CN1894325A - Oxygen scavenging composition - Google Patents

Abstract

Oxygen scavenging composition comprising a copolymer comprising polypropylene oxide 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 segments. The invention also provides the process for the preparation of this composition.

Description

Deoxidizing compositions

The present invention relates to a kind of deoxidizing compositions, said composition comprises a kind of multipolymer and oxide catalyst that comprises polyoxytrimethylene (polypropylene oxide) fragment and polymer segments.

By WO 99/15433 known such composition.In this document, deoxidizing compositions is extruded preparation by the polymer segments (concrete is polycondensate) and the reactivity of functionalized poly propylene oxide oligopolymer.The products therefrom former state that is called as co-condensation polymer is used in single thin film or the multilayer film, or dilutes with other polycondensate.

Obviously, this composition is limited in the effect of deoxygenation aspect of performance, and this makes and must adopt thicker layer to reach resistance active oxygen performance to a certain degree.

The objective of the invention is a kind of composition, said composition comprises a kind of multipolymer that comprises polyoxytrimethylene fragment and polymer segments, and said composition is compared with known compositions has better resistance active oxygen performance.

According to the present invention, this purpose realizes that wherein, multipolymer passes through the incompatible preparation of copolymerization in the presence of the functionalized poly propylene oxide is segmental of corresponding monomer.

Surprisingly, have been found that: polymer segments is formed by corresponding monomer and the copolymerization of functionalized poly propylene oxide fragment, rather than polyoxytrimethylene fragment that these are functionalized and polymeric polymer segments reaction, this makes the deoxygenation performance of composition significantly different.

Very advantageously remove the active oxygen performance according to composition exhibiting of the present invention.

Be also referred to as the polycondensate of condensation polymer, wherein polyester (particularly polymeric amide) forms certain obstacle to oxygen, and they can be used as film, wrapping paper, bottle or other container of feed, food and drink because of this and other reason.The packaged article of they protections avoid directly contacting with environment (comprising the oxygen in the ambient air).Because these polymer layers are oxygen flows not fully, so known a kind of compound is sneaked in this polymkeric substance, this compound can be removed by the oxygen that chemical reaction bonding oxygen will infiltrate in the polymer layer.

This compound is called as active oxygen scavenger.Among these, reported polyoxygenated alkene and polydiene example as active oxygen scavenger.Also known employing can with the oxygen scavenger of polycondensate reaction, and known scavenging agent and the polycondensate of making (for example, extruded) reaction by reactivity during mixture.

The example of polycondensate is polyester and polymeric amide.Suitable polyester example is polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PEN (PEN), polybutylene naphthalate (PBN).Suitable polyamide (PA) example is that (they can be branched polyamide to aliphatic polyamide as a result, for example PA6, PA4,6, PA6,6, PA11, PA12), partially aromatic polyamide is (as MXD6, PA6, I/6, T, PA6,6/6, T), the multipolymer and the blend of Wholly aromatic polyamide and listed polymeric amide and polyester.

The oxygen compound that removes as in the composition according to the present invention uses the multipolymer that comprises functionalized poly propylene oxide (PPO) fragment and polymer segments, and this multipolymer is by preparing the polymerization in the presence of polyoxytrimethylene is segmental of corresponding polymer monomer.These are different with multipolymer well known in the prior art, and known multipolymer is extruded by the reactivity of the polymer segments of functionalized PPO oligopolymer fragment and certain segment length or molecular weight and obtained.In WO 99/15433 known preparation method, PPO oligopolymer fragment is usually with the terminal group functional that can react with the avtive spot of polymkeric substance.For example, by the example in known this end functional groups of WO99/15433 and reactive polymer site.In the identical functionalized copolymerization process that can be used in multipolymer of the present invention.

Suitable PPO fragment is collinear PPO oligopolymer, preferably replaces type.In the IUPAC nomenclature, this PPO is named as polypropylene glycol (polyoxy-1,2-glyceryl).They are made up of 2-5000 polyoxytrimethylene monomeric unit, preferably, form by 10-2500 unit, and with this form and size, they and monomer copolymerization.In this scope, reach the uniform distribution of multipolymer in the polycondensate.During this copolymerization, the multipolymer of formation-ABABA-type, this multipolymer comprise the polymer segments A and propylene oxide (being propylene oxide) the fragment B of alternative variable-length.

In another embodiment, the PPO fragment is as two, three, four or the branch of more star branch compounds and existing, the center cell of this branch compound can be for example two, three, four or more ester, acid amides, ether, the carbamate of polyfunctionality.Be used in the method for the multipolymer in the composition of the present invention in preparation, polymer segments is then along the branched free terminal growth of PPO fragment.During this copolymerization, linear copolymer can form ABA type multipolymer or have branched minute graft copolymer of BA type.

Except the PPO fragment, also can randomly there be other ether fragment, for example, and polyoxyethylene, however its quantity is compared with PPO and will be lacked.Preferably, the segmental amount of other ether is lower than 40wt% with the ratio of the amount of PPO, more preferably, is lower than 30wt% or is lower than 10wt%.

Suitable polymers fragment in the multipolymer is that those form polycondensate described above (particularly polyester and aliphatic polyamide, preferably PA6 or PA6,6) the monomeric fragment of formation, this multipolymer is by forming the copolymerization in the presence of PPO is segmental of corresponding monomer.

These multipolymers can by with functionalized PPO in the presence of monomeric under known corresponding monomeric polymerizing condition reaction form or can form according to US 4590243 and EP 0067695.

In these methods, except monomer and PPO fragment, can also there be other compound, for example catalyzer, chain terminator, stablizer etc.In these reactions, introduce linear PPO fragment, can come functionalized end-blocking with hydroxyl, amino or carboxyl or other functional group of monomer (aggregating into those monomers of polymer fragments) reaction in the terminal employing of this fragment as divalent moiety.In star branch PPO fragment, free end promptly, is not connected to those ends of the segmental PPO part of PPO of star-shaped molecule centre portions, adopts above-mentioned group functionalization.

In can being used in according to the multipolymer in the composition of the present invention, the relative quantity of PPO is 0.5-40wt%, preferably 1-30wt%.Low amount will shorten can be with the deoxygenation property retention in high-caliber time span.Higher amount may cause forming the segmental external phase altogether of PPO in composition.This total resistance oxygen ability for composition is unfavorable, and therefore, the amount of PPO should make PPO form disperse phase in composition in the composition.

Advantageously, the deoxygenation PPO fragment that is present in the composition exists with small agglomerates (conglomerate) form in composition.These coacervates can be spheric, and can have (promptly up to the size of 500nm, diameter or minor axis, axle is defined as connecting the last radially-arranged line in coacervate surface at 2), preferably at most 30wt% or more preferably at most the coacervate of 25wt% have above diameter of 500nm or minor axis.Sphere is understood to be in has size identical or much at one on the three-dimensional space direction, only also be interpreted as and depart from spherical form with following degree, and departure degree is that axial length is the longest for having 1.3 times of diameter length of equal volume ball.Preferably, at least 50% coacervate has the size of maximum 300nm, preferred maximum 200nm.More preferably, at least 70,90 or even 99% coacervate in specified scope.The more for a short time oxygen resistance that causes of the size of coacervate is good more.

Also find,, comprise that the article according to composition layer of the present invention show the deoxygenation performance of raising when the shape of most of coacervate when to have length-to-diameter ratio and major part be directed.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 is bigger than the size on another direction in space at least in the size at least one direction in space.Ratio between the described size preferably at least 1.3, more preferably at least 2 or even 5 or even 50 or greater than 100.This differs greatly with the coacervate that has substantially the same size on three-dimensional space direction.Orientation herein means, overall dimension is extended being parallel on the direction in space of article surface, and this surface is the surface that is exposed in the oxygen to be removed.The overall dimension of this coacervate on described parallel direction can be greater than 500nm, even reaches several millimeters.Yet, perpendicular to the gravel size decision of the coacervate on described surface be to be lower than 400nm, more preferably be lower than 350nm.This has obviously improved the transparency of deoxygenation layer in the article.The article that contain the coacervate with length-to-diameter ratio can be by making article during its preparation or carry out orientation step (for example, by making article at the molten state down cut, by extruding, particularly, by stretching) later on obtain 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 with good grounds composition of the present invention, wherein, there is the segmental coacervate of polyoxytrimethylene, at least 50%, preferably, at least 70%, more preferably, at least 90% coacervate in the size at least one direction in space than at least 1.3 times greatly of the sizes on another direction in space at least, and wherein large-size extends on the direction of this at least one face that is parallel to article.

Also comprise oxide catalyst according to composition of the present invention, 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, 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, II or IV and ruthenium I, II or IV, titanium III or IV, vanadium III, IV or V.

Preferably, Co II or III in catalyzer as the metal part.

The suitable gegenion of 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, adopts polymeric counterion.This ionomer is known in the art.Phthalein cyanogen is as the example of suitable mating part.The amount of transistion metal compound can be 10ppm-10wt%.

Preferably, the amount of transistion metal compound is 50-5000wt.ppm in the composition.

Also can comprise other conventional additives according to compound of the present invention, they can give composition some other required character, and example is fiber, filler, nano particle, oxidation inhibitor, fire retardant, releasing agent and other other compound that is used for this purpose known in the art.

Composition according to the present invention has excellent oxygen resistance, and for example, when according to ASTM standard D3985, under drying conditions, when measuring on the thick film of 60 μ m, said composition has less than 0.3, preferably less than 0.1cc.mm/ (m ²It atm) resistance oxygen value.

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 constitutes, to compare with the layer that directly is exposed in the environment, the active lifetime of composition and effectiveness obviously improve.Other application is the layer in a bottle wall, wall of container or other wall of container, and concrete is is used to be packaged in oxygen influence those of the food that descends of quality or other material down.Therefore, the invention still further relates to the purposes that composition according to the present invention is used for application mentioned above.The proper method itself that is used to make above composition layer is known, is the technology that is generally used for moulding and makes polymer materials.

The deoxidizing compositions that comprises multipolymer and oxide catalyst can prepare by following process: multipolymer mixes in independent step with oxide catalyst, or mixes in the step of being made article by composition according to the present invention.

This mixing 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.This process using melting mixing, that is, it is above but carry out under the temperature that its decomposition temperature is following that this is blended in the fusing point of oxygen scavenging copolymers.

The present invention sets forth by following examples, but is not limited thereto.

Experiment 1: preparation oxygen scavenging copolymers

The preparation copolymer 1

The oligopolymer (Br ü ggemann P1-30, polypropylene glycol ester acyl caprolactam) that adds hexanolactam (88.8wt%) and contain PPO in the reaction flask that agitator, thermocouple and nitrogen inlet mouth are housed (11.2wt%).This mixture dilutes in 1: 1 mode with catalyst solution (Br ü ggemann C1,12% hexanolactam magnesium bromide in hexanolactam).After mixing under 100 ℃, the mixture of gained is poured in the mould, and kept 5 minutes down at 145 ℃.The solid copolyamide that will contain the 5wt% polypropylene glycol takes out from mould and pulverizes.

Preparation multipolymer 2

The oligopolymer (Br ü ggemann P1-30, polypropylene glycol ester acyl caprolactam) that adds hexanolactam (55.6wt%) and contain PPO in the reaction flask that agitator, thermocouple and nitrogen inlet mouth are housed (44.4wt%).This mixture dilutes in 1: 1 mode with catalyst solution (Br ü ggemann C1,12% hexanolactam magnesium bromide in hexanolactam).After mixing under 100 ℃, the mixture of gained 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.

Preparation multipolymer 3 (contrast)

The oligopolymer (Br ü ggemann P1-30, polypropylene glycol ester acyl caprolactam) that adds hexanolactam (29.9wt%) and contain PPO in the reaction flask that agitator, thermocouple and nitrogen inlet mouth are housed (70.1wt%).This mixture dilutes in 2: 1 mode with catalyst solution (Br ü ggemann C1,15% hexanolactam magnesium bromide in hexanolactam).After mixing under 100 ℃, the mixture of gained is poured in the mould, and kept 5 minutes down at 145 ℃.The solid copolyamide that will contain the 42wt% polypropylene glycol takes out from mould and pulverizes.

Preparation multipolymer 4

In being housed, the 2L reactor of distillation column and agitator adds 790g dimethyl terephthalate (DMT), 560g 1,4-butyleneglycol, 100g poly-(ethylene oxide-propylene oxide-ethylene oxide), 250mg titanium tetrabutoxide and 150mg four hydration magnesium acetates.After with reactor usefulness nitrogen wash 3 times, the material in the reactor was heated to 150 ℃ temperature 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 ℃ temperature.Then, with the ester exchange offspring that obtains like this further under 240 ℃ of vacuum (being low to moderate 2mbar) with the stirring velocity polymerization of 20RPM 150 minutes.With institute's polymerized product under nitrogen pressure from reactor strip deviate from cooling and in tablets press, form particle in water.

Preparation multipolymer 5 (contrast)

In being housed, the 2L reactor of distillation column and agitator adds 800g dimethyl terephthalate (DMT), 495g 1,4-butyleneglycol, 100g poly-(tetrahydrofuran (THF)-1000), 480mg titanium tetrabutoxide and 300mg four hydration magnesium acetates.After with reactor usefulness nitrogen wash 3 times, the material in the reactor was heated to 150 ℃ temperature 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 ℃ temperature.Then, the ester exchange offspring that obtains like this further (is reduced 2mbar) with the stirring velocity polymerization of 20RPM 150 minutes under 240 ℃ of vacuum.With institute's polymerized product under nitrogen pressure from reactor strip deviate from cooling and in tablets press, form particle in water.

Experiment 2: preparation deoxygenation sample

With copolymer 1,2,3,4 and 5 and oxide catalyst cobaltous acetate melting mixing.This is blended under residence time of 260 ℃ the speed of rotation of charging basket temperature, 120rpm and 3 minutes and carries out.All experiments are implemented under nitrogen atmosphere.Multipolymer is dry before processing.Prepared material is stored in the sealing bag after processing.Information about these samples is listed in the table 1.

In order to contrast, based on functionalized PPO oligopolymer (the Jeffamine D-2000 of Huntsman) and polyamide 6 (DSM Akulon F132-E, viscosity number 210ml/g ISO 307, the relative viscosity of measuring in 90% formic acid under 30 ℃: sample C1 3.20) and C2 are by preparing with the employing of the reaction extrusion process in the twin screw extruder 3 minutes and 5 minute residence time in the laboratory.

Also preparation does not contain reference polyamide 6 (sample D) except that oxygen compound as the reference of sample 1,2, A, C1 and C2.

(DSM Arnite T04200, the relative viscosity of measuring in 25 ℃ of following 1wt% m-cresol solutions: 1.85) reference sample (sample E) as the reference of sample 3 and B, sees Table 1 also to prepare the polybutylene terephthalate that does not contain except that oxygen compound.

Table 1

Sample	Remove oxygen compound	PPO content (wt%)	Co(Ac) 2Content (ppm)
				1	Copolymer 1	5	1000
2	Multipolymer 2	20	1000
				A	Multipolymer 3	42	1000

3	Multipolymer 4	6.8	1000
				B	Multipolymer 5	10	1000
C1	Jeffamine *D-2000	4.8	1000
				C2 **	Jeffamine *D-2000	4.8	1000
D	Do not have	0	1000
				E	Do not have	0	1000

^*The amine end-blocking PPO of Huntsman

^*: 5 minutes residence time

Experiment 3: preparation oxygen scavenging film

All samples is pulverized under cold condition.The gained powder is pushed the film that forms thick 55-75 micron between smooth hot plate.This film is of a size of 13 * 13cm ²Extruding condition is: the plate temperature: 260 ℃, and the time between no pressing plate: 5 minutes, under 10kN, pressurizeed 3 minutes then.

Experiment 4: the oxygen-permeable of MEASUREMENTS OF THIN

The oxygen-permeable of prepared film is measured according to ASTMD3985 (film one side is exposed under the nitrogen environment, and it is 1bar that opposite side is exposed to the oxygen partial pressure difference that makes under the oxygen atmosphere between the film) by MOCON OX-TRAN 2/21 permeameter.Testing permeability is under drying conditions, and (23 ℃) carry out under the room temperature.Under measuring condition, after 50 hours, measure.

In table 2, show the oxygen-permeable of various films.Oxygen-permeable has been carried out stdn with thickness.

Table 2

Sample	Oxygen-permeable cc mm/ (m 2It atm)
		1	0.0
2	0.0
		A	87.34
3	＜0.2
		B	4.55
C1	0.46

C2 **	0.47
		D	1.03
E	14.92

The limit of detection of Oxtran permeameter is 5 * 10 ^-3Cc mm/ (m ²It atm).For the sample of given thickness range, this makes inherent permeation limit is 4 * 10 ^-4Cc mm/ (m ²It atm).Sample 1 and 2 intrinsic oxygen-permeable are less than 4 * 10 ^-4Cc mm/ (m ²It atm).

Relatively polyamide-based deoxygenation sample (sample 1,2, A, C1, C2) and the resistance oxygen result of reference sample D accordingly, as can be known:, have less than 4 * 10 according to sample of the present invention (that is sample 1 and 2) for the composition of the oxide catalyst that contains 1000ppm ^-4Cc mm/ (m ²It atm) oxygen value.The numerical value of these numeric ratio comparative sample A1 and A2 is much lower, and this comparative sample is according to disclosed method preparation among the WO 99/15433.The numerical value of these numeric ratio reference samples D is also much lower.Under the situation of sample A, oxygen resistance is on duty mutually, and most probable reason is that ether is phase-changed into successive.Under the situation of sample 1 and 2, ether is dispersed mutually.

Relatively polyester based deoxygenation sample (sample 4,5) and the resistance oxygen result of reference sample C accordingly, as can be known:, have (m less than 0.2cc mm/ according to sample of the present invention (that is, sample 4) for the composition of the oxide catalyst that contains 1000ppm ²It atm) oxygen value.It is much lower that this numeric ratio contains the numerical value of sample B of tetrahydrofuran base ether system (substitute PPO ether system), and this has proved that PPO is better than the deoxygenation ability of other ether.It is also much lower that this numeric ratio does not contain the numerical value of reference sample E of deoxygenation component.

Claims (15)

1. deoxidizing compositions, described composition comprises a kind of multipolymer and oxide catalyst that comprises polyoxytrimethylene fragment and polymer segments, it is characterized in that described multipolymer passes through the incompatible preparation of copolymerization in the presence of the functionalized poly propylene oxide is segmental of corresponding monomer.

2. deoxidizing compositions as claimed in claim 1, wherein, described polymer segments is polymeric amide or polyester.

3. deoxidizing compositions as claimed in claim 1 or 2, wherein, the segmental amount of described polyoxytrimethylene is 0.5-40wt% with respect to described composition.

4. deoxidizing compositions as claimed in claim 3, wherein, described amount is 1-30wt%.

5. as any described deoxidizing compositions among the claim 1-4, wherein, do not have polycondensate, and wherein, described polyoxytrimethylene fragment exists as spherical agglomerates, and maximum 25% coacervate has the above size of 300nm.

6. as any described deoxidizing compositions among the claim 1-5, wherein, described oxide catalyst is transition metal salt or title complex.

7. as any described deoxidizing compositions among the claim 1-6, when according to ASTM standard D3985, under drying conditions, when measuring on the thick film of 60 μ m, described deoxidizing compositions has the (m less than 0.3cc.mm/ ²It atm) resistance oxygen value.

8. deoxidizing compositions as claimed in claim 7, when according to ASTM standard D3985, under drying conditions, when measuring on the thick film of 60 μ m, described deoxidizing compositions has the (m less than 0.1cc.mm/ ²It atm) resistance oxygen value.

9. be used to prepare the purposes of deoxygenation article according to any described deoxidizing compositions among the claim 1-8.

10. purposes as claimed in claim 9, wherein, described article are the containers that are used for food, drink or feed package, for example film, bottle, container or wrapping paper.

11. purposes as claimed in claim 10, wherein, described article are multi-layer articles, and wherein said deoxidizing compositions layer is clipped between two-layer other material layer.

12. article, at least the one side of described article is exposed in the oxygenated environment, and described article comprise the layer that contains any described composition among the claim 1-8, wherein, there is the segmental coacervate of described polyoxytrimethylene, than at least 1.3 times greatly of the sizes on another direction in space at least, and described large-size extends being parallel on the direction of described at least one face at least 90% coacervate in the size at least one direction in space.

13. article as claimed in claim 12, wherein, maximum 25% described coacervate perpendicular to the size on the direction of described at least one face less than 350nm.

14. article as claimed in claim 13, wherein, described article are packaging vessels of food, drink or feed, for example film, bottle, container or wrapping paper.

15. article as claimed in claim 13, wherein, described article are multi-layer articles, and wherein said deoxidizing compositions layer is clipped between two-layer other material layer.