CN101351492A - Late addition to effect compositional modifications in condensation polymers - Google Patents

Late addition to effect compositional modifications in condensation polymers Download PDF

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CN101351492A
CN101351492A CNA2006800338100A CN200680033810A CN101351492A CN 101351492 A CN101351492 A CN 101351492A CN A2006800338100 A CNA2006800338100 A CN A2006800338100A CN 200680033810 A CN200680033810 A CN 200680033810A CN 101351492 A CN101351492 A CN 101351492A
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stream
slip
polymer
acid
melt
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CN101351492B (en
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F·L·科尔霍恩
K·L·维内特
B·R·德布勒因
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Eastman Chemical Co
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Eastman Chemical Co
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Abstract

A process for preparing modified polymer by withdrawing a slip stream of polymer melt from the discharge line of a continuous polymerization reactor, admixing in a highly modified polymeric additive into the polymer melt within the slip stream, then introducing the modifier containing slip stream late in the manufacturing process prior to the slip stream withdrawal point. The improved processes of the invention have particular utility for large-scale, continuous reactor where transitions and short production runs are economically prohibitive thereby limiting the product breath. The process is particularly suited for producing a family of copolyesters using a continuous melt phase production process.

Description

Back adding method realizes the composition modification of polycondensate
1. invention field
The present invention relates to prepare a kind of polymkeric substance of modification, method is that a kind of properties-correcting agent of forming is introduced in the slip-stream of the polymer melt of discharging continuously, generates the modification slip-stream and before the slip-stream point of draw modification slip-stream is introduced in the polymer melt more then.More particularly, the present invention relates to the preparation of condensed type copolyesters, by from continuous polymerization reactor, extracting out unmodified or the slightly slip-stream of the polyester fondant of modification, in this slip-stream, introduce a kind of polymkeric substance of high modification, and then with this modification slip-stream introducing continuous polymerization reactor, to generate a kind of multipolymer of medium co-monomer content.
2. background of invention
Polycondensate such as thermoplastic polyester, polycarbonate and polymeric amide have many desirable physics and chemical attribute, make them can be applicable to prepare moulded product miscellaneous, fiber and film etc.But for some specialized application, also there is the defective that must reduce or eliminate in these polymkeric substance.In order to overcome these defectives, polymkeric substance contains the needs that one or more additives or comonomer depend on the end-use of polymkeric substance usually.For example, for polyester polymers, introduce one or more UV light absorber usually, improve particle, toning agent or the pigment of polyester polymers bottle base second-heating or Masterbatch, acetaldehyde scavenger or inhibitor, catalyst passivating agent or stablizer, oxygen barrier material, antifriction auxiliary agent, crystallization auxiliary, impact modifier or the like.
One of prevailing thermoplastic polyester polymer is polyethylene terephthalate (PET).Pet polymer is widely used in packaging industry, particularly makes the beverage bottle of soda pop and noncarbonated beverage products.In soda pop industry, consider to comprise the speed that carbonic acid gas is overflowed from container, because the taste that the content photodegradation causes is rotten and the separating out of the additive that adds in melt polymerization or when producing the desired melt of this container subsequently.In order to overcome these problems, the PET resin often passes through to introduce unique comonomer modification on main polymer chain, thereby generates PET copolyesters miscellaneous.
Produce the existing several processing methodes of PET copolyesters.In traditional production of polyester, copolyesters is usually by two kinds of different route productions: transesterify adds polycondensation (DMT technology) or direct esterification adds polycondensation (direct esterification technology).In older ester exchange process or DMT technology, dimethyl terephthalate (DMT) (DMT), ethylene glycol (EG) and modified copolymer monomer normally merge when production process begins and add the slurry tank or first esterifier; The modified copolymer monomer that adds can be a kind of diacid, this sour dialkyl derivative, perhaps a kind of glycol.In the presence of catalyzer, under normal atmosphere and about 180 ℃～230 ℃ temperature, these components stand acidic two (hydroxyethyl ester) substituted monomer intermediates of transesterification reaction and methyl alcohol.This reaction is a reversible, and by removing methyl alcohol reaction is carried out fully.After transesterification reaction is finished, add stablizer then and make the transesterification catalyst inactivation and add polycondensation catalyst.Then, in the presence of the polymerizing catalyst (for example antimony) that is fit to, the monomer intermediate is by polycondensation polymerized, and wherein temperature is raised to about 265 ℃～about 305 ℃, and pressure reduces to below the 2mm mercury column vacuum.This reaction generates pet copolymer and ethylene glycol.Because this reaction is a reversible, the direction that the glycol of removing release can be forced to react to generating polyester moves.
Second method, or direct ester exchange process, this is the differentiation of DMT technology as everyone knows, it is to utilize pure terephthalic acid (PTA) (PTA) to replace DMT.The first step, PTA and ethylene glycol (EG) and the monomeric diacid of modified copolymer or glycol mix.Usually react without any catalyzer, about 5 pounds of/square inch (psia)～85 of pressure pound/square inch (psia), about 155 ℃～305 ℃ of temperature, these components generate two (hydroxyalkyl) ester substituted monomer intermediates and the water of acid through direct esterifications.After direct esterification was finished, this monomer intermediate passed through then as the described polycondensation polymerized of ester exchange process.That is to say that the monomer intermediate is raised to about 265 ℃～about 305 ℃ by temperature then, pressure reduces to below the 2mm mercury column vacuum, carries out polymerization in the presence of the polymerizing catalyst (for example antimony) that is fit to.This reaction generates pet copolymer and ethylene glycol.Because this reaction is a reversible, the direction that the glycol of removing release can be forced to react to generating polyester moves.
Along with pure terephthalic acid (PTA) supplies the property increase, the direct esterification technology of renewal provides many advantages, comprises from interrupter method being transformed into continuous processing.When big relatively weight polyester of needs or multipolymer, the economic benefit height that continuous processing is produced.But, when needs relatively in a small amount copolyesters and/or when needing a class copolyesters of different copolymer monomer content, there is other problem in the continuation method of preparation copolyesters.Particularly, the residence time of continuous polymerization technique generally is about 4～12 hours, so any change that polymkeric substance is formed just can produce a large amount of suborder materials.The problem relevant with the suborder material can be on large-scale production line more further worsens during high productivity makes this device be not suitable for the various modified thermoplastic resins that contain heterogeneity of small-scale production.
Produce the PET copolyesters and also use several post polymerization methods.One of method is to use forcing machine or reaction vessel to make PET base polymer and second kind of condensation-type polymerization thing melting mixing, makes two kinds of polymkeric substance experience transesterification reactions, thereby produces a kind of random copolymers.This technology has several shortcomings.The first, reach the melt randomization, need to prolong the reaction times until 1/3～2 hour, thereby cause the thermal destruction of polymkeric substance, lose its physicals simultaneously, produce color, and produce other undesirable degraded product such as acetaldehyde.The second, for prolonging melt residence time, need the utility appliance of large-scale heating container or forcing machine.The 3rd, can add extra catalyzer in order to promote transesterification reaction, thereby reduce melt residence time; But the catalyzer that replenishes can have a negative impact to the color and the thermostability of the homogenizing multipolymer that obtains.Last and most important, this method does not have the economic advantages relevant with the large-scale continuous polyester production process.
The post polymerization method of another preparation copolyesters, comprise two kinds of reactor melt-flow are combined, wherein a kind of copolyesters melt-flow of high modification is injected the discharge line of low or unmodified successive polymerization polyester, makes resin carry out static state and dynamically mixing in discharge line.A kind of variation of this method, comprise from the discharge line of continuous generation PET base resin and extract an effluent out, effluent is delivered to a kneading extruder, the copolyesters of high modification is introduced this kneading extruder, the effluent of modification returns the discharge line of continuous generation PET base resin again, carries out the static mixing of resin and dynamically mixing then in discharge line.Though the static state of these methods and dynamically blended mix in conjunction with the distribution that may improve this two component, do not provide time enough to allow to transesterification reaction realization response randomization via two kinds of polyester.In addition, in large-scale continuous polymerization supply line, add static state and dynamic mixer, limit the polyester product that they produce combination neatly.
According to the above, just needs are a kind of can be when melt polymerization be produced the product of conjugated polyester resin, at the suborder material product transition point still less that produces, implement change of component faster, particularly for the large-scale continuous operating gear that is designed to produce this polyester.Thereby, be desirable to provide a kind of method, in polymer molten fluid, add a kind of polymer-modifiedly, the time that allows is in some sense carried out good mixing and chemical equilibrium.
3. invention summary
The invention discloses a kind of polymkeric substance method for preparing modification, comprise: the polymer melt of a) discharging polycondensation from polymerization reactor, form the polymer molten fluid of discharging continuously, b) from the polymer molten fluid of continuous discharge, extract a part of polymer melt out and form a slip-stream, c) in this slip-stream, introduce a kind of composition properties-correcting agent, forming a kind of slip-stream that contains properties-correcting agent, and d) slip-stream that will contain properties-correcting agent is incorporated in the step b) and extracts the upstream of polymer melt out from discharging polymer molten fluid.
Of the present invention improving one's methods has special practicality for the large-scale continuous reactor, and these flow reactors are because economic reasons is to forbid carrying out product conversion and short-term production, thereby limited the vitality of product.This method is particularly suitable for using successive molten phase production technique to produce a class copolyesters.These and other aspect of the present invention just can become apparent by following description.
Should be appreciated that general introduction above and subsequent describing the both in detail only is the demonstration and the explanation of claim, can not be as restriction of the present invention.A part and character narrate that accompanying drawing constitutes this specification sheets illustrate several embodiments of the present invention together, and are used for illustrating principle of the present invention.
4. accompanying drawing summary
Fig. 1 is a process method flow chart, illustrates that forming properties-correcting agent introduces slip-stream by forcing machine.
Fig. 2 is a process method flow chart, illustrates that forming properties-correcting agent introduces slip-stream by a kind of online forcing machine.
Fig. 3 is a process method flow chart, illustrates to form properties-correcting agent and another additive introducing slip-stream.
5. detailed Description Of The Invention
By with reference to Fig. 1 of following detailed description and three embodiments of diagram～3, with here more Other embodiments that describe in detail can more easily be understood the present invention.
Before disclosure and description this method, should be appreciated that to the invention is not restricted to concrete synthetic method Or detailed prescription, these aspects certainly can be different. Also should be appreciated that, here use Term, just to describing specific embodiment, can not think a kind of restriction.
Also must be noted that, the form of the odd number that specification and appended claim are used " ", " a kind of " and " being somebody's turn to do " comprises a plurality of objects, unless context has clearly regulation in addition. For example, Mention processing or prepare a kind of " polymer ", a kind of " prefabricated blank ", " goods ", " container " Or " bottle ", the meaning is processing or prepares many polymer, prefabricated blank, goods, container or bottle Son. Mention composition and contain " a kind of " component or " a kind of " polymer, the meaning is except this Also comprise respectively other component or other polymer outside the title.
" comprise " or the meaning of " containing " or " having " is; at least this compound of mentioning, element, particle or method steps etc.; must be present in said composition or goods or the method; but do not get rid of the compound that there is other, catalyzer, material, particle, method steps etc.; even other this compounds, material, particle, method steps etc. with mention those have same effect, unless in claim, be explicitly excluded.
Should be appreciated that also mentioning that one or more method stepss are not got rid of exists and the front and rear combined additional method steps of described step, or the method steps that between those steps that obviously are equal to, inserts.In addition, the processing step lettering is to be convenient to discern discontinuous job step, and unless otherwise mentioned, described processing step can any series arrangement.
The expression of scope is included in whole integers and mark within this scope.Temperature of in a kind of method, representing or temperature range, or the temperature or the temperature range of reaction mixture or melt or the melt that applies or polymkeric substance or the polymkeric substance that applies, the meaning refer to if or the temperature that applies, the actual temperature of this melt or polymkeric substance, perhaps its both, all be the regulation temperature or within specific scope, then in all case, the temperature of qualification is gratifying.
Word " composition " meaning refers to that each listed component is present in the said composition, and any component that is not illustrated in the composition is uncombined or unreacted.Said composition can be solid or liquid.Described component can be bonded in composition, and is uncombined, reaction, unreacted and unless otherwise mentioned, can be any oxidation state.
In full described limiting viscosity (It.V.) value is to be unit with dL/g, and by at 25 ℃, the logarithmic viscosity number of measuring in the phenol/tetrachloroethane of 60/40 (w/w) (Ih.V.) value calculates.Polymer samples is dissolved in this solvent, and concentration is 0.25g/50mL.The mensuration of polymer solution viscosity is used the differential viscometer of Viscotek modification.The description of differential viscometer principle of operation can be referring to ASTM D 5225.Logarithmic viscosity number is to be calculated by the soltion viscosity of measuring.Following equation has been described the mensuration of these soltion viscosities and has been calculated Ih.V. subsequently, calculates It.V. by Ih.V. then:
η inh＝[ln(t s/t o)]/C
Wherein: η Inh=logarithmic viscosity number is measured under 25 ℃ of polymer concentrations in the phenol/sym.-tetrachloroethane of 0.50g/100mL 60/40 (w/w)
The ln=natural logarithm
t s=sample stream is through the time capillaceous
t o=blank solvent is flowed through the time capillaceous
The C=polymer concentration, g/100mL solvent (0.50%)
Ultimate value when polymer property viscosity is its specific viscosity infinite dilution.It is defined by following equation:
η int＝lim? C→0(η sp/C)＝lim? C→0ln(η r/C)
Wherein: η Int=limiting viscosity
η r=relative viscosity=t s/ t o
η Sp=specific viscosity=η r-1
Instrument calibration comprises the revision test of standard reference material, produces " acceptance " Ih.V. value with the appropriate mathematical equation then.
The mean value of the Ih.V./replicate(determination) of the material of the reference of calibration factor=acceptance
Ih.V. * calibration factor that gauged Ih.V.=calculates.
Limiting viscosity (It.V. or η Int) can use following Billmeyer equation estimation:
η Int=0.5[e 0.5 * gauged Ih.V-1]+(0.75 * gauged Ih.V).
The reference of estimated performance viscosity (Billmeyer relation) is J.Polymer Sci, 4, and 83-86 (1949).
In other words, It.V. can use above-mentioned solvent and measure concentration, utilizes the differential viscometer of measuring IV to measure according to the method for ASTM D 5225-98.
In one embodiment of the invention, a kind of method for preparing the polymkeric substance of modification is disclosed, comprise: the polymer melt of a) discharging polycondensation from polymerization reactor, form a polymer molten fluid of discharging continuously, b) from the polymer molten fluid of continuous discharge, extract a part of polymer melt out and form slip-stream, c) in this slip-stream, introduce a kind of properties-correcting agent of forming and form a kind of slip-stream that contains properties-correcting agent, and d) slip-stream that will contain properties-correcting agent is incorporated in the step b) and extracts the upstream of polymer melt out from discharging polymer molten fluid.
In another embodiment of the invention, the method for the polymkeric substance of a series of modifications with different blocks (blockiness) degree of a kind of preparation is disclosed.Term block, the meaning are to contain to derive from the monomer molecule segment that links up of forming properties-correcting agent, and join the polymer melt segment of the polycondensation that generates by continuous polymerization reactor technology, form a kind of segmented copolymer.Be not subject to any theory, the degree of block is considered to be controlled by composition properties-correcting agent and is under the condition of fusion phase temperature, with the interactional time length of the polymer melt of polycondensation.By selecting the appropriate location, introduce contain polycondensation polymer melt that properties-correcting agent slip-stream polymerization process generates just can be adjusted at time length under this fusion phase temperature.Particularly suitable composition properties-correcting agent of the present invention is the condensation-type polymerization thing, because they can carry out transesterification reaction when the melt-processed with the polymer melt of polycondensation of polyester, forms a kind of block modified polymkeric substance.The useful condensation-type polymerization thing of the present invention is formed properties-correcting agent and is comprised polyester, polycarbonate and polymeric amide.The degree of transesterify can be passed through nucleus magnetic resonance (NMR) and measure.
In another embodiment of the present invention, disclose a kind of a series of polymkeric substance methods that contain the modification of different copolymer monomer composition that prepare, wherein the polymkeric substance of this modification is a kind of random copolymers.The term random copolymers, the meaning is each polymer chain of the polymkeric substance of modification, contain the monomer of the polymer melt that derives from the polycondensation of forming properties-correcting agent and generating by continuous polymerization reactor, in addition, these monomers are arranged in the polymer chain of modification randomly.The polymer melt of particularly suitable composition properties-correcting agent and polycondensation all is the polyester type polycondensate, because they carry out transesterification reaction easily when melt processing temperature, forms the ester modified polymkeric substance of a kind of random copolymerization.
Fusion phase technology is suitable for a kind of polymkeric substance of polycondensation continuously, thereby a kind of polymer molten fluid of discharging is provided.The polymer melt of polycondensation is a kind of liquid state or molten state, is suitable for holding additive.The example of the polymer melt of this polycondensation is a thermoplastic polymer, preferably polyester.
The polymer melt of polycondensation contains the polyester of any haplotype, comprise, rather than be limited to equal polyester, copolyesters and ternary polyester, be appreciated that the meaning is the synthetic polymer by one or more dual functional carboxylic acids and one or more dual functional oxy-compound prepared in reaction.Usually, dual functional carboxylic acid can be a dicarboxylic acid, and dual functional oxy-compound can be a dibasic alcohol, for example, and ethylene glycol and glycol.Perhaps, dual functional carboxylic acid can be a kind of hydroxycarboxylic acid, and for example P-hydroxybenzoic acid and dual functional oxy-compound can be a kind of aryl nucleus that has 2 hydroxyl substituents, for example, and Resorcinol.The polyester polymers of polycondensation wishes it is a kind of unregulated polymer, and the monomer whose unit is to arrange randomly in polymer chain, rather than arranges in the mode of block.
The polyester polymers of preferred polycondensation contains the unit of multiple alkylidene aryl, as terephthalic acid alkylene ester or alkylene naphthalate unit in polymer chain.The more specifically example of these repeating units comprises ethylene glycol terephthalate, naphthalic acid second diester and terephthalic acid propylene diester.Preferred polyester polymers is to comprise:
(i) a kind of carboxyl acid component comprises terephthalic acid, terephthaldehyde acid derivative, the naphthalene-2 of at least 80 moles of %, 6-dicarboxylic acid, naphthalene-2, the derivative of 6-dicarboxylic acid, or the residue of its mixture and
(ii) a kind of hydroxy component comprise the ethylene glycol of at least 80 moles of % and 0～20 mole %'s or 1,4-cyclohexanedimethanol unit, glycol ether unit, 2,2,4,4-tetramethyl--1, has the modification ethylene glycol unit of 2～16 carbon at 3-cyclobutanediol unit, the perhaps residue of its mixture is based on the carboxyl acid component residue of 100 moles of % in the polyester polymers and the hydroxy component residue of 100 moles of %.
Usually, the polyester polymers such as the polyethylene terephthalate of preparation polycondensation are by a kind of glycol such as ethylene glycol and a kind of dicarboxylic acid (for example free acid or its C 1～C 4Dialkyl) reaction, generate ester monomer and/or oligopolymer, polycondensation becomes polyester then.More than one the compound that contains the carboxyl or derivatives thereof can participate in reaction in this technological process.All those enter the compound that contains the carboxyl or derivatives thereof of technological process, all become the part of " carboxyl acid component " in the described polyester product.The product mole % that all contain the compound of carboxyl or derivatives thereof amounts to 100 in product.In described polyester product, " residue " that contains carboxyl or derivatives thereof compound, described compound with contain the oxy-compound condensation, further polycondensation forms after the different chain length degree polyester polymers again, still remains on the part of this compound in this polyester product.More than one the compound that contains the hydroxyl or derivatives thereof can become the part of the polyester polymers of this polycondensation.All that enters the compound of the hydroxyl or derivatives thereof of technological process, all becomes the part of hydroxy component in the described polyester product.The mole % that all contain hydroxyl or derivatives thereof compound becomes the part of described polyester product, amounts to 100.In described polyester product, " residue " of hydroxyl or derivatives thereof compound, at described compound and the compound condensation that contains the carboxyl or derivatives thereof, further polycondensation forms after the different chain length degree polyester polymers again, still remains on the part of this compound in this polyester product.
Carboxylic acid residues and the hydroxyl residue mole % in product can measure by proton N MR.
When the polyester polymers of preparation polycondensation, the reaction of carboxyl acid component and hydroxy component can not be confined to described molecular fraction, because if need, can adopt excessive hydroxy component, for example, maximum about 200 moles of % (with respect to the carboxyl acid component of 100 moles of %).But, just can contain the aromatic dicarboxylic acid residue and the glycol residue of described amount by the polyester polymers of this prepared in reaction.
Remove terephthalic acid, the derivative of terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2, the derivative of 6-dicarboxylic acid, or outside the diacid component of its mixture, the carboxyl acid component of the polyester polymers of this polycondensation can comprise one or more carboxyl acid modified dose of other components.This carboxyl acid modified dose of other component comprises monocarboxylic acid compound, dicarboxylic acid compound and has higher carboxyl number purpose compound.Example comprises the aromatic dicarboxylic acid that preferably has 8～14 carbon atoms, preferably has an aliphatic dicarboxylic acid of 4～12 carbon atoms, or preferably has the alicyclic dicarboxylic acid of 8～12 carbon atoms.The more specifically example that is used as the dicarboxylic acid of properties-correcting agent acid constituents is, phthalic acid, m-phthalic acid, naphthalene-2,6-dicarboxylic acid, hexanaphthene-1,4-dicarboxylic acid, cyclohexanediacetic, phenylbenzene-4,4 '-dicarboxylic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid or the like, wherein most preferably m-phthalic acid, naphthalene-2,6-dicarboxylic acid and hexanaphthene-1,4-dicarboxylic acid.Should be appreciated that, adopt the corresponding acid anhydrides of these acid, ester and chloride of acid, also be included in the term " carboxylic acid ".Also can adopt three carboxyl branching agents and the compound that has higher carboxyl number, and the monocarboxylic acid chain terminator, the polyester polymers of modification polycondensation.
Except that the hydroxy component that comprises ethylene glycol, the hydroxy component of polycondensation polyester polymers of the present invention also comprises other glycols modifier components.This glycol-modified dose of other component comprises single alcohol, glycol or has the compound of higher hydroxyl value.The example of properties-correcting agent oxy-compound comprises, preferably has the cycloaliphatic diol of 6～20 carbon atoms and/or preferably has the aliphatic diol of 3～20 carbon atoms.This glycol example more specifically comprises, glycol ether, triglycol, 1, the 4-cyclohexanedimethanol, propane-1, the 3-glycol, butane-1, the 4-glycol, pentane-1, the 5-glycol, hexane-1, the 6-glycol, 3-methyl pentanediol-(2,4), 2 hexylene glycol-(1,4), pure isooctane-glycol-(1,3), 2,5-Rutgers 612-(1,3), 2,2-diethyl propane-glycol-(1,3), hexylene glycol-(1,3), 1,4-two-(hydroxy ethoxy)-benzene, 2,2-pair-(4-hydroxy-cyclohexyl)-propane, 2,4-dihydroxyl-1,1,3,3-tetramethyl--tetramethylene, 2,2-pair-(3-'-hydroxyethoxy phenyl)-propane and 2,2-pair-(4-hydroxyl propoxy phenyl)-propane.As carboxyl acid modified dose of residue, the polyester polymers of this polycondensation can contain m-phthalic acid and naphthalene dicarboxylic acids.
The amount that carboxyl acid modified dose and glycol modification agent residue exist is until 20 moles of %, or until 10 moles of %, or until 5 moles of %, or until 3 moles of %, or until 2mole%, based on the total mole number of they corresponding components in the polyester polymers of polycondensation.Single, three and the properties-correcting agent of high functionality more, the preferred sum that exists is only until about 8 moles of %, or until 4 moles of %.
The term of Cai Yonging " residue " here, the meaning is by corresponding monomeric polycondensation and/or esterification, and adds any organic structure of polymkeric substance.The term of Cai Yonging " repeating unit " here, the meaning is to have a dicarboxylic acid residue and the organic structure that diol residue is got up by the ketonic oxygen bonding.Therefore, for example, this dicarboxylic acid residue can derive from dicarboxylic acid monomer or its relevant acid halide, ester, salt, acid anhydride, or its mixture.So the term of Cai Yonging " dicarboxylic acid " is intended that any derivative that comprises dicarboxylic acid and dicarboxylic acid here, comprises its relevant carboxylic acid halides, ester, half ester, salt, half salt, acid anhydride, mixed anhydride, or its mixture, be used for and glycol prepared in reaction polyester.Here the term of Cai Yonging " terephthalic acid ", be intended that and comprise terephthalic acid itself and its residue, and any derivative of terephthalic acid, comprise its relevant carboxylic acid halides, ester, half ester, salt, half salt, acid anhydride, mixed anhydride, or its mixture, be used for and glycol prepared in reaction polyester.
Polycondensation polymer melt of the present invention also can comprise the additive that is fit to that is generally used for polymkeric substance.This additive can be to use conventional amount used and can directly add to form matrix polymer in the reaction.The example of this additive known in the art is, tinting material, pigment, carbon black, glass fibre, filler, impact modifier, antioxidant, stablizer, fire retardant, hot auxiliary agent, crystallization auxiliary, acetaldehyde reduce compound, reclaim and discharge auxiliary agent, softening agent, nucleator, releasing agent, expanding material, processing aid or the like again, or their combination.These additives can import slurry tank, esterifier, pre-polymerization reactor, finishing reactor and its any point between the two.In addition, the polymer melt of polycondensation also can contain forms properties-correcting agent and additive, and this additive imports polycondensation reactor via the slip-stream that contains properties-correcting agent in advance.
These all additives and many other auxiliary agents, their use all is known in the art, there is no need to set off a discussion.So only limited additive will be referred to, should be appreciated that any of these compound can anyly be used in combination, as long as they do not have overslaugh the present invention to reach its target.
The slip-stream that contains properties-correcting agent is added into the polymer melt of polycondensation, perhaps at pre-polymerization reactor, and in the final polycondensation reactor, the perhaps any point before extracting slip-stream out.The slip-stream that contains properties-correcting agent comprises composition properties-correcting agent.
Useful " the composition properties-correcting agent " of the present invention is the condensation-type polymerization thing, preferred polyamide, polycarbonate and polyester.One embodiment of the invention are that polymeric amide is formed the method that properties-correcting agent is introduced the polycondensation polymer melt of PET, for example, and to improve the barrier property of PET.Another embodiment is a kind of method that generates the polymkeric substance of modification, wherein polycarbonate modified polymkeric substance is mixed the polyester polymers of precondensation, for example, the modified poly ester that has high glass-transition temperature (Tg) and corresponding increase maximum operation (service) temperature with generation.Still another embodiment is a kind of method, a kind of thus composition properties-correcting agent, as comprise the copolyesters of high comonomer content, be introduced into the polycondensation polyester polymers melt-flow of homopolymerization PET, thereby the polymkeric substance that each independent polyester raw material is all had the modification of middle co-monomer content is provided.
Term " composition properties-correcting agent ", the meaning refers to a kind of polycondensate, except that comprising the terephthalic acid residue who is present in the continuous generation polymer melt, also comprises or the more or diacid residues of molecular fraction still less; Or comprise except that the glycol residue that is present in continuous generation polymer melt, also comprise hydroxyl residue more or still less molecular fraction.In addition, the polymkeric substance of this modification may comprise a kind of in the polymer molten fluid of polycondensation non-existent monomer residue.For example, generation comprises the polymkeric substance of the modification of 6 moles of % cyclohexanedimethanols (CHDM) residue, can will comprise greater than 6 moles of %CHDM residues, or greater than 10 moles of %CHDM residues, or greater than 25 moles of %CHDM, or greater than 50 moles of %CHDM, or greater than 75 moles of %CHDM, or, join in the polycondensation polyester polymers melt that comprises less than 6 moles of %CHDM properties-correcting agent residues until the PET of 100 moles of %CHDM composition properties-correcting agent.Another example, generation comprises the polymkeric substance of the modification of CHDM residue, can will comprise greater than 6 moles of %CHDM residues, or greater than 10 moles of %CHDM residues, or greater than 25 moles of %CHDM, or greater than 50 moles of %CHDM, or greater than 75 moles of %CHDM, or, join in the polycondensation pet polymer melt-flow that comprises 2 moles of %CHDM glycol modification agent residues until the PET of 100 moles of %CHDM composition properties-correcting agent.Another example, generation comprises the polymkeric substance of the modification of CHDM residue, can will comprise greater than 6 moles of %CHDM residues, or greater than 10 moles of %CHDM residues, or greater than 25 moles of %CHDM, or greater than 50 moles of %CHDM, or greater than 75 moles of %CHDM, or, join in the polycondensation PET homopolymer melt that neither comprises dicarboxylic acid properties-correcting agent or also do not comprise glycol modification agent residue until the PET of 100 moles of %CHDM composition properties-correcting agent.In another example still, generation comprises the polymkeric substance of the modification of m-phthalic acid (IPA) residue, can will comprise greater than 6 moles of %IPA residues, or greater than 10 moles of %IPA residues, or greater than 25 moles of %IPA, or greater than 50 moles of %IPA, or greater than 75 moles of %IPA, or form properties-correcting agent until the PET of 100 moles of %, join and neither comprise dicarboxylic acid properties-correcting agent or also do not comprise in the unmodified polycondensation pet polymer melt-flow of glycol modification agent residue.In another example, generation comprises the polymer-modified of 6 moles of % m-phthalic acids (IPA) residue, can will comprise greater than 6 moles of %IPA residues, or greater than 10 moles of %IPA residues, or greater than 25 moles of %IPA, or greater than 50 moles of %IPA, or greater than 75 moles of %IPA, or, join in the polycondensation polyester polymers melt that comprises less than 6 moles of %IPA glycol modification agent residues until the PET of 100 moles of % composition properties-correcting agent.In another example, generation comprises the polymkeric substance of the modification of 6 moles of % naphthalene dicarboxylic acids (NDA) residue, can will comprise greater than 6 moles of %NDA residues, or greater than 10 moles of %NDA residues, or greater than 25 moles of %NDA, or greater than 50 moles of %NDA, or greater than 75 moles of %NDA, or, join in the polycondensation polyester polymers melt that comprises less than 6 moles of %NDA until the PET of 100 moles of %NDA composition properties-correcting agent.In another example, generation comprises 2,4-dihydroxyl-1,1,3, the polymkeric substance of the modification of 3-tetramethyl-ring butane (TMCB) can will comprise greater than 6 moles of %TMCB residues, or greater than 10 moles of %TMCB residues, or greater than 25 moles of %TMCB, or greater than 50 moles of %TMCB, or greater than 75 moles of %TMCB, or, join in the polycondensation polyester polymers melt until the PET of 100 moles of %TMCB composition properties-correcting agent.Similarly, generation comprises the polymkeric substance of the modification of dicarboxylic acid properties-correcting agent and glycol modification agent residue, can will comprise greater than 6 moles of %IPA residues, or greater than 10 moles of %IPA residues, or greater than 25 moles of %IPA, or greater than 50 moles of %IPA, or greater than 75 moles of %IPA, or, join and comprise, or greater than 10 moles of %CHDM residues greater than 1 mole of %CHDM residue until 100 moles of %IPA, or greater than 25 moles of %CHDM, or greater than 50 moles of %CHDM, or greater than 75 moles of %CHDM, or in the polyester polymers melt of the polycondensation of 100 moles of %CHDM.Similarly, the dicarboxylic acid properties-correcting agent of the polymkeric substance of this modification and glycol modification agent residue, can be still less than the polyester polymers of polycondensation, reach these minimizings and be by add than the polyester polymers of polycondensation still less comprise dicarboxylic acid properties-correcting agent and glycol modification agent residue is formed properties-correcting agent, the polyester polymers of described polycondensation is a polyester polymers of forming the polycondensation that properties-correcting agent introduces.The example that this dicarboxylic acid properties-correcting agent and glycol modification agent reduce, it is a kind of polymkeric substance that comprises less than the modification of 6 moles of % m-phthalic acids (IPA) residue, generate the polymkeric substance of this modification, can be by comprising less than 6 moles of %IPA residues, or less than 4 moles of %IPA residues, or less than 2 moles of %IPA, or the PET of 0 mole of %IPA forms properties-correcting agent, join comprise 6 or the polycondensation polyester polymers melt of more moles of %IPA glycol modification agent residues in.These examples are exemplary, are not the restrictions of claim of the present invention, are to be used for proving that the present invention prepares the practicality of an analog copolymer, and described multipolymer comprises the various comonomer residues that add with different molecular fractions.
The polymeric amide that is fit to is formed properties-correcting agent and is comprised, is partially aromatic polymeric amide, fatty polyamide, Wholly aromatic polyamide and its mixture and the multipolymer that raw material is produced with diamines and dicarboxylic acid and/or aminocarboxylic acid or its corresponding lactam." partially aromatic polymeric amide " meaning is that the amido linkage of partially aromatic polymeric amide comprises at least a aromatic ring and a kind of nonaromatic material.
Polymeric amide is normally by method preparation well-known in the art.A kind of typical method is to carry out melt phase polymerization by diacid-diamine complexes (can be or original position or prepare in independent step), any method, and starting material all are diacid and diamines.Additionally, a kind of ester that is formed by diacid also can use, preferably dimethyl ester.If use ester, reaction must be to carry out, common 80 ℃～120 ℃, become acid amides up to ester under relatively low temperature.Then mixture heating up is arrived polymerization temperature.The polymeric amide that is fit to has film forming molecular weight, about 0.25～approximately 1.5dL/g of preferred I.V., preferably approximately 0.4～about 1.2dL/g, more preferably about 0.7～approximately 0.9dL/g, I.V. is in phenol/1,1,2, measure concentration 0.5 gram/100ml, 25 ℃ of temperature in 60/40 (by weight) mixture of 2 tetrachloroethane.Wholly aromatic polyamide, the structural unit that its molecular chain comprises at least 70 moles of % derives from m-xylene diamine, or comprise m-xylene diamine and until the dimethylphenylene diamine mixture of 30% p-Xylol diamines, with α with 6～10 carbon atoms, ε-aliphatic dicarboxylic acid, also further see and be set forth in Japanese Patent open No.1156/75, No.5751175, No.5735/75 and No.10196/75, postpone prospectus No.29697/75 with Japanese patent application, these open source literatures here add as a reference.
By m-phthalic acid, terephthalic acid, cyclohexane dicarboxylic acid ,-or right-dimethylphenylene diamine, 1,3-or 1,4-hexanaphthene two methylamine, the aliphatic diacid with 6～12 carbon atoms, aliphatic amino acids, have 6～12 carbon atoms lactan, have the polymeric amide that the aliphatie diamine of 4～12 carbon atoms forms, and the polymeric amide that other common known diacid and diamines form can use.Low molecular polyamides can comprise the comonomer of small amount of trifunctional degree or four functionality simultaneously, as trihemellitic acid acid anhydride, pyromellitic dianhydride, or other polymeric amide that form with polyamines by polyacid known in the art.
The partially aromatic polymeric amide comprises: poly-(-the xylylene hexanediamide), poly-(-the xylylene hexanediamide-altogether-isophthaloyl amine), poly-(hexa-methylene isophthaloyl amine), poly-(hexa-methylene isophthaloyl amine-altogether-terephthalamide), poly-(hexamethylene adipamide-altogether-isophthaloyl amine), poly-(hexamethylene adipamide-altogether-terephthalamide), poly-(hexa-methylene isophthaloyl amine-be total to-terephthalamide) or the like or its mixture.Preferred partially aromatic polymeric amide includes, but are not limited to gather (-xylylene hexanediamide), poly-(hexa-methylene isophthaloyl amine-altogether-terephthalamide), poly-(-xylylene hexanediamide-altogether-isophthaloyl amine) and composition thereof.
The fatty polyamide that is fit to comprises polycaprolactam (nylon 6), poly-aminoheptylic acid (nylon 7), polyaminononanoic acid (nylon 9), nylon 11 (Ni Long11), nylon 12 (nylon 12), poly hexamethylene adipamide quadrol (nylon 2,6), nylon 46 (nylon 4,6), polyhexamethylene adipamide (nylon 6,6), polyhexamethylene sebacamide (nylon 6,10), poly-12 acyl hexanediamine (nylon 6,12), polyoctamethylene adipamide (nylon 8,6), polydecamethylene adipamide (nylon 10,6), poly hexamethylene adipamide 12 diamines (nylon 12,6) and polyhexamethylene sebacamide (nylon 12,8).
The polycarbonate that is fit to is formed the condensation product that properties-correcting agent comprises carbonate source and glycol source, and wherein carbonate component comprises the carbonate unit of 100 moles of %, and diol component comprises 100 moles of % diol units, and monomeric unit is 200 moles of % altogether.Term used herein " glycol " comprises aliphatics and aromatic substance with two hydroxyls.
Polycarbonate can comprise transesterify, melting polymerization and interfacial polymerization by various routines and the preparation of well-known method.The preparation polycarbonate is usually by a kind of dihydric phenol and a kind of carbonate precursor, and as phosgene, haloformate or carbonic ether react in melt or solution.The suitable method of polycarbonate for preparing of the present invention sees to be set forth in United States Patent(USP) Nos. 2,991,273,2,999,846,3,028,365,3,153,008,4,123,436, and all patents here are incorporated herein by reference.
The use of dihydric phenol is known, and its active group is thought phenolic hydroxyl group.Some typical dihydric phenols are bis-phenols, as 2,2-pair-(4-hydroxyphenyl)-propane (dihydroxyphenyl propane), 3,3,5 trimethylammoniums-1, two (4-the hydroxyphenyl)-hexanaphthenes of 1-, 2,4 pairs-(4-hydroxyphenyl)-2-methyl-butane, 1,1-pair-(4-hydroxyphenyl)-hexanaphthene, α, α '-two-(4-hydroxyphenyl)-p-Diisopropylbenzene, 2,2-pair-(3-methyl-4-hydroxyphenyl)-propane, 2,2-pair-(3-chloro-4-hydroxyphenyl) propane, two-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-pair-(3,5-dimethyl-4-hydroxyphenyl)-propane, two-(3,5-dimethyl-4-hydroxyphenyl)-thioether, two-(3,5-dimethyl-4-hydroxyphenyl)-sulfoxide, two-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, dihydroxy benaophenonel, 2,4-two-(3,5-dimethyl-4-hydroxyphenyl)-hexanaphthene, α, α '-two-(3,5-dimethyl-4-hydroxyphenyl)-right-diisopropylbenzene(DIPB) and 4,4 '-sulphonyl xenol.Other dihydric phenol can comprise Resorcinol, Resorcinol, two-(hydroxyphenyl)-alkane, two-(hydroxyphenyl)-ether, two-(hydroxyphenyl)-ketone, two-(hydroxyphenyl) sulfoxide, two-(hydroxyphenyl)-thioether, two-(hydroxyphenyl)-sulfone and α, α-two-(hydroxyphenyl) diisopropylbenzene(DIPB), and their nuclear-alkylating compound.The dihydric phenol that these and other are fit to sees to be set forth in that for example United States Patent(USP) Nos. 2,991,273,2,999,835,2,999,846,3,028,365,3,148,172,3,153,008,3,271,367,4,982,014,5,010,162, all patents here are incorporated herein by reference.Polycarbonate of the present invention may require their structure and derive from the unit of one or more bis-phenols that are fit to.
Normally a kind of carbonylic halide of carbonate precursor, diaryl carbonate or bishaloformate.Carbonylic halide comprises, for example, and carbonyl bromide, phosgene and its mixture.Bishaloformate comprises the bishaloformate of dihydric phenol, as 2, and the bischloroformate of two (4-hydroxyphenyl) propane of 2-, Resorcinol etc., or the bishaloformate of glycol, or the like.Although above-mentioned all carbonate precursors are useful, preferably carbonyl chloride also claims phosgene, and diphenyl carbonate.
The weight-average molecular weight of polycarbonate of the present invention is determined by gel permeation chromatography, and is about 10,000～200,000g/mol, preferred 15,000～80,000g/mol, its melt flow index, through ASTM D-1238, at 300 ℃ of mensuration, about 1～65g/10min, preferably approximately 2～30g/10min.This polycarbonate can be branching or non-branching.Can expect that this polycarbonate has various known end group.These resins are well-known, obtain from the market easily.
The polyester that is fit to is formed properties-correcting agent, be those condensed type polyester, when being introduced into the polyester polymers melt of polycondensation, with or import one or more new monomer residues, perhaps change the diacid residues of polyester polymers of polycondensation or the molecular fraction of diol residue, form a kind of polymkeric substance of modification of medium co-monomer content.This composition properties-correcting agent can be used for reducing or improve in the polyester polymers of polycondensation the content of carboxyl acid modified dose of residue or glycol modification agent residue.Monomer ratio in the polymkeric substance of modification depends on the relative content of forming comonomer in the properties-correcting agent and the ratio that is added to the composition properties-correcting agent of polycondensation polyester polymers.The polymerization process of aforesaid production polycondensation polyester polymers melt, also suitable preparation polyester is formed properties-correcting agent.
Polyester of the present invention is formed properties-correcting agent, comprise the polyester of introducing one or more carboxyl acid modified dose of residue and glycol modification agent residue, so that be included in the properties-correcting agent residue sum in this polyester composition properties-correcting agent, at least be 0.1 mole of %, or at least 1 mole of %, or at least 5 moles of %, or at least 10 moles of %, or at least 25 moles of %, or at least 50 moles of %, or at least 75 moles of %, or at least 100 moles of %, until about 125 moles of %, or until 150 moles of %, or until 200 moles of %, based on total molecular fraction (diol residue that comprises sour residue and the 100 moles of % of 100 moles of %) of 200 moles of %.
Remove terephthalic acid, the derivative of terephthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2, the derivative of 6-dicarboxylic acid, or outside the diacid component of its mixture, this polyester is formed the carboxyl acid component of properties-correcting agent, can utilize one or more carboxyl acid modified dose of other component preparations.This carboxyl acid modified dose of other component comprises monocarboxylic acid compound, dicarboxylic acid compound and has higher carboxyl number purpose compound.Example comprises the aromatic dicarboxylic acid that preferably has 8～14 carbon atoms, preferably has an aliphatic dicarboxylic acid of 4～12 carbon atoms, or preferably has the alicyclic dicarboxylic acid of 8～12 carbon atoms.The object lesson that is used as the dicarboxylic acid of properties-correcting agent acid constituents is, phthalic acid, m-phthalic acid, naphthalene-2,6-dicarboxylic acid, hexanaphthene-1,4-dicarboxylic acid, cyclohexanediacetic, phenylbenzene-4,4 '-dicarboxylic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid or the like, wherein most preferably m-phthalic acid, naphthalene-2,6-dicarboxylic acid and hexanaphthene-1,4-dicarboxylic acid.Should be appreciated that, adopt the corresponding acid anhydrides of these acid, ester and these sour chloride of acid, also be included in the term " carboxylic acid ".Also can adopt three carboxyl branching agents and the compound modified polyester that has higher carboxyl number, and the monocarboxylic acid chain terminator.
Except that the hydroxy component that comprises ethylene glycol, the hydroxy component that this polyester is formed properties-correcting agent can utilize one or more other glycol modification agent component preparations.This other glycol modification agent component comprises single alcohol, glycol, or has the compound of higher hydroxyl value.The example of properties-correcting agent oxy-compound comprises preferably having the cycloaliphatic diol of 6～20 carbon atoms, and/or preferably has the aliphatic diol of 3～20 carbon atoms.This glycol example more specifically comprises, glycol ether, triglycol, 1, the 4-cyclohexanedimethanol, propane-1, the 3-glycol, butane-1, the 4-glycol, pentane-1, the 5-glycol, hexane-1, the 6-glycol, 3-methyl pentanediol-(2,4), 2 hexylene glycol-(1,4), pure isooctane-glycol-(1,3), 2,5-Rutgers 612-(1,3), 2,2-diethyl propane-glycol-(1,3), hexylene glycol-(1,3), 1,4-two--(hydroxy ethoxy)-benzene, 2,2-pair-(4-hydroxy-cyclohexyl)-propane, 2,2,4,4-tetramethyl--1,3-cyclobutanediol unit, 2,2-pair-(3-'-hydroxyethoxy phenyl)-propane and 2,2-pair-(4-hydroxyl propoxy phenyl)-propane.As glycol modification agent component, this polyester is formed properties-correcting agent can preferably comprise such as 1 4-cyclohexanedimethanol, 2,2,4,4-tetramethyl--1, the comonomer of 3-cyclobutanediol unit and glycol ether.
In order to ensure the composition properties-correcting agent of introducing the physicals of polycondensation polyester polymers there is not adverse influence, the It.V. that polyester composition properties-correcting agent of the present invention should have is at least 0.45, or at least 0.50, or at least 0.55, or at least 0.60, or at least 0.65, or at least 0.70, this It.V. is under 25 ℃, measures in the solvent of being made up of the tetrachloroethane of the phenol of 60 weight % and 40 weight %.
The polymer molten fluid of discharging can be provided by any polymerization reactor that uses in the fusion phase technology of preparation polymkeric substance continuously, if having only a kind of polymer melt to exist here.For condensation-type polymerization thing and particularly polyester, this reactor wishes it is polycondensation reactor, they can have one or more titles, comprise pre-polymerization reactor, prefinishing reactor, first step reactor, second stage reactor, or finishing reactor (finishing reactor), or their coordinator.Polycondensation continues to carry out usually in one or more post polymerization stills, yet be not definitely, the slow liter until the temperature higher, in 250 ℃～310 ℃ scope than prepolymerization district, be more typically 270 ℃～300 ℃, be increased to the It.V. of last needs until the It.V. of melt.Final reactor, common industrial being called " high polymerization reactor ", " final polycondensation reactor ", or " polycondensation vessel ", its working pressure is also low than prepolymerization district usually, further removing glycol and/or other by product, and increase the molecular weight of polymer melt.The pressure in post polymerization district can be about 0.1～20mmHg, or 0.1～10mm Hg, or 0.1～2mm Hg.Though the post polymerization district is usually directed to the Essential Chemistry same as the pre-polymerization district, because bulk of molecule, thereby the difference of viscosity, reaction conditions is also just different.But as prepolymerization reactor, each post-polymerization device all is to operate under vacuum or rare gas element, does not need mechanical stirring to promote the removal of glycol and/or other by product.Although in certain discontinuous It.V. value, but with reference to various operational conditions, but also can within the described It.V. value or outside carry out different process conditionss, or apply described operational condition at the It.V. point that is not described melt.In addition, can come the adjusting process operational condition based on the melt It.V. of reaction times rather than mensuration or expectation.This technology also is not limited to utilize series connection or parallel tank reactor, or adopts different reactors in each district.For example, reactor can be one or more tubular reactors.Polycondensation neither be divided into pre-polymerization district and post polymerization district, because polycondensation can be carried out in a kind of Continuous Flow, its operational condition and a polycondensation reactor, or the slightly change in numerous tandem reactor, both intermittently, semi-batch technology, also continuous processing.
At the polyester fondant of discharging in the polymer molten fluid, the It.V. that has is at least 0.2dL/g, or 0.3dL/g at least, or 0.4dL/g at least, or 0.5dL/g at least.Preferably, this polymer melt is to be discharged by the final reactor that is used for fusion phase technology.More preferably, this polymer melt is to be discharged by bottom that is used for fusion phase technology end reaction device or final stage.As shown in Figure 1, the polymer melt 101 of polycondensation is to inject post polymerization (or aftercondensated) reactor 102, carry out polycondensation therein constantly, by toothed gear pump 103 or other the power that is fit to, discharge polymer molten fluid 104 continuously then by this reactor.In an embodiment, discharge the polyester polymers in the polyester polymers melt-flow continuously, its It.V. is 0.60dL g at least, or 0.68dL/g at least, or 0.72dL/g at least, or 0.74dL/g at least, or 0.76dL/g at least.
After arriving target It.V. in the final reactor, discharge polymer molten fluid continuously as the polymkeric substance of the modification of fusion phase technology, solidify by any method at last.The curing of the polymkeric substance of the modification of fusion phase technology without limits.The hot granulation of any routine or pellet cutting method and equipment can use, and include, but not limited to cut lines granulation and lines (forced conveyance) granulation, tablets press, water ring tablets press, fervent tablets press, underwater pelletizer and centrifugal granulator.For example, the polymkeric substance of melt modification can be directly by a die orifice, or only pelletizing, or directly by die orifice subsequently with the polymkeric substance pelletizing of melt modification.Can be used as power with toothed gear pump and order about the melt modification polymkeric substance and pass through die orifice.As not using toothed gear pump, the polymkeric substance of melt modification can inject list or twin screw extruder, extrudes by die orifice, and the temperature of extruder nozzle can randomly be 190 ℃ or higher.In case by die orifice, the polymkeric substance of modification can be drawn as tape, contact with a cold fluid, and be cut into bead, or this polymkeric substance can, carry out granulation randomly under water at die head.The polymkeric substance of modification can randomly filter by strainer 114, to remove overgauge particulate before cutting.
The polymer processing of modification becomes required form, as amorphous granular.The shape of the polymer beads of modification without limits, the moulding discrete particles regular or irregular, that size is not limit be can include, star, sphere, spheroid, class sphere, columniform moulding bead comprised, conventional bead, lozenge, and any other shape.
The present invention can further understand by consulting Fig. 1-3, and these are described, and is used for illustrating a kind of of within the scope of the present invention many embodiments separately.The embodiment of other in the scope of the invention can be described design, the unlikely spirit that departs from the scope of the invention with reference to these.
As shown in Figure 1, in the step a), the polymer molten fluid 101 of discharging is to utilize volumetric pump 103 to put into discharge line 104 from polymerization reactor 102 continuously continuously.In step b), a part of polymer molten fluid of discharging continuously is by extraction in the discharge line 104, and divides and draw formation slip-stream 105.The amount that shifts can be regulated by a valve or the known appropriate method that other regulate flow rate.A slip-stream plunger valve 106 is to enter in the slip-stream 105 in order to remove part discharge polymer molten fluid.If desired, slip-stream valve 106 can adopt a kind of optional volumetric pump that power is provided, and orders about the reactor that the slip-stream polymer melt got back to by the reactor of take out discharging polymkeric substance or the reactor of any other upstream.
In step c), will form properties-correcting agent 107 and inject slip-stream 105, comprise the slip-stream 109 of properties-correcting agent with formation.For example, as shown in Figure 1, form properties-correcting agent 107 and at first import forcing machine 110, inject slip-stream 105 after the fusion.For purposes of the invention, single screw rod and twin screw extruder all can be used.Randomly, when forcing machine 110 dischargings, can provide a toothed gear pump 108, to help the regulating load of forming properties-correcting agent and to be that the slip-stream component of polymer returns the pressure that the fusion phase reactor provides necessity.In another embodiment as shown in Figure 2, forcing machine 110 is and slip-stream 105 Configuration Online, so that form the properties-correcting agent fusion, and mix in the high hybird environment of forcing machine with slip-stream, forcing machine is twin screw extruder preferably.The usage quantity of forming properties-correcting agent can be regulated by any loss-in-weight feeder that common twin screw extruder has.In another embodiment of the present invention, forming properties-correcting agent 107 is to be introduced directly into slip-stream 105 from second polymerization reactor with the melting attitude.Polymer-modified usage quantity can be passed through a setter, as plunger valve, under meter, or volumetric pump, regulate.
Randomly, in step c), additive 112 can be introduced directly into slip-stream 105.In an embodiment, this additive 112 can be with the polymer-modified forcing machine 111 that imports.In another embodiment, additive can be at first and the vector resin melting mixing, forms a kind of masterbatch, and this vector resin is polyester preferably, more preferably or the polymer melt of this polycondensation, or forms the composition of properties-correcting agent.In another embodiment as shown in Figure 3, additive 112 is to be introduced into slip-stream before polymer-modified introducing.In another embodiment, additive is to introduce slip-stream again after composition properties-correcting agent is introduced into.In another embodiment still, optional liquid or solid additive composition can add the downstream that point and first adds point first and inject slip-stream, second additive component can inject pipeline in a similar fashion; The adding point that both additives inject slip-stream has nothing to do with the adding point of forming properties-correcting agent.The introducing point of optional additive depends on a number of factors, and comprises the temperature-sensitivity of this additive, the chemical action that may exist between other components in additive and the melt, and needed mixed-level.
For the ease of additive is directly introduced slip-stream, additive injection ozzle (not shown) should be designed to prevent to stop up.For example, this injection nozzle can allow nozzle segment stretch out the medullary ray of slip-stream pipe.Preferably, the leading-out end of this nozzle should stretch into the distance of the radius 1/3 of slip-stream pipe within the slip-stream, enters within the slip-stream mobile high shear zone.The opening of nozzle tip is limited in the quite little diameter, in case on-slip stream polymer melt enters nozzle.This small restriction makes when compositions of additives is injected into the polymer melt slip-stream, produces a pressure drop in nozzle tip.When plunger valve cut out, piston extended the insertion nozzle, and stretches into by injector head, has prevented that polymkeric substance from entering nozzle.
This additive can be a kind of liquid additive or solid additive.An example of liquid additive is a phosphorio compound, is used for stable in discharging polymer molten fluid or polycondensation catalyst makes inactivation.A kind of example of solid additive can comprise metal-powder or dispersion, as reheat additive, surface slip agent, or the material that intercepts or purify, they randomly can fusion before the charging.Preferably, any solid additive is introduced directly into and is used for melting and introduces polymer-modified forcing machine, perhaps at first sneaks into a kind of similar or homotype polymkeric substance for preparing in reactor, forms a kind of enriched material, and this enriched material is imported melt again and formed slip-stream.Enter the amount of the additive of slip-stream, depend on the additive concentration of preparing requirement in the solidified final polymer melt-flow 120.
For example, a kind of It.V. is the solid concentrates that comprises additive and polyester polymers of 0.60dL/g at least, can be in predetermined speed, and corresponding predetermined additive is melted and pumps into slip-stream under the concentration of discharging in the polymer molten fluid.By the concentration of additive in enriched material, additive can be determined delivery rate at the flow velocity that requires concentration and slip-stream of discharging in the polymer molten fluid.The preparation of solid additive composition can be different with the method for charging.For example, as mentioned above, pre-produce comprise the solid concentrates pellet that concentrates the amount additive, can be input into single screw extrusion machine, then fusion and be metered into slip-stream.Also pure additive directly can be entered by a step and be used to introduce within the forcing machine 111 of forming properties-correcting agent.
The example that can add the additive of discharging polymer molten fluid comprises, crystallization auxiliary, impact modifier, surface lubricant, denesting (denesting) agent, antioxidant, ultraviolet absorbers, metal passivator, tinting material, nucleator, acetaldehyde minimizing compound, raising reheat rate auxiliary agent, viscosity bottle additive such as talcum and filler, oxygen barrier material or the like.
In another embodiment, Ren Xuan additive is to use the polyester polymers (" PCR ") that reclaim the back.PCR can utilize to add simultaneously after the loss-in-weight feeder metering and be used for fusion and introduce within the polymer-modified forcing machine that enters slip-stream.So, be adding and the fusion of PCR just, or carry out the method that transesterification reaction is provided convenience with new polyester polymers.In an embodiment, finished polymer compositions comprises at least 5 weight %PCR, or at least 10 weight %PCR, or at least 15 weight %PCR.In another embodiment, scrap stock, waste material, or the new polyester polymers of heavily pulverizing, can be added into slip-stream, so that final polyester polymer composition also comprises the scrap stock of at least 0.5 weight % or at least 1 weight % or at least 5 weight %, heavily pulverize or useless polymkeric substance or even underproof polymkeric substance.
The flow of slip-stream can be regulated at the pressure of discharging generation in the polymer molten fluid 104 continuously by toothed gear pump 103.Be a kind of pressure-actuated slip-stream line 105 as shown in Figure 1.By the concentration of additive adding slip-stream, additive can be determined the slip-stream flow discharging the concentration that requires in the polymer molten fluid.The slip-stream flow rate can be in 2%～50% of the polymer melt speed of discharging continuously, or change between 5%～25%, depend on adding additive type and discharge the concentration of the additive that requires in the melt-flow.In a kind of pressure-driven slip-stream, the flow that slip-stream 105 will be by increasing this slip-stream carries out the homeostasis of flow with the pressure drop in the regulating loop.
Also can a under meter be installed on slip-stream line 105, be used for measuring and adjusting slip-stream variable valve 106, to change the flow of this slip-stream.Select as another kind, a positive-displacement pump can be installed at slip-stream line 105 places, so that fixing or constant flow, randomly a predetermined flow to be set.The slip-stream toothed gear pump both can be used as reliever, also the may command flow.If slip-stream divides wiring to adopt toothed gear pump, just do not need variable valve 106.
After the additive of forming properties-correcting agent and choosing wantonly adds slip-stream, sometimes can find, randomly adopt a mixing device so that to reach good mixing between polymer-modified, optional additive and the slip-stream polymer melt be desirable, particularly between significantly different densify fluid or between solid and the liquid.On pipeline, can use online mixing tank, maybe can adopt baffle plate or overflow plate, or as shown in Figure 1, can adopt static mixer 112.The type of used mixing device is unrestricted.
Along any point of this slip-stream, can heat or remove heating to the polymer melt of slip-stream.Need thermoregulator example to comprise, if exist under the situation of thermo-negative reaction or thermopositive reaction between the polymer melt in polymer-modified, optional additive and the slip-stream.Add optional thermally sensitized additive, to improve the polymer-modified and optional additive and the mixed performance of the polymer melt in the slip-stream.
If use corrosive additive, then the material of pipeline, mixing tank, valve and pump can adopt hastelloy or titanium or other corrosion resistant materials that is fit to.Also can adopt the material of corrosion resistant silvered film or liner protector corrosion-vulnerable influence.
In case the additive of forming properties-correcting agent and choosing wantonly has added slipstream line 105, forms a slip-stream that comprises properties-correcting agent, in step d), this slip-stream that comprises properties-correcting agent is imported into the upstream position that forms this slip-stream feed points.This will comprise that the slip-stream that comprises properties-correcting agent is infused in slip-stream tapping point 105 pipeline 104 before, inject toothed gear pump 103, inject the reactor 102 of the polymer melt of discharging polycondensation, or inject the upstream reactor of a pipeline or this final reactor 102.As shown in Figure 1, the slip-stream that comprises properties-correcting agent is to reactor 102 by plunger valve 113 feed backs.Randomly, this slip-stream that comprises properties-correcting agent can be by a mixing tank such as static mixer 112 uniform mixing.
Best, the slip-stream that comprises properties-correcting agent is to be input in the bottom of reactor 102.Like this, the slip-stream that comprises properties-correcting agent is in this technology later stage, polycondensation adds after finishing basically, just working as one or more following conditions is satisfied, or polyester fondant solidify before or after the time: a) It.V. of polyester fondant reaches 0.50dL/g at least, or b) if the vacuum that has pair polyester fondant to apply, remove, or c) if there is the melt phase polymerization process in polyester fondant, in a final reactor or between the tapping point of end reaction device and formation slip-stream, add additive, the preparation polyester polymers, or d) if there is the melt phase polymerization process in polyester fondant, at least 85% the time of following is used for this polyester fondant of polycondensation, or e) the highest It.V. that before curing, reaches of the It.V. of polyester fondant+/-0.05dl/g, or f) in before this curable polyester 20 minutes or the shorter time.
After the tapping point of slip-stream 105, the polymkeric substance of the modification of discharge is input into a solidification equipment (not shown) and randomly passes through strainer 114.
This technology is a successive circulation loop, therefore under steady state operation, polymer melt slip-stream 105 has comprised the composition properties-correcting agent and the optional additive of some amounts, inject the composition properties-correcting agent and the optional additive of additional content along with slipstream line, form a kind of slip-stream of being rich in properties-correcting agent, its concentration of forming properties-correcting agent and optional additives is higher than the slip-stream that additive adds before the implantation site.
By method of the present invention, just can produce product when conversion of multipolymer in melt phase polymerization, implement change of component faster, produced simultaneously suborder material still less, particularly for the large-scale continuous operating gear that is designed to produce this polyester.In addition, provide the polymer-modified method of adding in a kind of polyester polymers melt-flow, so that the time that allows is carried out good mixing and chemical equilibrium.This method also allows the back to add optional additive, thereby makes the thermal destruction of additive reduce to minimum, and can mix the final polymer melt equably.
Polyester polymer composition of the present invention is particularly suitable for preparing fiber, sheet material, film, plate, makeup bottle and the pallet of stretch blow bottle, extrusion-blown modling bottle, bottle base, carpet or clothes or filler, or medicine bottle and pallet.
The present invention has used with reference to its embodiment preferred and has been described in detail, but very clear, can implement change and modification within the spirit and scope of the present invention.In addition, above-mentioned all patents, patent application (delivering with unpublished, external or domestic), reference or other publication are all here introduced as any disclosed reference relevant with enforcement of the present invention.

Claims (56)

1. one kind prepares polymer-modified method, comprise: the polymer melt of a) discharging polycondensation from polymerization reactor, form a polymer molten fluid of discharging continuously, b) from the polymer molten fluid of continuous discharge, extract a part of polymer melt out and form slip-stream, c) in described slip-stream, introduce a kind of properties-correcting agent of forming and form a kind of slip-stream that contains properties-correcting agent, and d) slip-stream that will contain properties-correcting agent is incorporated in the step b) and extracts the upstream position of polymer melt out from discharging polymer molten fluid.
2. the process of claim 1 wherein that the polymer melt of described polycondensation is a kind of polyester or a kind of copolyesters.
3. the method for claim 2, the polymer melt of wherein said polycondensation is a kind of polyester, it comprises:
(i) a kind of carboxyl acid component comprises terephthalic acid, terephthaldehyde acid derivative, the naphthalene-2 of at least 80 moles of %, 6-dicarboxylic acid, naphthalene-2, the derivative of 6-dicarboxylic acid, or the residue of its mixture and
(ii) a kind of hydroxy component, what comprise the glycol residue of at least 80 moles of % and 0～20 mole of % is selected from 1,4-cyclohexanedimethanol unit, the glycol ether unit, 2,2,4,4-tetramethyl--1,3-cyclobutanediol unit, modification ethylene glycol unit with 2～16 carbon, or the residue of its mixture, based on the carboxyl acid component residue of 100 moles of % in the polyester polymers and the hydroxy component residue meter of 100 moles of %, wherein the logarithmic viscosity number of polymer melt Continuous Flow is 0.50～1.2dL/g, in 25 ℃, measures in the solvent of being made up of 60 weight % phenol and 40 weight % tetrachloroethane.
4. the method for claim 3, comprise 0～20 mole of % dicarboxylic acid units, its be selected from m-phthalic acid, phthalic acid, hexanaphthene-1,4 dicarboxylic acid, cyclohexanediacetic, phenylbenzene-4,4 '-dicarboxylic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid and its mixture.
5. the method for claim 3 comprises 0～20 mole of % and is selected from the unitary dicarboxylic acid units of m-phthalic acid.
6. the method for claim 3 comprises the diol residue greater than 0～20 mole of %, and it is selected from 1,4-cyclohexanedimethanol unit, glycol ether unit, 2,2,4,4-tetramethyl--1,3-cyclobutanediol unit and its mixture.
7. the method for claim 3, wherein said polymer molten fluid is a kind of polyester that comprises additive, described additive comprises UV light absorber, hot rate accelerating material(RAM), oxygen scavenger, acetaldehyde reduce agent, catalyst passivating agent or its combination again.
8. the method for claim 3, wherein acetaldehyde reduces agent and is not present in the described polymer molten fluid.
9. the process of claim 1 wherein the described polymer-modified polycondensate that comprises.
10. the method for claim 9, wherein said polymer-modified be polymeric amide, polycarbonate or polyester.
11. the method for claim 10, wherein said polyamide modified polymkeric substance are to introduce in the described slip-stream with the speed that enough adds 0.1 weight %～10 weight % polymeric amide in discharging polymer molten fluid.
12. the method for claim 10, wherein said polycarbonate modified polymkeric substance are to import in the described slip-stream with the speed that enough adds 0.1 weight %～50 weight % polycarbonate in discharging polymer molten fluid.
13. the method for claim 9, wherein said polymer-modified be a kind of copolyesters.
14. the method for claim 13, the polymer-modified carboxyl acid modified dose of residue that comprises 0.1～100 mole of % of wherein said copolyesters, or the glycol modification agent residue of 0.1～100 mole of %.
15. the method for claim 14, wherein said carboxyl acid modified dose of residue comprises the aromatic dicarboxylic acid with 8～14 carbon atoms, the aliphatic dicarboxylic acid with 4～12 carbon atoms, or has the cycloaliphatic dicarboxylic acid of 8～12 carbon atoms.
16. the method for claim 14, wherein said carboxyl acid modified dose of residue comprises phthalic acid, m-phthalic acid, naphthalene-2,6-dicarboxylic acid, hexanaphthene-1,4-dicarboxylic acid, cyclohexanediacetic, phenylbenzene-4,4 '-dicarboxylic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid or the like, wherein preferred m-phthalic acid, naphthalene-2,6-dicarboxylic acid and hexanaphthene-1,4-dicarboxylic acid.
17. the method for claim 14, wherein said carboxyl acid modified dose of residue comprises phthalic acid, m-phthalic acid, naphthalene-2,6-dicarboxylic acid, hexanaphthene-1,4-dicarboxylic acid, cyclohexanediacetic, phenylbenzene-4,4 '-dicarboxylic acid, Succinic Acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid.
18. the method for claim 14, wherein said carboxyl acid modified dose of residue comprises m-phthalic acid, naphthalene-2,6-dicarboxylic acid and hexanaphthene-1,4-dicarboxylic acid.
19. the method for claim 14, wherein said glycol modification agent residue comprise the cycloaliphatic diol with 6～20 carbon atoms and have the aliphatic diol of 3～20 carbon atoms.
20. the method for claim 14, wherein said glycol modification agent residue comprises glycol ether, triglycol, 1, the 4-cyclohexanedimethanol, propane-1, the 3-glycol, butane-1, the 4-glycol, pentane-1, the 5-glycol, hexane-1, the 6-glycol, 3-methyl pentanediol-(2,4), 2 hexylene glycol (1,4), 2,2,4-trimethylpentane-glycol-(1,3), 2,5-Rutgers 612-(1,3), 2,2-diethyl propane-glycol-(1,3), hexylene glycol-(1,3), 1,4-two-(hydroxy ethoxy)-benzene, 2,2-pair-(4-hydroxy-cyclohexyl)-propane, 2,4 dihydroxyl-1,1,3,3-tetramethyl--tetramethylene, 2,2-pair-(3-'-hydroxyethoxy phenyl)-propane and 2,2-pair-(4-hydroxyl propoxy phenyl)-propane.
21. the method for claim 14, wherein said glycol modification agent residue comprises 1,4-cyclohexanedimethanol, 2,2,4,4 tetramethyl-s-1,3-cyclobutanediol unit and glycol ether.
22. the method for claim 14, the limiting viscosity of wherein said composition properties-correcting agent greater than 0.45, in 25 ℃, are measured in the solvent of being made up of 60 weight % phenol and 40 weight % tetrachloroethane.
23. the process of claim 1 wherein that variable valve 106 telomerized polymer melts pass the flow rate of described slip-stream.
24. the process of claim 1 wherein that it is the flow rate that the telomerized polymer melt passes described slip-stream that a kind of Melt Pump adds described slip-stream.
25. the process of claim 1 wherein that it is the flow rate that the telomerized polymer melt passes described slip-stream that a kind of under meter adds described slip-stream.
26. the process of claim 1 wherein that the flow rate of slip-stream is 2%～50% of a described discharge polymer molten fluid throughput rate.
27. the process of claim 1 wherein and reduce the melt temperature of regulating described slip-stream more than the 0.2dL/g with the It.V. that prevents described slip-stream.
28. the process of claim 1 wherein that the melt temperature of described slip-stream is arranged on does not exceed in polymer-modified 10 ℃ of scopes.
29. the process of claim 1 wherein the described melt temperature that comprises the slip-stream of properties-correcting agent, the temperature difference that is set up or is adjusted in and leave the continuous discharge polymer melt outlet of polyreaction is not more than in 10 ℃ of scopes.
30. the process of claim 1 wherein that described composition properties-correcting agent imports forcing machine, fusion, pumps into described slip-stream then, to generate a kind of slip-stream that comprises properties-correcting agent.
31. the process of claim 1 wherein from the described composition modifier polymer and the polymer melt of described slip-stream, all import along the forcing machine of the online arrangement of described slip-stream, and melting mixing.
32. the process of claim 1 wherein that described composition properties-correcting agent is to be provided by the Continuous Flow of second polymerization reactor as a kind of polymer melt, and utilize Melt Pump or online forcing machine directly to inject the polymer melt of described slip-stream.
33. the process of claim 1 wherein additive with the described polymer-modified forcing machine that is injected into, and introduce described slip-stream.
34. the process of claim 1 wherein described additive be as master batch with the polymer-modified forcing machine that is injected into, and introduce described slip-stream.
35. the process of claim 1 wherein that described additive master batch is fused and pumps into described slip-stream.
36. the method for claim 34, wherein said additive master batch comprises the polyester support resin that a kind of It.V. is at least 0.6dL/g.
37. the process of claim 1 wherein that described additive randomly utilizes a kind of pump,, inject described slip-stream as liquid or slurry.
38. the process of claim 1 wherein that described additive is to inject described slip-stream before introducing described composition properties-correcting agent.
39. the process of claim 1 wherein that described additive is to inject described slip-stream after introducing described composition properties-correcting agent.
40. the process of claim 1 wherein that first additive adds the implantation site first and injects described slip-stream, second additive injects described slip-stream in first downstream that adds the implantation site.
41. the method for any one in the claim 33～40, wherein said additive comprise UV light absorber, hot rate accelerating material(RAM), oxygen scavenger, acetaldehyde reduce agent, catalyst passivating agent or its combination again.
42. the process of claim 1 wherein that a kind of polyester polymers discarded, that reclaim is added in the polymer melt of described continuous generation.
43. the method for claim 1 comprises the online static mixer of a kind of slip-stream, is in after the position of described composition properties-correcting agent adding slip-stream.
44. the method for claim 1 comprises a kind of and the online static mixer of slip-stream, is in after the position that first additive adds described slip-stream.
45. the process of claim 1 wherein randomly to add a kind of Melt Pump, pressure to be provided and to control through-rate at the described slip-stream place of drawing.
46. the process of claim 1 wherein that the material of the pipeline, mixing tank, valve and the pump that comprise described slip-stream is hastelloy or titanium.
47. the process of claim 1 wherein that the described slip-stream that comprises properties-correcting agent is the upstream end injection polycondensation reactor at the discharge point that forms described slip-stream.
48. the process of claim 1 wherein that the described input point that comprises the slip-stream of properties-correcting agent is at final polycondensation reactor and forms between the tapping point of slip-stream.
49. the process of claim 1 wherein the input position of the described slip-stream that comprises properties-correcting agent within final polycondensation reactor, and before described polymer melt solidifies, import.
50. the process of claim 1 wherein that the described slip-stream that comprises properties-correcting agent is to inject finishing reactor in the final polycondensation reactor series, or inject in the reactor line of connection finishing reactor of described final polycondensation reactor upstream.
51. the process of claim 1 wherein that the described slip-stream that comprises properties-correcting agent is input to the position after at least 85% polymer melt polycondensation time.
52. the process of claim 1 wherein the described slip-stream that comprises properties-correcting agent be the It.V. of described polyester fondant for the highest It.V. that reaches before solidifying+/-0.1dL/g after, import described polyester fondant stream.
53. the process of claim 1 wherein that the described slip-stream that comprises properties-correcting agent is to solidify preceding 20 minutes or inject described reactor in shorter time at described polycondensation polymer melt.
54. goods, it is by the polymer-modified melt district that is added to forcing machine with claim 1, and is shaped and is obtained by described polymer melt, and the It.V. of wherein said melt is at least 0.72dL/g.
55. goods, it is added to a kind of melt-processed district of forcing machine by the polymer-modified pellet that the method for claim 1 is produced, the described pellet of fusion forms a kind of polymer melt, and be configured as goods and obtain by the polymer melt of described modification, the It.V. of wherein said pellet is at least 0.72dL/g.
56. a method, wherein slip-stream from discharge continuously be removed the polymer molten fluid before or after static mixer is installed.
CN2006800338100A 2005-09-16 2006-09-05 Late addition to effect compositional modifications in condensation polymers Expired - Fee Related CN101351492B (en)

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CN105463594A (en) * 2015-11-09 2016-04-06 浙江易彤色纺科技有限公司 Melt spinning method by directly adding functional materials and/or pigments

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CN113512779A (en) * 2020-04-09 2021-10-19 中国石油化工股份有限公司 Production method and device of low-VOC (volatile organic compound) polyester fiber
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US6664413B1 (en) * 1998-11-19 2003-12-16 A. E. Staley Manufacturing Co. Process for production of esters
DE10022889B4 (en) * 2000-05-25 2007-12-20 Lurgi Zimmer Gmbh Process for producing synthetic threads from a polyester-based polymer blend
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CN104264244B (en) * 2014-09-19 2016-05-25 江苏江南高纤股份有限公司 Online polyester fondant Direct Spinning method and system of adding functional modification agent
CN105463594A (en) * 2015-11-09 2016-04-06 浙江易彤色纺科技有限公司 Melt spinning method by directly adding functional materials and/or pigments

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