CN1894324A - Oxygen scavenging composition - Google Patents
Oxygen scavenging composition Download PDFInfo
- Publication number
- CN1894324A CN1894324A CN200480037751.5A CN200480037751A CN1894324A CN 1894324 A CN1894324 A CN 1894324A CN 200480037751 A CN200480037751 A CN 200480037751A CN 1894324 A CN1894324 A CN 1894324A
- Authority
- CN
- China
- Prior art keywords
- deoxidizing compositions
- article
- multipolymer
- polycondensate
- segment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Oxygen scavenging composition comprising a copolymer comprising polypropylene oxide chain segments and polymer segments and an oxidation catalyst, characterized in that the copolymer has been prepared by copolymerising the corresponding monomers in the presence of functionalised polypropylene oxide chain segments. The invention also provides the process for the preparation of this composition.
Description
The present invention relates to deoxidizing compositions, it comprises polycondensate, contains the multipolymer and the oxide catalyst of poly(propylene oxide) segment and polymer segment.
From the so as can be known composition of WO 99/15433.In this document, by polymer segment, particularly the preparation deoxidizing compositions is extruded in the reaction of polycondensate and functionalized propylene oxide oligopolymer.The product that is expressed as co-condensation polymer of gained itself is used for the single or multiple lift film or dilutes with other polycondensate.
Show that this dilute compositions is limited in efficient aspect oxygen characteristic, this causes adopting thicker layer to obtain the active oxygen barrier properties of specific degrees.
The purpose of this invention is to provide a kind of composition, the multipolymer that said composition comprises polycondensate and contains poly(propylene oxide) segment and polymer segment, and have better active oxygen barrier properties than known composition.
According to the present invention, prepare multipolymer by the corresponding monomer of copolymerization in the presence of functionalized poly(propylene oxide) segmental, thereby realize above-mentioned purpose.
Show surprisingly, form polymer segment by corresponding monomer of copolymerization and functionalized poly propylene oxide segment, rather than with these functionalized poly propylene oxide segments and polymeric polymer segment reaction, this fact causes final diluted composition having significant difference except that on the oxygen characteristic.
Composition according to the present invention provides very favourable oxygen scavenging activity characteristic for the polycondensate in the composition.Polyester in the polycondensate (also claiming condensation polymer) particularly polymeric amide forms blocking layer to oxygen, and in view of the above and other is former thereby be used as the container of film, outer packaging, bottle, vessel or other splendid attire feed, food and drink.They prevent that package food article from directly contacting with environment (comprising the oxygen in the atmosphere).Because oxygen is not the layer of these polymkeric substance of porous not fully, therefore knownly can in polymkeric substance, sneak into compound, thereby this compound can combine the oxygen that removing infilters polymer layer by chemical reaction with oxygen.
This compound is called as active oxygen scavenger.Report, the example of active oxygen scavenger is polyalkylene oxide and polydiene.Can and make oxygen scavenger and polycondensate reacts with the oxygen scavenger of polycondensate reaction about how using in mixing process (for example extruding by reaction), this also is known.The example that can be used for the polycondensate of composition of the present invention with good result is polyester and polymeric amide.The example of suitable polyester is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PEN (PEN), polybutylene naphthalate (PBN).The example of suitable polyamide (PA) is can be finally to be the aliphatic polyamide of cladodification polymeric amide (for example PA6, PA4,6, PA6,6, PA11, PA12), partially aromatic polyamide (for example MXD6, PA6, I/6T, PA6,6/6, T), the multipolymer and the mixture of Wholly aromatic polyamide and listed polymeric amide and polyester.Comprising aliphatic polyamide in the composition makes best results of the present invention, reason be that aliphatic polyamide itself compares with for example aromatic poly and have lower resistance oxygen characteristic as polycondensate.
The oxygen compound that removes as in the composition of the present invention uses the multipolymer that comprises functionalized poly propylene oxide (PPO) segment and polymer segment, and this multipolymer prepares by polymerization corresponding polymer monomer in the presence of the poly(propylene oxide) segmental.This is different from, and prior art is known extrudes the multipolymer that functionalized PPO oligomeric segment and the preformed polymer segment with length-specific or molecular weight obtain by reaction.From WO 99/15433 preparation method as can be known, usually with coming to carry out functionalized with the end group that the reactive moieties of polymkeric substance is reacted to the PPO oligomeric segment.The example at such end functional groups and reactive polymer position can for example be learnt from WO 99/15433.In the copolymerization process of the used multipolymer of the present invention, can use identical functionality.
Suitable PPO segment is the linear oligomer of PPO, preferably its replacement form.In the IUPAC nomenclature, this PPO is expressed as polypropylene glycol (polyoxy-1,2-glyceryl).Its by 2 to 5000, preferred 10 to 2500 poly(propylene oxide) monomeric units form, and with this form and size and corresponding monomer copolymerizable.In this scope, can reach the uniform distribution of multipolymer in polycondensate.In this copolymerization process, formed the multipolymer of adjustable length polymer segment A and propylene oxide segment B alternative-ABABA-type.
In another embodiment, the PPO segment be with two, three, four or the side chain of higher star cladodification compound exist, the center cell of this compound can for example be two, three, four or higher functional ester, acid amides, ether and carbamate.In the preparation method of the multipolymer that is used for composition of the present invention, polymer segment begins growth from the free end of PPO segment side chain.In this copolymerization process, can form the linear copolymer of ABA type or have the cladodification multipolymer of the side chain of BA type.
Except that the PPO segment, other ether segment of also optional existence, polyethylene oxide for example, but its amount is less than PPO.Preferably, other ether segmental amount is preferably the 40wt% less than the PPO amount, is more preferably less than the 30wt% of PPO amount or the 10wt% that measures less than PPO.
In by the multipolymer that the corresponding monomer of copolymerization forms in the presence of the PPO segmental, the suitable polymers segment is the polycondensate, particularly polyester (preferred PBT) of those above definition and the segment of aliphatic polyamide (preferred PA6 or PA6,6).
Can form these multipolymers by making functionalized PPO reaction in the presence of monomeric, reaction conditions is that corresponding monomeric polymerization is known or according to US 4590243 and EP 0067695.
In these methods, beyond demonomerization and the PPO segment, also can there be other compound, for example catalyzer, chain terminator, stablizer etc.These reactions are introduced linear PPO segment as divalent moiety, its end for example by hydroxyl, amino sour or other can be with the group of the monomer reaction that aggregates into polymer moieties the functionality end-blocking.In star cladodification type PPO segment, free end (being PPO those ends partly that the PPO segmental is not connected with the star centre portions) is functionalized with above-mentioned group.
In can be used for the multipolymer of composition of the present invention, the relative quantity of PPO can be 0.5-95wt% or 1-95wt%, preferred 2-85wt% or 5-75wt% or 5-60wt%.
In the composition that comprises polycondensate and multipolymer, because the diluting effect of polycondensate, the relative quantity of PPO will be lower.In final composition, the relative quantity of the relative multipolymer total amount of PPO (if the change that is suitable for comprises compound and the polycondensate that is obtained by its polymerization process) can change in the scope of 0.5-50wt%, preferred 1-30wt%.Especially, lower amount will reduce and remove oxygen characteristic and keep the high-caliber time.Higher amount may cause forming PPO segmental external phase altogether in composition.This is unfavorable for total resistance oxygen ability of composition, and the PPO that therefore should choose in the composition measures so that PPO forms disperse phase in composition.Should be appreciated that in composition of the present invention, can measure and sneak into the required PPO relative quantity of multiple combination acquisition of the multipolymer amount of composition by PPO in the multipolymer.
In this regard, multipolymer and polycondensate fully compatible (that is, can be miscible on submicron-scale) also be correlated with.This compatibility is influenced by the amount of the polymkeric substance in the multipolymer and the amount of the PPO in type and the final composition really.By change this tittle in above-mentioned scope, those skilled in the art can make oxygen scavenging copolymers good dispersion in polycondensate, and advantageously make deoxygenation PPO segment form little coacervate in composition, thereby obtain required deaerating effect.These coacervates can be spheric, and its size (is diameter or minimum axle, it is defined as and connects 2 the line segment length that is positioned on the coacervate surface on the diameter) can reach 500nm, preferred at the most 30% or more preferably at the most the diameter of 25% coacervate or minimum axle more than 500nm." spheric " should be understood to be in has size identical or much at one on the three-dimensional space direction, depart from the spheric degree only is at most the ball with equal volume for axial length 1.3 times of diameter length.Preferably, at least 50% coacervate is of a size of 300nm at the most, preferably 200nm at the most.More preferably, at least 70,90 or even 99% coacervate in above-mentioned specified scope.The size of coacervate is more little, and the resistance oxygen characteristic is good more.
Also find, when the shape of most of coacervate have length-to-diameter ratio and major part be orientation the time, comprise that the article of the layer of the present composition present enhanced deoxygenation performance.This coacervate can have elongated or smooth shape, as cigar shape or pancake shape.Coacervate with length-to-diameter ratio is characterised in that, this coacervate in the size at least one direction in space greater than the size on another direction in space at least.Ratio between the described size is preferably at least 1.3, and more preferably at least 2 or even 5 or even 50 or greater than 100.This obviously is different from the coacervate that has substantially the same size on three-dimensional space direction.Orientation herein is meant, overall dimension is extended being parallel on the direction in space of article surface, and this surface is exposed in the oxygen to be removed.The overall dimension on described parallel direction of this coacervate can be greater than 500nm, even reaches several millimeters, and the accessible upper limit is limited by the actual techniques limit only.Yet, be preferably dimensioned to be less than 400nm perpendicular to the coacervate on described surface, be more preferably less than 350nm.This has significantly improved the transparency of deoxygenation layer in the article.Can be by making article during its preparation or carry out the article that orientation step (for example, being sheared under molten state by making article, by extruding, particularly, by stretching) obtains to contain the coacervate with length-to-diameter ratio later on one or more directions.
Therefore, the invention still further relates to a kind of article, these article have at least one and are exposed to surface in the oxygenated environment, these article comprise the layer that contains composition of the present invention, wherein there is poly(propylene oxide) segmental coacervate, at least 50%, preferably at least 70%, more preferably at least 90% coacervate is being of a size of at least 1.3 times of size on another direction in space at least at least one direction in space, and wherein large-size extends being parallel on described at least one surperficial direction in space of article.
When the polymer moieties of oxygen scavenging copolymers and polycondensate were same type, for example when it was polymeric amide or polyester, compatibility was improved.Yet some polyester also can present the enough consistencies with some polymeric amide, thereby obtains comprising the composition of the coacervate with desired size as described below.Can known method or interpolation itself is known to be can be used for the compound of this purpose or is used for the polymer segment of multipolymer and the catalyzer of the rearrangement reaction between the polycondensate improves consistency by using.
Composition of the present invention preferably also comprises oxide catalyst, and this oxide catalyst promotes to remove the oxygen activity that removes of oxygen compound.
Suitable oxide catalyst comprises transition-metal catalyst, and this catalyzer can easily be changed between at least two oxidation state.Preferably, transition metal is the form of transition metal salt or transition metal complex, and wherein, this metal is selected from 4,5,6,7,8,9,10,11 and 12 families of the periodic table of elements.Suitable metal comprises manganese II or III, iron II or III, chromium II or III, cobalt II or III, copper I or II, nickel II or III, rhodium II or II or IV and ruthenium I, II or IV, titanium III or IV, vanadium III, IV or V.
Preferred Co II or the III of using is as the metal part in catalyzer.
The gegenion of suitable metal includes, but not limited to chlorion, acetate ion, methyl ethyl diketone acid ion, stearate radical ion, propionate ion, palmitinic acid radical ion, 2 ethyl hexanoic acid radical ion, neodecanoic acid radical ion or naphthalene two acid ions.Metal can also be an ionomer, in this case, uses polymeric counterion.This ionomer is known in the art.The example of suitable coordination part is a phthalein cyanogen.The consumption of transistion metal compound can be 10ppm-10wt%.
Preferably, the amount of transistion metal compound is 50-5000ppm.
Compound of the present invention also can comprise other conventional additives, they can give composition some other desired characteristic, and the example of additive is for example enhancement type material, filler, oxidation inhibitor, fire retardant, releasing agent and other other compound that is used for this purpose known in the art of fiber.
Composition of the present invention has excellent resistance oxygen characteristic, and for example, when being the film of 60 μ ms when measuring to thickness according to ASTM standard D3985 under drying conditions, said composition has less than 0.3, preferably less than 0.1cc.mm/ (m
2It atm) resistance oxygen.
Composition of the present invention can preferably be clipped between other layer as internal layer as the one deck in the multilayer film.In this sandwich structure, the active lifetime of composition is compared obvious raising with the layer of rendeing a service with directly being exposed to environment.Other application is the layer on a bottle wall, vessel wall or other container (particularly those are used to be packaged in oxygen influence food or other material of the degradation down) wall.Therefore, the invention still further relates to the purposes that composition of the present invention is used for above-mentioned application.The proper method itself that is used for this is known, is moulding of using always and the technology of making polymer materials.
The invention still further relates to the method for deoxidizing compositions that preparation comprises polycondensate and contains the multipolymer of poly(propylene oxide) segment and polymer segment, it is characterized in that polycondensate and the multipolymer melting mixing of preparing by the corresponding monomer of the formation of polymerization in the presence of poly(propylene oxide) segmental polymkeric substance.
The method of deoxidizing compositions that preparation comprises polycondensate and contains the multipolymer of poly(propylene oxide) segment and polymer segment can be learnt from WO 99/15433.In this currently known methods, the functionalized moiety can with the condition of functional group reactions in the polycondensate under, can in forcing machine, be mixed with the functionalized PPO segment of the part of polycondensate reaction terminal, promptly this method is the reaction extrusion method.
Have surprisingly been found that with the oxygen scavenging copolymers that mixing condition is suitable and the time is suitable of method preparation of the present invention, compare with the composition for preparing with currently known methods, the deoxygenation performance is better.
Method of the present invention can be carried out in the device (for example, forcing machine and mixing tank) that is used for the mixture heat thermoplastic polymer known in the art.Present method adopts melting mixing, that is, this mixing is to carry out more than the fusing point of polycondensate and oxygen scavenging copolymers, below the decomposition temperature.
Set forth the present invention by following examples, but the invention is not restricted to these embodiment.
Experiment 1: preparation oxygen scavenging copolymers
The preparation copolymer 1
The phosphate aqueous solution and the 36.4g hexanodioic acid that in the 2L reactor of distillation column and agitator is housed, add 332.0g ∈-hexanolactam, 500.0g polyoxy propylene diamine, 2.0g 85m%.After with reactor usefulness nitrogen wash 3 times, the material in the reactor was heated to 205 ℃ gradually under stirring and normal atmosphere, and under this temperature, kept 19 hours in 1 hour.Subsequently, in 3 hours, further be heated to 210 ℃.Polymerisate is taken out from reactor under nitrogen pressure and grinds.Then it was used boiling water extraction three times, and under 90 ℃, under nitrogen atmosphere, dry overnight in vacuum drying oven.
Preparation multipolymer 2
In being housed, the 2L reactor of distillation column and agitator adds 410g dimethyl terephthalate (DMT), 290g 1,4-butyleneglycol, 550g propylene oxide base oligopolymer, 250mg tetrabutyl titanate, 150mg four hydration magnesium acetates and 590mg N, N '-hexa-methylene two (3,5-two-tertiary butyl-4-hydroxy hydrocinnamamide).After with reactor usefulness nitrogen wash 3 times, the material in the reactor was heated to 150 ℃ gradually under stirring and normal atmosphere, and under this temperature, keeps half an hour in 1 hour.Subsequently, in 2 hours, further be heated to 220 ℃.Then, with the ester exchange offspring that obtains like this further under 240 ℃, vacuum (being low to moderate 2mbar) with the stirring velocity polymerization of 20 RPM 180 minutes.Polymerisate is taken out with the material strips from reactor under nitrogen pressure, in water, cool off and granulation in tablets press.
Preparation multipolymer 3
In the flask that agitator, thermocouple and nitrogen inlet are housed, add hexanolactam (55.6wt%) and contain the oligopolymer (Br of PPO
Ggemann P1-30, polypropylene glycol ester acyl caprolactam) (44.4wt%).With this mixture catalyst solution (Br
Ggemann C1,12% the hexanolactam Manganese dibromide in hexanolactam) dilute in 1: 1 mode.After mixing under 100 ℃, the gained mixture is poured in the mould, and kept 5 minutes down at 145 ℃.The solid copolyamide that will contain the 20wt% polypropylene glycol takes out from mould and pulverizes.
Experiment 2: make each deoxygenation blend l-7, A1, A2 and B
Preparation have that different blend is formed and the oxidation catalysis agent content based on copolymer 1 and polyamide 6 (DSM Akulon F132-E, viscosity number 210ml/g ISO 307, the relative viscosity of under 30 ℃, measuring in 90% formic acid: four kinds of blends (1-4) 3.20).In addition, preparation is based on multipolymer 2, contain the blend (5) of 0.05wt%Irganox 1098 and based on the blend (6) of multipolymer 3 in addition, and the two contains the polyamide 6 identical with blend l-4.And, based on multipolymer l and the cladodification polyamide 6 (relative viscosity of under 30 ℃, measuring in 90% formic acid: 3.12) preparation blend (7).All these blends all prepare in the full meshed double screw forcing machine of laboratory scale conical parallel dual.Cobaltous acetate adds as oxide catalyst.
Carrying out the blended condition is: 260 ℃ of barrel temperatures, speed of rotation 120rpm, 3 minutes residence time.All experiments are all carried out under nitrogen atmosphere.Before processing with the polymeric amide drying.Blend with preparation after the processing is stored in the sealing bag.In order to contrast, carry out reaction extrusion process by the residence time in laboratory scale twin screw extruder, prepare composition A1 and A2 based on functionalized PPO oligopolymer (the Jeffamine D-2000 of Huntsman) and polyamide 6 with 3 minutes and 5 minutes.Also preparation does not contain the blend B except that oxygen compound.Table l has provided blend composition.
Table 1
| Blend | Remove oxygen compound (OSC) | OSC measures (wt%) | Akulon F132- E(wt％) | Akulon XP 36- E(wt％) | PPO blend content (wt%) | Co(Ac) 2Content (ppm) |
| 1 | Copolymer 1 | 8 | 91.9 | - | 4.8 | 1000 |
| 2 | Copolymer 1 | 8 | 91.99 | - | 4.8 | 100 |
| 3 | Copolymer 1 | 11 | 88.9 | - | 6.6 | 1000 |
| 4 | Copolymer 1 | 17 | 82.9 | - | 10.2 | 1000 |
| 5 | Multipolymer 2 | 8 | 91.9 | - | 3.0 | 1000 |
| 6 | Multipolymer 3 | 25 | 74.9 | - | 5 | 1000 |
| 7 | Copolymer 1 | 8 | 0 | 91.9 | 4.8 | 1000 |
| A1 | Jeffamine *D- 2000 | 4.8 | 95.1 | - | 4.8 | 1000 |
| A2 ** | Jeffamine *D- 2000 | 4.8 | 95.1 | - | 4.8 | 1000 |
| B | Do not have | - | 99.9 | - | - | 1000 |
*The amine end-blocking PPO of Huntsman
*: 5 minutes residence time
Experiment 3: the deaerating membrane of preparation blend 1-7, A1, A2 and B
All blends are ground under cold condition.The gained powder is pressed into the film that thickness is the 55-75 micron between flat plate heat.Film is of a size of 13 * 13cm
2Pressing conditions is: the plate temperature: 260 ℃, and the no pressure time between plate: 5 minutes, subsequently with the time of 10kN: 3 minutes to the system pressurization.Form with the film of determination of transmission electron microscopy blend 5 (containing 8% multipolymer 2).Dispersive multipolymer 2 coating of particles are the sphere of the about 0.5 μ m of diameter in the PA6 matrix.
Experiment 4: preparation deoxygenation blend 8
Preparation is based on polyamide 6 (DSM AkulonF132-E on ZSK 25mm parallel dual-screw extruding machine, viscosity number 210ml/g ISO 307, the relative viscosity of under 30 ℃, measuring in 90% formic acid: the blend of the multipolymer 2 of the 8wt% 3.20), the cobaltous acetate of 0.1wt% (with handing the melt temperature that thermometer is measured at outlet of extruder: 290 ℃, screw speed: 300rpm).
Experiment 5: the deaerating membrane of preparation blend 8 and pure PA6 (composition C)
Coming preparation size in order to following equipment and arrange accordingly by film casting method is the transparent film of the blend 8 of 300mm (wide)/40 μ m (thick): forcing machine: G ttfert 32mm/3D, screw speed: 90rpm, design temperature: 260 ℃, membrana oralis size: 320mm (wide)/0.4mm (thick), cooling roller: 110 ℃, and governing speed is to obtain the film that thickness is 40 μ m.
Form with this film of determination of transmission electron microscopy.Dispersive multipolymer 2 coating of particles are oval in the PA6 matrix, and its major axis I is 7.8 (standard deviation 2.3 and d＜400 μ m) with the ratio of minor axis d.Particle is orientated extruding on the direction.
At the film that has on the identical device of identical setting the pure PA6 of preparation (DSM Akulon F132-E) as reference.
Experiment 5: preparation is based on PET and multipolymer 2 with based on the deaerating membrane of pure PET
With the wetting of particulates of the cobaltous acetate solution in the tetrahydrofuran (THF) with multipolymer 2, subsequent drying.With these particles and polyethylene terephthalate (Amite D04300) (PET) particle do the PET composition (blend 9) that mixes to obtain containing 8wt% multipolymer 2 and 1000ppm cobaltous acetate.Prepare film that thickness be 50 μ ms by film casting method from said mixture in order to following equipment and arrange accordingly: forcing machine: Battenfeld 45mm, design temperature: 270 ℃, screw speed: 15rpm, mouth mould size: 250mm (wide)/0.5mm (thick), cooling roller: 18 ℃, governing speed is to obtain the film that thickness is 50-54 μ m.
Has on the identical device of identical setting the pure PET film of preparation as reference.
Example I-XI and Comparative experiment A-E: the oxygen transmission rate of measuring film
According to ASTM D3985, be exposed to nitrogen environment and opposite side is exposed to oxygen atmosphere so that the oxygen partial pressure difference of film both sides is 1bar by a side with film, measure the oxygen transmission rate of prepared film with MOCON OX-TRAN 2/21 permeameter.The oxygen transmission rate test is carried out under drying conditions (except as otherwise noted), room temperature (23 ℃).For the PA6 basement membrane, under measuring condition, keep beginning after 50 hours to measure; For PET base blend, under measuring condition, keep 50 hours (embodiment X) and began measurement in 130 hours after (embodiment XI).
Table 2 has been listed the oxygen transmission rate of various films.The relative thickness of oxygen transmission rate has carried out stdn.
Table 2
| Embodiment/comparative example | Be used to prepare the blend of film | Oxygen transmission rate cc mm/ (m2 days atm) |
| I | 1 | 0.00 |
| II | 1 | (0.00 relative humidity 85%) |
| III | 2 | 0.19 |
| IV | 3 | 0.00 |
| V | 4 | 0.00 |
| VI | 5 | 0.07 |
| VII | 6 | 0.00 |
| VIII | 7 | 0.00 |
| IX | 8 | 0.01 |
| X | 9 | 2.24 |
| XI | 9 | 2.56 |
| Contrast A | A1 | 0.46 |
| Contrast B | A2 | 0.47 |
| Contrast C | B | 1.03 |
| Contrast D (PA6 reference) | 1.01 | |
| Contrast E (PET reference) | 3.89 |
The detectability of Oxtran permeameter is 5 * 10
-3Cc.mm/ (m
2. day .atm).For the sample of given thickness range, this causes the intrinsic permeability limit is 4 * 10
-4Cc.mm/ (m
2. day .atm).By the intrinsic oxygen transmission rate of samples of blend 1,3,4 and 6 preparations less than 4 * 10
-4Cc mm/ (m
2It atm).
These results show that the oxygen transmission rate numerical value of PA6 base deoxidizing compositions of the present invention is for the composition that contains the 1000ppm oxide catalyst, and under drying conditions and under 85% the relative humidity, scope is at 0.00-0.07cc mm/ (m
2It atm).These numerical value are far below Comparative Examples A that is prepared by WO 99/15433 disclosed method and the numerical value of B, and comparison is also more much lower than the numerical value of Embodiment C.Even when composition of the present invention only contained the oxide catalyst (EXAMPLE III) of 100ppm, oxygen transmission rate still was starkly lower than the oxygen transmission rate of the blend membrane of prior art.The oxygen transmission rate result of comparing embodiment VI and example I X finds out, compares with the composition that contains spherical eliminating particle, and the oxygen transmission rate that comprises the grains of composition with length-to-diameter ratio is lower.Comparing embodiment X, XI and embodiment E (PET reference) show that interpolation deoxygenation material (multipolymer 2) and transition-metal catalyst can reduce oxygen transmission rate in PET.
Claims (19)
1. deoxidizing compositions, it comprises polycondensate, contains the multipolymer and the oxide catalyst of poly(propylene oxide) segment and polymer segment, it is characterized in that described multipolymer prepares by the corresponding monomer of copolymerization in the presence of functionalized poly propylene oxide segmental.
2. deoxidizing compositions as claimed in claim 1, wherein said polymer segment are polymeric amide or polyester.
3. as the deoxidizing compositions of claim 1 or 2, wherein said polycondensate is (being total to) polymeric amide or (being total to) polyester or its mixture.
4. as any one deoxidizing compositions among the claim 1-3, the type of wherein said polycondensate and described polymer segment is identical.
5. as any one deoxidizing compositions among the claim 1-4, wherein said poly(propylene oxide) segment is 0.5-50wt% with respect to the amount of described composition.
6. deoxidizing compositions as claimed in claim 5, wherein said amount are 1-30wt%.
7. as any one deoxidizing compositions among the claim 1-6, wherein said poly(propylene oxide) segment exists with coacervate, and at the most the size of 25% described coacervate greater than 500nm.
8. as any one deoxidizing compositions among the claim 1-7, wherein said oxide catalyst is the salt or the complex compound of transition metal.
9. as any one deoxidizing compositions among the claim 1-8, it is characterized in that when being the film of 60 μ ms when measuring to thickness according to ASTM standard D3985, the oxygen transmission rate of described deoxidizing compositions is less than 0.3cc.mm/ (m under drying conditions
2It atm).
10. deoxidizing compositions as claimed in claim 9 is characterized in that, when being the film of 60 μ ms when measuring to thickness according to ASTM standard D3985 under drying conditions, the oxygen transmission rate of described deoxidizing compositions is less than 0.1cc.mm/ (m
2It atm).
11. preparation is as the method for the deoxidizing compositions of any one among the claim 1-10, it is characterized in that, polycondensate with constitute the multipolymer melting mixing that the corresponding monomer of described polymer segment is prepared by copolymerization in the presence of functionalized poly propylene oxide segmental, and it is characterized in that adding oxide catalyst.
12. preparation is as the method for the deoxidizing compositions of any one among the claim 1-10, it is characterized in that, described multipolymer is to constitute that the corresponding monomer of described polymer segment prepares and described multipolymer and polycondensate melting mixing by copolymerization in the presence of functional poly propylene oxide segmental, and it is characterized in that adding oxide catalyst.
13. be used to prepare the purposes of deoxygenation article as the deoxidizing compositions of any one or the preparation of the method by claim 11 or 12 among the claim 1-10.
14. as the purposes of claim 13, wherein said article are the containers that are used for food, beverage or feed package, for example film, bottle, vessel or outer packaging.
15. as the purposes of claim 13, wherein said article are multi-layer articles, wherein the described deoxidizing compositions of one deck is sandwiched between two-layer other material.
16. article, it has at least one surface that is exposed to oxygenated environment, and comprise contain just like among the claim 1-10 any one or by the layer of the composition of the method for claim 11 or 12 preparation, wherein there is described poly(propylene oxide) segmental coacervate, at least 90% described coacervate is being of a size of at least 1.3 times of size on another direction in space at least at least one direction in space, and wherein said bigger size is extended being parallel on described at least one surperficial direction.
17. as the article of claim 16, wherein at the most 25% described coacervate perpendicular to the size on described at least one surperficial direction less than 350nm.
18. as the article of claim 16, wherein said article are the containers that are used for food, beverage or feed package, for example film, bottle, vessel or outer packaging.
19. as the article of claim 16, wherein said article are multi-layer articles, wherein the described deoxidizing compositions of one deck is sandwiched between two-layer other material.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03078901.0A EP1544239A1 (en) | 2003-12-17 | Oxygen scavenging composition | |
| EP03078901.0 | 2003-12-17 | ||
| EP04077094.3 | 2004-07-19 | ||
| EP04077094 | 2004-07-19 | ||
| PCT/NL2004/000854 WO2005059019A1 (en) | 2003-12-17 | 2004-12-09 | Oxygen scavenging composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1894324A true CN1894324A (en) | 2007-01-10 |
| CN1894324B CN1894324B (en) | 2011-12-14 |
Family
ID=34924034
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800377765A Expired - Fee Related CN100432128C (en) | 2003-12-17 | 2004-12-09 | Oxygen scavenging composition |
| CN2004800377515A Expired - Fee Related CN1894324B (en) | 2003-12-17 | 2004-12-09 | Oxygen scavenging composition |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800377765A Expired - Fee Related CN100432128C (en) | 2003-12-17 | 2004-12-09 | Oxygen scavenging composition |
Country Status (2)
| Country | Link |
|---|---|
| CN (2) | CN100432128C (en) |
| ES (1) | ES2360525T3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102016118551A1 (en) * | 2016-09-29 | 2018-03-29 | Rkw Se | Covering system for silage preparation |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6083585A (en) * | 1996-09-23 | 2000-07-04 | Bp Amoco Corporation | Oxygen scavenging condensation copolymers for bottles and packaging articles |
| US6455620B1 (en) * | 1999-08-10 | 2002-09-24 | Eastman Chemical Company | Polyether containing polymers for oxygen scavenging |
-
2004
- 2004-12-09 CN CNB2004800377765A patent/CN100432128C/en not_active Expired - Fee Related
- 2004-12-09 ES ES04808770T patent/ES2360525T3/en active Active
- 2004-12-09 CN CN2004800377515A patent/CN1894324B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1894324B (en) | 2011-12-14 |
| CN1894325A (en) | 2007-01-10 |
| ES2360525T3 (en) | 2011-06-06 |
| CN100432128C (en) | 2008-11-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103261327B (en) | Daiamid composition | |
| EP2588528B1 (en) | Oxygen scavenging plastic material | |
| TWI491640B (en) | Polyamide resin composition | |
| CN1396208A (en) | Polyester resin composition and its moulding product | |
| JP2008523170A (en) | Polyester-based cobalt concentrate for oxygen scavenging compositions | |
| WO2009032560A1 (en) | Oxygen scavenging plastic compositions | |
| EP1701999B1 (en) | Oxygen scavenging composition | |
| CN1237117C (en) | Polyamide resin composition | |
| EP1701998B1 (en) | Oxygen scavenging composition | |
| TW201920478A (en) | Resin composition, shaped article, and film | |
| CN1894324B (en) | Oxygen scavenging composition | |
| CN102802947B (en) | Have and improve oxygen reactive polyamide-polydiene blend | |
| CN101198466A (en) | Oxygen scavenging multilayer film | |
| CN103228699A (en) | Block copolymers comprising poly(1,3-rimethylene terephthalate) and poly(1,3-trimethylene 2,6-naphthalate) | |
| DK1883516T3 (en) | Resinpellets compartmentalized to remove oxygen and method for thermally treating said resinpellets |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20111214 Termination date: 20161209 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |