about 0.003 weight % into the final of extruder The concentration of copper acetate in nylon product.Such as compared with comparative example 1a, observed at least in the product crossed in final aftercondensated Copper foil less 100x provides the product that the aftercondensated of higher quality is crossed.Such as compared with comparative example 1a, generate in systems about The less gel of 2Kg/ weeks, this provide it is longer between system maintenance during.
Embodiment 3a- acetic acid copper additives to finisher downstream transmission pipeline addition.
The mixture of 6,6 and 5 weight % copper acetates (II) of nylon is added in the biography between polymer reactor and flash vessel It passs in pipeline, flash vessel and finisher downstream, and the nylon polymer blends transferred in pipeline of extruder upstream.It will Mixture is preheated to about 280 DEG C before addition, and is added in about 2.1L/h.
As in Example 2, copper does not plate out in flash vessel so that flash vessel has about 36 between maintenance and cleaning The run time of the moon.As in Example 2, maintenance/broom closet of flash vessel is every being tolerable so that the system is only with single Flash vessel build.When flash vessel and finisher are taken out offline for safeguarding and cleaning, the removal of copper need not be used for Program.
Transferring the condition in pipeline causes seldom plating of the copper metal in pipeline or extruder is transferred, and is mixed in polymer The only copper acetate of 0.000,001 weight % plates out in pipeline is transferred and in extruder as copper in conjunction object, provides about 0.003 The concentration of copper acetate in the extruded material of weight %.Do not observe copper foil in final product, provide than comparative example 1a and The product that the aftercondensated of 2 higher quality of embodiment is crossed.
Embodiment 3b- acetic acid copper additives use shunting product stream to the addition of the transmission pipeline in finisher downstream.
The mixture of 6,6 and 5 weight % copper acetates (II) of nylon is added in the biography between polymer reactor and flash vessel It passs in pipeline, flash vessel and finisher downstream, and the nylon polymer blends transferred in pipeline of extruder upstream.It will Nylon 6,6 from occurred by finisher product stream shunting, shunt with about 2.1L/h occur, and by pure copper acetate add in Nylon is shunted to form mixture.About 280 DEG C are held the mixture in, is added in afterwards to transmission pipeline, and with about 2.1L/h It adds in.
As in Example 2, copper does not plate out in flash vessel so that flash vessel has about 36 between maintenance and cleaning The run time of the moon.As in Example 2, maintenance/broom closet of flash vessel is every being tolerable so that the system is only with single Flash vessel build.When flash vessel and finisher are taken out offline for safeguarding and cleaning, the removal of copper need not be used for Program.
Transferring the condition in pipeline causes seldom plating of the copper metal in pipeline or extruder is transferred, and is mixed in polymer The only copper acetate of 0.000,001 weight % plates out in pipeline is transferred and in extruder as copper in conjunction object, provides about 0.003 The concentration of copper acetate in the extruded material of weight %.Do not observe copper foil in final product, provide than comparative example 1a and The product that the aftercondensated of 2 higher quality of embodiment is crossed.
Embodiment 4- iodate copper additives to finisher downstream transmission pipeline addition.
The mixture of 6,6 and 5 weight % cupric iodides of nylon is added in the transmission pipe between polymer reactor and flash vessel In line, flash vessel and finisher downstream, and the nylon polymer blends transferred in pipeline of extruder upstream.It will mixing Object is preheated to about 280 DEG C before addition, and is added in about 2.1L/h.
As in Example 2, copper does not plate out in flash vessel so that flash vessel has about 36 between maintenance and cleaning The run time of the moon.As in Example 2, maintenance/broom closet of flash vessel is every being tolerable so that the system is only with single Flash vessel build.When flash vessel and finisher are taken out offline for safeguarding and cleaning, the removal of copper need not be used for Program.
Transferring the condition in pipeline causes seldom plating of the copper metal in pipeline or extruder is transferred, and is mixed in polymer The only cupric iodide of 0.000,001 weight % plates out in pipeline is transferred and in extruder as copper in conjunction object, provides about 0.003 The concentration of cupric iodide in the material of the extrusion of weight %.Copper foil is not observed in final product, is provided than comparative example 1b The product crossed with the aftercondensated of 2 higher quality of embodiment.
Embodiment 5- copper bromides (II) additive to finisher downstream transmission pipeline addition.
The mixture of 6,6 and 5 weight % copper bromides (II) of nylon is added in the biography between polymer reactor and flash vessel It passs in pipeline, flash vessel and finisher downstream, and the nylon polymer blends transferred in pipeline of extruder upstream.It will Mixture is preheated to about 280 DEG C before addition, and is added in about 2.1L/h.
As in Example 2, copper does not plate out in flash vessel so that flash vessel has about 36 between maintenance and cleaning The run time of the moon.As in Example 2, maintenance/broom closet of flash vessel is every being tolerable so that the system is only with single Flash vessel build.When flash vessel and finisher are taken out offline for safeguarding and cleaning, the removal of copper need not be used for Program.
Transferring the condition in pipeline causes seldom plating of the copper metal in pipeline or extruder is transferred, and is mixed in polymer It closes the copper bromide (II) for only having 0.000,001 weight % in object to be used as copper in pipeline is transferred and plate out in extruder, provide about The concentration of copper bromide (II) in the extruded material of 0.003 weight %.Copper foil is not observed in final product, is provided frequently The product crossed compared with the aftercondensated of 2 higher quality of example 1c and embodiment.
Illustratively term uses and not restrictive, and in this term and table for used term and statement There is no any equivalent for excluding given and description feature or part thereof of intention in the use stated, and should be appreciated that It is that in the range of the theme of the present invention for required protection, a variety of modifications are possible.Although it is to be understood, therefore, that Embodiment of the present invention, the modifications and variations of concept disclosed herein are specifically disclosed through passing through example and optional feature It can be taken by those skilled in the art, and this modifications and variations are considered within by this hair of appended claims In the range of bright theme.
Other embodiments
The present invention provides the example below embodiment, and sequence number is not interpreted to provide significance level：
Embodiment 1 can include theme (such as device, device, method or the one or more modes acted), such as It can include a kind of system of preparation for polyamide.The theme can include：Main paradigmatic system, the main polymerization system One or more raw material are converted into polyamide products by under unified central planning be set to；The conduit in the main paradigmatic system downstream, the conduit It is configured to transfer the polyamide products；And feeding line, the feeding line are configured to feed cupric composition to conduit In.
Embodiment 2 can include or can be optionally with embodiment 1 theme combine, to optionally include, institute Stating feeding line includes the feed screw for receiving the heating of the cupric composition.
Embodiment 3 can include or can optionally with one in embodiment 1 and 2 or any combination master Topic combination, to optionally include, the cupric composition includes the particle of copper-containing compound and the mixture of polymer support.
Embodiment 4 can include or can optionally with one in embodiment 1-3 or any combination theme Combination, to optionally include, the polymer support is melted to be formed by the feed screw of the heating includes melt polymerization The mixture of object and the copper-containing compound.
Embodiment 5 can include or can optionally with one in embodiment 1-3 or any combination theme Combination, to optionally include, the feed screw of the heating is configured to feed the mixture into the conduit.
Embodiment 6 can include or can optionally with one in embodiment 1-5 or any combination theme Combination, to optionally include, the polymer support includes at least one in nylon 6 and nylon 6,6.
Embodiment 7 can include or can optionally with one in embodiment 1-6 or any combination theme Combination, to optionally include, the main paradigmatic system includes polymer reactor, and the polymer reactor is configured to will be a kind of or more Kind raw material are converted into the first polyamide；With the back segment system in the polymer reactor downstream, the back segment system configuration is increasing The molecular weight of first polyamide is added to form the polyamide products.
Embodiment 8 can include or can optionally with one in embodiment 1-7 or any combination theme Combination, to optionally include, the back segment system includes the flash vessel in the polymer reactor downstream, wherein the flash vessel is matched somebody with somebody Being set to increases the molecular weight of first polyamide to form the second polyamide.
Embodiment 9 can include or can optionally with one in embodiment 1-8 or any combination theme Combination, to optionally include, conduit, the conduit is in fluid communication with the flash vessel, and the polyamide products include institute State the second polyamide.
Embodiment 10 can include or can optionally with one in embodiment 1-9 or any combination master Topic combination, to optionally include, the back segment system further includes the finisher in the flash vessel downstream, wherein the aftercondensated Device is configured to increase the molecular weight of second polyamide to form melamine.
Embodiment 11 can include or can optionally with one in embodiment 1-10 or any combination master Topic combination, to optionally include, the conduit is in fluid communication with the finisher, and the polyamide products are including described Melamine.
Embodiment 12 can include or can optionally with one in embodiment 1-11 or any combination master Topic combination, to optionally include, polyamide products that the main paradigmatic system is configured so that in the conduit are containing being less than The water of about 5 weight %.
Embodiment 13 can include or can optionally with one in embodiment 1-12 or any combination master Topic combination, to optionally include, the polyamide products that the main paradigmatic system is configured so that in the conduit have extremely Few about 2 relative viscosity.
Embodiment 14 can include or can optionally with one in embodiment 1-13 or any combination master Topic combination, to optionally include, the polyamide products that the main paradigmatic system is configured so that in the conduit have extremely Few about 5 relative viscosity.
Embodiment 15 can include or can optionally with one in embodiment 1-14 or any combination master Topic combination, to optionally include, the polyamide products that the main paradigmatic system is configured so that in the conduit have extremely Few about 9 relative viscosity.
Embodiment 16 can include or can optionally with one in embodiment 1-15 or any combination master Topic combination, to optionally include, the polyamide products that the main paradigmatic system is configured so that in the conduit have extremely Few about 15 relative viscosity.
Embodiment 17 can include or can optionally with one in embodiment 1-16 or any combination master Topic combination, to optionally include, the polyamide products that the main paradigmatic system is configured so that in the conduit have extremely Few about 20 relative viscosity.
Embodiment 18 can include or can optionally with one in embodiment 1-17 or any combination master Topic combination, to optionally include, the polyamide products that the main paradigmatic system is configured so that in the conduit have extremely Few about 25 relative viscosity.
Embodiment 19 can include or can optionally with one in embodiment 1-18 or any combination master Topic combination, to optionally include, the polyamide products that the main paradigmatic system is configured so that in the conduit have extremely Few about 30 relative viscosity.
Embodiment 20 can include or can optionally with one in embodiment 1-19 or any combination master Topic combination, to optionally include, the polyamide products that the main paradigmatic system is configured so that in the conduit have extremely Few about 40 relative viscosity.
Embodiment 21 can include or can optionally with one in embodiment 1-19 or any combination master Topic combination, to optionally include, the polyamide products that the main paradigmatic system is configured so that in the conduit have extremely Few about 50 relative viscosity.
Embodiment 22 can include or can optionally with one in embodiment 1-21 or any combination master Topic combination, to optionally include, the polyamide products that the main paradigmatic system is configured so that in the conduit have extremely Few about 75 relative viscosity.
Embodiment 23 can include or can optionally with one in embodiment 1-22 or any combination master Topic combination, to optionally include, is connected to the extruder of the conduit in the feeding line downstream, the extruder is configured to squeeze out The polyamide products are to form one or more polyamide strands.
Embodiment 24 can include or can optionally with one in embodiment 1-23 or any combination master Topic combination, to optionally include, the cupric composition includes mantoquita.
Embodiment 25 can include or can optionally with one in embodiment 1-24 or any combination master Topic combination, to optionally include, the cupric composition includes at least one of copper (I) salt and copper (II) salt.
Embodiment 26 can include or can optionally with one in embodiment 1-25 or any combination master Topic combination, to optionally include, the cupric composition includes at least one of copper halide (I) salt and copper halide (II) salt.
Embodiment 27 can include or can optionally with one in embodiment 1-26 or any combination master Topic combination, to optionally include, the cupric composition includes at least one mantoquita derived from carboxylic acid.
Embodiment 28 can include or can optionally with one in embodiment 1-27 or any combination master Topic combination, to optionally include, the cupric composition includes cupric iodide (I), copper bromide (I), copper bromide (II), copper acetate (II) it is at least one and in copper chloride (II).
Embodiment 29 can include or can optionally with one in embodiment 1-28 or any combination master Topic combination, to optionally include, the one or more raw material include the dicarboxylic acids of straight chain and the diamines of straight chain or by straight chains Dicarboxylic acids and straight chain diamines formed oligomer.
Embodiment 30 can include or can optionally with one in embodiment 1-29 or any combination master Topic combination, to optionally include, the dicarboxylic acids has structure HO C (O)-R1- C (O) OH, wherein R1It is C1-C15Alkylidene.
Embodiment 31 can include or can optionally with one in embodiment 1-30 or any combination master Topic combination, to optionally include, the dicarboxylic acids is adipic acid.
Embodiment 32 can include or can optionally with one in embodiment 1-31 or any combination master Topic combination, to optionally include, the diamines has structure H2N-R2-NH2, wherein R2It is C1-C15Alkylidene.
Embodiment 33 can include or can optionally with one in embodiment 1-32 or any combination master Topic combination, to optionally include, the diamines is hexamethylene diamine.
Embodiment 34 can include or can optionally with one in embodiment 1-33 or any combination master Topic combination, to optionally include, the one or more raw material include adipic acid and hexamethylene diamine mixture or by The oligomer that the mixture of adipic acid and hexamethylene diamine is formed.
Embodiment 35 can include or can optionally with one in embodiment 1-34 or any combination master Topic combination, to optionally include, the polyamide is nylon 6,6.
Embodiment 36 can include or can optionally with one in embodiment 1-35 or any combination master Topic combination, by include theme (such as device, device, method or acted it is one or more in a manner of), such as can include one kind The method for forming daiamid composition.The theme can include one or more raw material in main paradigmatic system polymerizeing To form polyamide products, the polyamide products from the main paradigmatic system are transferred in the catheter and combine cupric Object is fed into the conduit in the paradigmatic system downstream.
Embodiment 37 can include or can optionally with one in embodiment 1-36 or any combination master Topic combination, to optionally include, described feed the cupric composition to the conduit is included the grain of copper-containing compound The mixture of son and polymer support is fed into feeding line.
Embodiment 38 can include or can optionally with one in embodiment 1-37 or any combination master Topic combination, to optionally include, described feed the cupric composition to the conduit is included the polymer support It melts to form the mixture for including molten polymer and the copper-containing compound in the feeding line.
Embodiment 39 can include or can optionally with one in embodiment 1-38 or any combination master Topic combination, to optionally include, described feed the cupric composition to the conduit includes feeding in the mixture Into the conduit.
Embodiment 40 can include or can optionally with one in embodiment 1-39 or any combination master Topic combination, to optionally include, the polymer support includes at least one in nylon 6 and nylon 6,6.
Embodiment 41 can include or can optionally with one in embodiment 1-40 or any combination master Topic combination to optionally include, one or more raw material polymerizations is included one or more raw material are converted into the One polyamide.
Embodiment 42 can include or can optionally with one in embodiment 1-41 or any combination master Topic combination, it is described to include increasing point of the first polymer by one or more raw material polymerizations to optionally include Son is measured to form the polyamide products.
Embodiment 43 can include or can optionally with one in embodiment 1-42 or any combination master Topic combination to optionally include, one or more raw material polymerizations is included forming the polyamide products in the conduit With the water having less than about 5 weight %.
Embodiment 44 can include or can optionally with one in embodiment 1-43 or any combination master Topic combination to optionally include, one or more raw material polymerizations is included forming the polyamide products in the conduit To have at least about 2 relative viscosity.
Embodiment 45 can include or can optionally with one in embodiment 1-44 or any combination master Topic combination, it is described to include forming the polyamide in the conduit by one or more raw material polymerizations to optionally include Product is to have at least about 5 relative viscosity.
Embodiment 46 can include or can optionally with one in embodiment 1-45 or any combination master Topic combination, it is described to include forming the polyamide in the conduit by one or more raw material polymerizations to optionally include Product is to have at least about 9 relative viscosity.
Embodiment 47 can include or can optionally with one in embodiment 1-46 or any combination master Topic combination, it is described to include forming the polyamide in the conduit by one or more raw material polymerizations to optionally include Product is to have at least about 15 relative viscosity.
Embodiment 48 can include or can optionally with one in embodiment 1-47 or any combination master Topic combination, it is described to include forming the polyamide in the conduit by one or more raw material polymerizations to optionally include Product is to have at least about 20 relative viscosity.
Embodiment 49 can include or can optionally with one in embodiment 1-48 or any combination master Topic combination, it is described to include forming the polyamide in the conduit by one or more raw material polymerizations to optionally include Product is to have at least about 25 relative viscosity.
Embodiment 50 can include or can optionally with one in embodiment 1-49 or any combination master Topic combination, it is described to include forming the polyamide in the conduit by one or more raw material polymerizations to optionally include Product is to have at least about 30 relative viscosity.
Embodiment 51 can include or can optionally with one in embodiment 1-50 or any combination master Topic combination, it is described to include forming the polyamide in the conduit by one or more raw material polymerizations to optionally include Product is to have at least about 40 relative viscosity.
Embodiment 52 can include or can optionally with one in embodiment 1-51 or any combination master Topic combination, it is described to include forming the polyamide in the conduit by one or more raw material polymerizations to optionally include Product is to have at least about 50 relative viscosity.
Embodiment 53 can include or can optionally with one in embodiment 1-52 or any combination master Topic combination, it is described to include forming the polyamide in the conduit by one or more raw material polymerizations to optionally include Product is to have at least about 75 relative viscosity.
Embodiment 54 can include or can optionally with one in embodiment 1-53 or any combination master Topic combination, to optionally include, squeezes out the polyamide products to form one or more polyamide strands.
Embodiment 55 can include or can optionally with one in embodiment 1-54 or any combination master Topic combination, to optionally include, the cupric composition includes mantoquita.
Embodiment 56 can include or can optionally with one in embodiment 1-55 or any combination master Topic combination, to optionally include, the cupric composition includes at least one of copper (I) salt and copper (II) salt.
Embodiment 57 can include or can optionally with one in embodiment 1-56 or any combination master Topic combination, to optionally include, the cupric composition includes at least one of copper halide (I) salt and copper halide (II) salt.
Embodiment 58 can include or can optionally with one in embodiment 1-57 or any combination master Topic combination, to optionally include, the cupric composition includes at least one mantoquita derived from carboxylic acid.
Embodiment 59 can include or can optionally with one in embodiment 1-58 or any combination master Topic combination, to optionally include, the cupric composition includes cupric iodide (I), copper bromide (I), copper bromide (II), copper acetate (II) it is at least one and in copper chloride (II).
Embodiment 60 can include or can optionally with one in embodiment 1-59 or any combination master Topic combination, to optionally include, the one or more raw material include the dicarboxylic acids of straight chain and the diamines of straight chain or by straight chains Dicarboxylic acids and straight chain diamines formed oligomer.
Embodiment 61 can include or can optionally with one in embodiment 1-60 or any combination master Topic combination, to optionally include, the dicarboxylic acids has structure HO C (O)-R1- C (O) OH, wherein R1It is C1-C15Alkylidene.
Embodiment 62 can include or can optionally with one in embodiment 1-61 or any combination master Topic combination, to optionally include, dicarboxylic acids is adipic acid.
Embodiment 63 can include or can optionally with one in embodiment 1-62 or any combination master Topic combination, to optionally include, the diamines has structure H2N-R2-NH2, wherein R2It is C1-C15Alkylidene.
Embodiment 64 can include or can optionally with one in embodiment 1-63 or any combination master Topic combination, to optionally include, the diamines is hexamethylene diamine.
Embodiment 65 can include or can optionally with one in embodiment 1-64 or any combination master Topic combination, to optionally include, the one or more raw material include adipic acid and hexamethylene diamine mixture or by The oligomer that the mixture of adipic acid and hexamethylene diamine is formed.
Embodiment 66 can include or can optionally with one in embodiment 1-65 or any combination master Topic combination, to optionally include, the polyamide is nylon 6,6.

Claims (20)

1. a kind of method for forming daiamid composition, the described method includes：
One or more raw material are polymerize in main paradigmatic system to form polyamide products；
The polyamide products from the main paradigmatic system are transferred in the catheter；With
Cupric composition is fed into the conduit in the paradigmatic system downstream, wherein the polyamide products contain described Water content at the position of the charging of copper composition is 0.0001 weight % to 2 weight %, wherein the conduit be evaporator, Reactor and the transmission pipeline in flash vessel downstream.
2. method described in claim 1, wherein the cupric composition, which is fed to the conduit, to be included：
The mixture of the particle of copper-containing compound and polymer support is fed into feeding line；
Polymer support is melted in the feeding line formed mixed comprising molten polymer and the copper-containing compound Close object；With
The mixture is fed into the conduit.
3. method described in claim 1, wherein one or more raw material polymerizations are included：
One or more raw material are converted into the first polyamide；With
Increase the molecular weight of first polyamide to form the polyamide products.
4. method described in claim 1, wherein one or more raw material polymerizations are included being formed in the conduit Polyamide products are with the water having less than 5 weight %.
5. method described in claim 1, wherein one or more raw material polymerizations are included being formed in the conduit Polyamide products are to have at least 5 relative viscosity.
6. method described in claim 1, wherein the cupric composition includes mantoquita.
7. method described in claim 1, wherein the cupric composition includes at least one in copper (I) salt and copper (II) salt Kind.
8. method described in claim 1, wherein the cupric composition includes cupric iodide (I), copper bromide (I), copper bromide (II), at least one of copper acetate (II) and copper chloride (II).
9. method described in claim 1, wherein the one or more raw material include having HOC (O)-R1- C (O) OH structures Dicarboxylic acids, wherein R1It is C1-C15Alkylidene.
10. method described in claim 1, wherein the one or more raw material include having H2N-R2-NH2The two of structure Amine, wherein R2It is C1-C15Alkylidene.
11. method described in claim 1, wherein the one or more raw material include adipic acid and hexamethylene diamine Mixture or the oligomer formed by the mixture of adipic acid and hexamethylene diamine.
12. method described in claim 1, wherein the polyamide products are nylon 6,6.
13. a kind of system for being used to prepare polyamide, the system comprises：
Main paradigmatic system, the main paradigmatic system are configured to one or more raw material being converted into polyamide products；
The conduit in the main paradigmatic system downstream, the conduit are configured to transfer the polyamide products；With
Feeding line, the feeding line are configured to feed cupric composition into the conduit, wherein the polyamide produces Water content of the object at the position of the charging of the cupric composition is 0.0001 weight % to 2 weight %, wherein the conduit It is the transmission pipeline in evaporator, reactor and flash vessel downstream.
14. the system described in claim 13, wherein the feeding line includes receiving the heating of the cupric composition Feed screw.
15. the system described in claim 14, wherein the cupric composition includes the particle of copper-containing compound and polymer supported The mixture of body, wherein the feed screw of the heating is configured to melt to be formed to include to melt by the polymer support to gather Close the mixture of object and the copper-containing compound, wherein the feed screw of the heating be configured to by the mixture feed to In the conduit.
16. the system described in claim 13, wherein the main paradigmatic system includes：
Polymer reactor, the polymer reactor are configured to one or more raw material being converted into the first polyamide；With
The back segment system in the polymer reactor downstream, the back segment system configuration are to increase the molecular weight of first polyamide To form the polyamide products.
17. the system described in claim 16, wherein the back segment system includes the flash vessel in the polymer reactor downstream, Described in flash vessel be configured to increase the molecular weight of first polyamide to form the second polyamide.
18. the system described in claim 17, wherein the conduit is in fluid communication with the flash vessel, and the polyamide produces Object includes second polyamide.
19. the system described in claim 17, wherein the back segment system further includes the finisher in the flash vessel downstream, Described in finisher be configured to increase the molecular weight of second polyamide to form melamine.
20. the system described in claim 19, wherein the conduit is in fluid communication with the finisher, and the polyamide Product includes the melamine.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3431236A (en) * 1966-01-13 1969-03-04 Du Pont Method of adding an antioxidant to a continuous polymerization process
CN86103842A (en) * 1985-06-13 1986-12-31 罗纳·布朗克纤维公司 The masterbatch that is used for delustring polyamides
CN1294611A (en) * 1998-03-09 2001-05-09 美国Basf公司 Light and thermally stable polyamide
CN204058324U (en) * 2013-05-01 2014-12-31 因温斯特技术公司 For the preparation of the system of polymeric amide

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002074838A1 (en) * 2001-03-15 2002-09-26 Dsm N.V. Process for the production of a polylactam composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3431236A (en) * 1966-01-13 1969-03-04 Du Pont Method of adding an antioxidant to a continuous polymerization process
CN86103842A (en) * 1985-06-13 1986-12-31 罗纳·布朗克纤维公司 The masterbatch that is used for delustring polyamides
CN1294611A (en) * 1998-03-09 2001-05-09 美国Basf公司 Light and thermally stable polyamide
CN204058324U (en) * 2013-05-01 2014-12-31 因温斯特技术公司 For the preparation of the system of polymeric amide

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