CN109705321A - A kind of polyester material with oxygen absorption function, preparation and application - Google Patents
A kind of polyester material with oxygen absorption function, preparation and application Download PDFInfo
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- CN109705321A CN109705321A CN201811653095.1A CN201811653095A CN109705321A CN 109705321 A CN109705321 A CN 109705321A CN 201811653095 A CN201811653095 A CN 201811653095A CN 109705321 A CN109705321 A CN 109705321A
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Abstract
This application involves polymeric material fields, specifically disclose a kind of polyester material with oxygen absorption function, and the diol monomer and/or diacid monomer that oxidation reaction easily occurs with oxygen are contained on PEN molecule segment.The glycol of oxidation reaction is occurred the present invention for easy oxygen or diacid monomer introduces PEN molecule segment, these oxygen uptake monomers contain double bond or phenyl ring, since neighbour double strong or phenyl ring methylene can be oxidized at normal temperature under the catalysis for having transition metal, in other words, this kind of organic macromolecular copolymer just has certain oxygen absorption function.PEN itself has extraordinary passive barriering effect, this also slows down the permeating speed of oxygen on the basis of very big simultaneously.The result is that extending oxygen in the residence time of polymer amorphous region, to more improve oxygen-absorption efficiency.Film made of thus or hollow container product, for all contents to oxygen sensitive.
Description
Technical field
The present invention relates to polymeric material fields, more particularly to one kind to have excellent oxygen absorption function PEN material and its preparation
Methods and applications.
Background technique
(ethylene naphthalate) (PEN) is commercialized polyester new varieties the 1990s.With poly terephthalic acid
Equally, PEN can be processed into film, fiber, hollow container and sheet material to class plastics (PET).Due to its excellent combination property, have wide
Wealthy potential market, thus cause the concern of Polyester industry.
The structure of PEN is similar to PET, the difference is that PEN is by the bigger naphthalene nucleus of rigidity instead of benzene in strand
Ring, it is the polymer as obtained by 2,6-naphthalenedicarboxylic acid dimethyl ester and ethylene glycol polycondensation.In the molecular structure of PEN, due to naphthalene
The structure of ring be easier be in it is planar, make PEN that there is better barrier properties for gases, for example PEN is PET to the barrier property of aqueous vapor
3-4 times, the shelf-life of product is greatly improved as packaging material.The introducing of naphthalene nucleus improves the fragrance of macromolecular in molecule
Degree, so that PEN reveals more excellent heat resistance than pet sheet.The fusing point of PEN is 265 DEG C, and glass transition temperature is at 120 DEG C
More than, 50 DEG C or so are higher by than PET；Long-term use temperature is up to 160 DEG C, PEN placed in 180 DEG C of dry air 10h with
Afterwards, elongation is still able to maintain 50%.And PET will become not being available under similarity condition.In addition, the copolymer of PET/PEN
Also there is apparent effect to the hot property for improving PET.Young modulus and tensile modulus of elasticity the ratio PET of PEN is higher by 50%,
At 170 DEG C, the mechanical performance of PEN is significantly larger than PET.Since the twin nuclei of naphthalene has very strong ultraviolet absorption ability, it
The ultraviolet light that wavelength is less than 380nm can be obstructed, photostability is about 5 times of PET, the radioresistens in vacuum and O2
Ability is respectively up to 10 times of PET and 5 times.Although the ester group in PEN strand meets water decomposition, its decomposition rate is only
The 1/4 of PET, the ability of acid and alkali resistance is also superior to PET.
Since the air-tightness of PEN is good, molecular mass is relatively large, therefore at a temperature of actual use, the tendency of oligomer is precipitated
Small, the low aldehyde decomposed to give off in the case where processing temperature is higher than PET is also less than PET.Although PEN is crystallization as PET
Property material, but PEN transparent can be formed in non-crystalline state.Innocenzo of DuPont Display et al. is in SID
2003 have delivered the PEN plastic supporting base correlative study PEN that can be applicable to flexible display in the coating for adding people to have smooth effect
After layer, maximum prominent defect is not above 0.02 μm, and substrate is greater than 80% in the light transmittance of visible region, thermal stability ratio
PET is good, is highly suitable as the substrate of flexible display.But since luminous organic material is very sensitive to steam and oxygen,
To meet requirement of the Flexible Displays to substrate, 10-6g/m2/day need to be reached to the obstructing capacity of aqueous vapor, and blocking oxygen
Ability need to reach 10-3cc/m2/day.PEN individually hinder oxygen characteristic can not fully meet requirements at the higher level barrier film it is for example soft
The application of property Electronic Packaging.
By active oxygen scavenger, can be incorporated into the skeleton for constituting the basic polymer material of package wall, thus shape
At the polymer for removing oxygen.The oxygen-scavenging polymer can be used for mixing with other polymers, or as the removing in laminated vessel
Oxygen layer.The oxygen in environment can be reduced or be exhausted, at least can be used to overcome some limitations of passive barrier system.
For example, US 8,921,487 discloses the method for oxygen molecule in the clear thermoplastic article in addition to polyamides of one kind,
A kind of structural polymer with the carbon-to-carbon unsaturated bond easily to react with oxygen molecule.The terpolymer is gathered by big ring
What (alkyl-dimethyl acid diesters) oligomer, unsaturated functional polymer and epoxide function cinnamic acrylic ester oligomer formed
Polymerizate.
US 9,617,375 discloses a kind of method for removing oxygen in the thermoplastic article other than polyester, including will
Oxygen molecule reducing agent is mixed into thermoplastic compound, and reducing agent is that there is one kind carbon-to-carbon unsaturated bond easily to react with oxygen molecule
Copolymer, the polymerizate including cycloaliphatic monomer and unsaturated functional polymer.The Oxygen scavenging performance of copolymer by
It is produced after copolymer polymerization as the presence of the carbon-to-carbon unsaturated bond of the non-reacted parts of unsaturated functional polymer's reduction components
It is raw.
Since this method is that unsaturated copolymer is added directly into matrix resin to mix, although carbon-to-carbon is unsaturated double
Bond energy reacts with oxygen, it is also possible to there are two kinds of resin compatibles, it is understood that there may be the mutually separation of resin, thus shadow
Ring the absorption barrier property of oxygen.
Summary of the invention
Regarding to the issue above with deficiency, the application offer is with a kind of with the polyester material of oxygen absorption function and its preparation side
Method and application.
The object of the invention is completed first is that the diacid or diol monomer and PEN monomer that have unsaturated double-bond are copolymerized,
To contain certain proportion carbon-to-carbon double bond on the molecule segment of PEN；Simultaneously because neighbour double strong methylene are having transition golden
It can be oxidized at normal temperature under the catalysis of category, in other words, this kind of organic macromolecular copolymer just has certain oxygen uptake function
Energy.PEN itself has extraordinary passive barriering effect, this also slows down the infiltration speed of oxygen on the basis of very big simultaneously
Degree.The result is that extending oxygen in the residence time of polymer amorphous region, to more improve oxygen-absorption efficiency.
The second object of the present invention is to film or hollow container product is made with such oxygen uptake macromolecule, for all to oxygen
Sensitive content.
The present invention provides a kind of polyester material with oxygen absorption function, contains on PEN molecule segment and oxygen easily occurs with oxygen
Change the diol monomer and/or diacid monomer of reaction.
In one embodiment, the diacid monomer content that oxidation reaction easily occurs with oxygen is 2,6-naphthalenedicarboxylic acid monomer
1~10mol%；The diol monomer content that oxidation reaction easily occurs with oxygen is 1~10mol% of ethylene glycol monomers.
In one embodiment, the diol monomer and/or diacid monomer that oxidation reaction easily occurs with oxygen, containing double bond or
Phenyl ring exists simultaneously the methylene group of the neighbour double bond or phenyl ring.
In one embodiment, the diol monomer that oxidation reaction easily occurs with oxygen is selected from Isosorbide-5-Nitrae-butylene glycol, 3- hexamethylene
Alkene -1,1- dimethanol, 4- cyclohexene -1,2- dimethanol, -1,4 dimethanol of 2- cyclohexene, 1,4- benzene dimethanol, 2,6 naphthalene dimethanols
One of or more than one；The diacid monomer that oxidation reaction easily occurs with oxygen, is selected from 2- cyclohexene -1,1 oxalic acid, 2-
One of -1,4 oxalic acid of cyclohexene or more than one.
The present invention also provides a kind of preparation methods of oxygen absorption function material, use the glycol list that oxidation reaction easily occurs with oxygen
Body and/or diacid monomer complete pet reaction with PEN monomer, contain on PEN molecule segment and oxidation reaction easily occurs with oxygen
Diol monomer and/or diacid monomer.It is to be understood that the diol monomer and/or diacid monomer that oxidation reaction will easily occur with oxygen
Part PEN monomer is substituted, polycondensation reaction one is completed and generates polyester material, so that oxygen uptake monomer enters PEN molecule segment.
In one embodiment, the diol monomer that oxidation reaction easily occurs with oxygen is selected from Isosorbide-5-Nitrae-butylene glycol, 3- hexamethylene
Alkene -1,1- dimethanol, 4- cyclohexene -1,2- dimethanol, -1,4 dimethanol of 2- cyclohexene, 1,4- benzene dimethanol, 2,6 naphthalene dimethanols
One of or more than one；The diacid monomer that oxidation reaction easily occurs with oxygen, is selected from 2- cyclohexene -1,1 oxalic acid, 2-
One of -1,4 oxalic acid of cyclohexene or more than one.
The present invention also provides a kind of applications of oxygen absorption function material, using the aforementioned polyester material with oxygen absorption function, or
Person uses the oxygen absorption function material of aforementioned preparation, and film or hollow container product is made.
In one embodiment, when film or hollow container product is made, transition-metal catalyst is added.
In one embodiment, the transition-metal catalyst is cobalt salt, is selected from cobalt naphthenate, cobalt iso-octoate, cobalt acetate, 2-
It is one or more kinds of in cobalt of ethyl hexanoate, cobaltous octadecanate cobalt oleate.
In one embodiment, the content of the transition-metal catalyst is the 0.3-3% parts by weight of oxygen absorption function material.
The invention has the following beneficial effects: the glycol or diacid monomer of oxidation reaction are occurred for easy oxygen by the present invention
PEN molecule segment is introduced, these oxygen uptake monomers contain double bond or phenyl ring, since neighbour double strong or phenyl ring methylene are having transition
It can be oxidized at normal temperature under the catalysis of metal, in other words, this kind of organic macromolecular copolymer just has certain oxygen uptake
Function.PEN itself has extraordinary passive barriering effect, this also slows down the infiltration of oxygen on the basis of very big simultaneously
Speed.The result is that extending oxygen in the residence time of polymer amorphous region, to more improve oxygen-absorption efficiency.Thus make
At film or hollow container product, for all contents to oxygen sensitive.
Detailed description of the invention
Fig. 1 is the composition principle figure of PEN；
Fig. 2 is the preparation principle figure of the application one embodiment oxygen absorption function material.
Specific embodiment
Technical solution of the present invention is described in detail in the following with reference to the drawings and specific embodiments, but the implementation
The explanation of example, only a part of the embodiments of the present invention, wherein most are not limited to that.
The present invention, which provides one kind, has excellent oxygen absorption function PEN material, containing a certain proportion of easy on PEN molecule segment
The glycol or diacid monomer of oxidation reaction occur with oxygen；Such oxygen uptake high molecular material can be added when film or hollow container is made
A certain amount of transition-metal catalyst.The glycol of oxidation reaction or diacid monomer easily, which occurs, with oxygen can hereafter be referred to as oxygen uptake list
Body, present invention meaning oxygen uptake monomer includes oxygen uptake diol monomer and oxygen uptake diacid monomer.PEN is by 2,6- naphthalenedicarboxylic acid (NDA)
It is formed with ethylene glycol (EG) polycondensation, reaction equation such as Fig. 1.
Meaning PEN monomer of the invention is NDA and EG, and molecular formula is as follows:
For example, the glycol or diacid monomer that oxidation reaction easily occurs with oxygen exists simultaneously ratio containing double bond or phenyl ring
The methylene group of adjacent double bond or phenyl ring.It preferably is selected from Isosorbide-5-Nitrae-butylene glycol, 3- cyclohexene -1,1- dimethanol, 2- cyclohexene -1,1-
Oxalic acid, 4- cyclohexene -1,2- dimethanol, 2- cyclohexene-Isosorbide-5-Nitrae oxalic acid, 2- cyclohexene-Isosorbide-5-Nitrae dimethanol, Isosorbide-5-Nitrae-benzene diformazan
Alcohol, one of 2,6 naphthalene dimethanols or more than one.Oxygen uptake diacid monomer content be preferably 2,6- naphthalene dicarboxylic acid monomers 1~
10mol%；And/or oxygen uptake diol monomer content is preferably 1~10mol% of ethylene glycol monomers.Each oxygen uptake diacid monomer molecule
Formula is as follows:
Each oxygen uptake glycol monomer molecule formula is as follows:
Wherein the glycol of oxidation reaction occurs for easy oxygen or diacid monomer contains double bond or phenyl ring, exist simultaneously neighbour double bond or
The methylene group of phenyl ring.Since neighbour double strong methylene at normal temperature can be by oxygen under the catalysis for having transition metal
Change, thus a certain amount of transition-metal catalyst can be added when film or hollow container is made for oxygen uptake high molecular material；It is preferred that
Cobalt salt is as catalyst, such as cobalt naphthenate, cobalt iso-octoate, cobalt acetate, 2 ethyl hexanoic acid cobalt, cobaltous octadecanate cobalt oleate, content
The preferably 0.3-3% parts by weight of oxygen uptake PEN polymer.
Here only using Isosorbide-5-Nitrae-butylene glycol as oxygen uptake monomer for illustrate the preparation process of oxygen absorption function material, Ke Yican
See Fig. 2.Similar, oxygen uptake PEN material is prepared using oxygen uptake monomer, specific reaction principle is identical, and it is anti-to will not repeat them here it
Answer formula.
Other PEN itself have extraordinary passive barriering effect, this also slows down oxygen simultaneously on the basis of very big
The permeating speed of gas.The result is that extending oxygen in the residence time of polymer amorphous region, while passing through neighbour double bond or benzene
The fast reaction of the methylene group and oxygen of ring, to substantially increase oxygen-absorption efficiency.
Embodiment 1
PEN polymer A synthesis
1mol diacid (wherein 96 mol% of 2,6-naphthalenedicarboxylic acid, 2- ring is added in 1 liter of polymer reactor filled with nitrogen
Hexene -1,1- oxalic acid 4mol%) and 1.3mol ethylene glycol, start hot-oil jacket heating, mixture stirs under the conditions of 210 DEG C
React 2h.Then the cobalt acetate of 400ppm is added, temperature is risen to 290 DEG C and continues to stir.When temperature reaches 290 DEG C, stop
Only lead to nitrogen and start to take out low vacuum, high vacuum is transferred to after 20 minutes and continues to stir 1h.Then stop stirring, with nitrogen solution
Polyester fondant is squeezed out except vacuum, and with nitrogen, reaction terminates.Obtain the poly- PEN polymer that inherent viscosity is 0.6dl/g.
In the present embodiment, the diacid monomer that oxidation reaction easily occurs with oxygen is 2- cyclohexene -1,1- oxalic acid, be can be used
Other are substituted with its kin diacid monomer, such as 2- cyclohexene-Isosorbide-5-Nitrae oxalic acid.
Such diacid monomer content that oxidation reaction easily occurs with oxygen is 1~10 mol% of 2,6-naphthalenedicarboxylic acid monomer,
With material rate difference, reaction condition such as temperature, time and agitating mode have slight change, finally can react completely
The polyester material with oxygen absorption function is generated, the diacid monomer content that easily oxidation reaction occurs with oxygen in such is higher, and synthesis gathers
Ester material oxygen absorption rate is fast.
The preparation of PEN oxygen absorbing film
Single screw extrusion machine is added in above-mentioned 100 parts by weight PEN polyester and 1 part of cobalt acetate, 290 DEG C of meltings is heated to and squeezes
Out, it and is sent into and carries out being cooled into length of a film in slab machine, then preheat and carry out transverse and longitudinal again and stretch film forming.
Embodiment 2
The synthesis of PEN polymer B
1mol 2,6-naphthalenedicarboxylic acid and 1.5mol ethylene glycol (wherein second are added in 1 liter of polymer reactor filled with nitrogen
Glycol 95mol%, 2- cyclohexene-Isosorbide-5-Nitrae dimethanol 5mol%), starting hot-oil jacket heating, mixture stirs under the conditions of 200 DEG C
Mix reaction 2.5h.Then the cobalt acetate of 300ppm is added, temperature is risen to 280 DEG C and continues to stir.When temperature reaches 280 DEG C
When, stop logical nitrogen and start to take out low vacuum, high vacuum is transferred to after 20 minutes and continues to stir 2h.Then stop stirring, use nitrogen
Gas releases vacuum, and squeezes out polyester fondant with nitrogen, and reaction terminates.Obtain the poly- PEN polymer that inherent viscosity is 0.56dl/g.
In the present embodiment, the diol monomer that oxidation reaction easily occurs with oxygen is 4- cyclohexene -1,2- dimethanol, be can be used
Other are substituted with its kin diol monomer, such as 3- cyclohexene -1,1- dimethanol, 2- cyclohexene-Isosorbide-5-Nitrae diformazan
Alcohol.
Such diol monomer content that oxidation reaction easily occurs with oxygen is 1~10mol% of ethylene glycol monomers, with raw material
Ratio is different, and reaction condition such as temperature, time and agitating mode have slight change, and finally can react completely generation has
The polyester material of oxygen absorption function, the diol monomer content that easily oxidation reaction occurs with oxygen in such is higher, the polyester material oxygen of synthesis
Aspiration rate is fast.
The preparation of PEN oxygen absorbing film
Single screw extrusion machine is added in above-mentioned 100 parts by weight PEN polyester and 2 parts of cobalt acetates, 290 DEG C of meltings is heated to and squeezes
Out, it and is sent into and carries out being cooled into length of a film in slab machine, then preheat and carry out transverse and longitudinal again and stretch film forming.
Embodiment 3
PEN polymer C synthesis
1mol 2,6-naphthalenedicarboxylic acid and 1.5mol glycol (wherein second are added in 1 liter of polymer reactor filled with nitrogen
Glycol 92mol%, Isosorbide-5-Nitrae-butylene glycol 8mol%), starting hot-oil jacket heating, mixture is stirred to react under the conditions of 230 DEG C
2h.Then the cobalt acetate of 500ppm is added, temperature is risen to 300 DEG C and continues to stir.When temperature reaches 300 DEG C, stop logical
Nitrogen simultaneously starts to take out low vacuum, is transferred to high vacuum after twenty minutes and continues to stir 1.5h.Then stop stirring, released with nitrogen true
Sky, and polyester fondant is squeezed out with nitrogen, reaction terminates.Obtain the poly- PEN polymer that inherent viscosity is 0.62dl/g.
In the present embodiment, easily with oxygen occur oxidation reaction diol monomer be Isosorbide-5-Nitrae-butylene glycol, can be used other with
Its kin diol monomer is substituted, such as Isosorbide-5-Nitrae-benzene dimethanol, 2,6 naphthalene dimethanols.
Such diol monomer content that oxidation reaction easily occurs with oxygen is 1~10mol% of ethylene glycol monomers, with raw material
Ratio is different, and reaction condition such as temperature, time and agitating mode have slight change, and finally can react completely generation has
The polyester material of oxygen absorption function, the diol monomer content that easily oxidation reaction occurs with oxygen in such is higher, the polyester material oxygen of synthesis
Aspiration rate is fast.
The preparation of PEN oxygen absorbing film
Single screw extrusion machine is added in above-mentioned 100 parts by weight PEN polyester and 2 parts of cobalt iso-octoates, is heated to 290 DEG C of meltings
It squeezes out, and is sent into and carries out being cooled into length of a film in slab machine, then preheat and carry out transverse and longitudinal stretching film forming again.
Embodiment 4
PEN polymer D synthesis
1mol diacid (wherein 96 mol% of 2,6-naphthalenedicarboxylic acid, 2- ring is added in 1 liter of polymer reactor filled with nitrogen
Hexene -1,1- oxalic acid 4mol%) and 1.3mol glycol (wherein ethylene glycol 95mol%, Isosorbide-5-Nitrae-butylene glycol 5mol%), it opens
Dynamic hot-oil jacket heating, mixture are stirred to react 2 h under the conditions of 220 DEG C.Then the cobalt acetate of 500ppm is added, by temperature liter
To 290 DEG C and continue to stir.When temperature reaches 290 DEG C, stops logical nitrogen and start to take out low vacuum, be transferred to height after twenty minutes
Vacuum simultaneously continues to stir 2h.Then stop stirring, release vacuum with nitrogen, and squeeze out polyester fondant with nitrogen, reaction terminates.?
The poly- PEN polymer for being 0.6dl/g to inherent viscosity.
In the present embodiment, containing the diacid monomer and diol monomer that oxidation reaction easily occurs with oxygen, easily aoxidized with oxygen
The diacid monomer of reaction is 2- cyclohexene -1,1- oxalic acid, other can be used and is replaced with its kin diacid monomer
Generation, such as 2- cyclohexene-Isosorbide-5-Nitrae oxalic acid；It is Isosorbide-5-Nitrae-butylene glycol that the diol monomer of oxidation reaction easily occurs with oxygen, be can be used
Other are substituted with its kin diol monomer, such as Isosorbide-5-Nitrae-benzene dimethanol, 2,6 naphthalene dimethanols or other glycol
Monomer such as 4- cyclohexene -1,2- dimethanol, 3- cyclohexene -1,1- dimethanol, -1,4 dimethanol of 2- cyclohexene are substituted.Tool
Body alternative and additive amount can be with reference implementation example 1-3.
The preparation of PEN oxygen absorbing film
Single screw extrusion machine is added in above-mentioned 100 parts by weight PEN polyester and 1 part of cobalt iso-octoate catalyst, is heated to 290 DEG C
Melting extrusion, and be sent into and carry out being cooled into length of a film in slab machine, it then preheats and carries out transverse and longitudinal stretching film forming again.
Comparative example 1
PEN polymer E synthesis
1mol 2,6-naphthalenedicarboxylic acid and 1.3mol ethylene glycol, starting heat are added in 1 liter of polymer reactor filled with nitrogen
Oil lagging heating, mixture are stirred to react 2h under the conditions of 230 DEG C.Then the cobalt acetate of 500ppm is added, temperature is risen to
300 DEG C and continue to stir.When temperature reaches 300 DEG C, stops logical nitrogen and start to take out low vacuum, be transferred to high vacuum after twenty minutes
And continue to stir 2h.Then stop stirring, release vacuum with nitrogen, and squeeze out polyester fondant with nitrogen, reaction terminates.Obtain spy
Property viscosity be 0.65dl/g poly- PEN polymer.
The preparation of PEN oxygen absorbing film
Single screw extrusion machine is added in above-mentioned 100 parts by weight PEN polyester, is heated to 290 DEG C of melting extrusions, and be sent into slab
It carries out being cooled into length of a film in machine, then preheats and carry out transverse and longitudinal stretching film forming again.
Evaluation method:
1, moisture-vapor transmission
The film of preparation is measured using rate of perviousness analyzer (MOCON company, U.S. Aquatran model 2),
Test condition is 37.8% DEG C, 100%RH.
2, OTR oxygen transmission rate
The film of preparation is measured using oxygen transmission rate tester (Biao Ji company N500), condition is 23 DEG C, 80%
RH。
3, oxygen absorption rate is tested
The film of preparation is cut into the rectangle of 30cm*24cm, along its length doubling, four sides use sealing machine edge sealing, packet
Enclosed volume of air 300ml in pack.O2 content in bag is detected using MOCON headspace analysis instrument.
Experimental result:
The experiment results show that joined the glycol or diacid list of oxidizable reaction in embodiment 1-4 relative to comparative example 1
Body and cobalt salt catalyst, it is very excellent that the oxygen barrier property of film promotes obvious and oxygen absorben effect.
Above embodiments further illustrate the contents of the present invention, but should not be construed as limiting the invention.Without departing substantially from
In the case where spirit of that invention and essence, to modification made by the method for the present invention, step or condition and replaces, belong to the present invention
Range.Unless otherwise specified, the conventional means that technological means used in embodiment is well known to those skilled in the art.
Claims (10)
1. a kind of polyester material with oxygen absorption function, which is characterized in that contain on PEN molecule segment and easily aoxidized with oxygen
The diol monomer and/or diacid monomer of reaction.
2. the polyester material according to claim 1 with oxygen absorption function, which is characterized in that described easily to be aoxidized with oxygen
The diacid monomer content of reaction is 1~10mol% of 2,6- naphthalene dicarboxylic acid monomers；The glycol that oxidation reaction easily occurs with oxygen
Content of monomer is 1~10mol% of ethylene glycol monomers.
3. the polyester material according to claim 1 or 2 with oxygen absorption function, which is characterized in that described easily to occur with oxygen
The diol monomer and/or diacid monomer of oxidation reaction exist simultaneously the methylene of the neighbour double bond or phenyl ring containing double bond or phenyl ring
Base group.
4. the polyester material according to claim 1 or 2 with oxygen absorption function, which is characterized in that described easily to occur with oxygen
The diol monomer of oxidation reaction is selected from 1,4- butylene glycol, 3- cyclohexene -1,1- dimethanol, 4- cyclohexene -1,2- dimethanol, 2-
One of -1,4 dimethanol of cyclohexene, 1,4- benzene dimethanol, 2,6 naphthalene dimethanols or more than one；It is described that oxygen easily occurs with oxygen
Change reaction diacid monomer, selected from one of 2- cyclohexene -1,1 oxalic acid, 2- cyclohexene-Isosorbide-5-Nitrae oxalic acid or more than one.
5. a kind of preparation method of oxygen absorption function material, which is characterized in that use the diol monomer that oxidation reaction easily occurs with oxygen
And/or diacid monomer, pet reaction is completed with PEN monomer, contains on PEN molecule segment and the two of oxidation reaction easily occurs with oxygen
Alcohol monomer and/or diacid monomer.
6. preparation method according to claim 5, which is characterized in that the diol monomer that oxidation reaction easily occurs with oxygen
Selected from 1,4- butylene glycol, 3- cyclohexene -1,1- dimethanol, 4- cyclohexene -1,2- dimethanol, -1,4 dimethanol of 2- cyclohexene,
One of 1,4- benzene dimethanol, 2,6 naphthalene dimethanols or more than one；The diacid monomer that oxidation reaction easily occurs with oxygen,
Selected from one of -1,1 oxalic acid of 2- cyclohexene, -1,4 oxalic acid of 2- cyclohexene or more than one.
7. a kind of application of oxygen absorption function material, which is characterized in that use the polyester with oxygen absorption function in claim 1-4
Material, or using the oxygen absorption function material prepared in claim 5-6, film or hollow container product is made.
8. application according to claim 7, which is characterized in that when film or hollow container product is made, transition gold is added
Metal catalyst.
9. application according to claim 8, which is characterized in that the transition-metal catalyst is cobalt salt, is selected from aphthenic acids
Cobalt, cobalt iso-octoate, cobalt acetate, it is one or more kinds of in 2 ethyl hexanoic acid cobalt, cobaltous octadecanate cobalt oleate.
10. application according to claim 9, which is characterized in that the content of the transition-metal catalyst is oxygen absorption function
The 0.3-3% parts by weight of material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021143435A1 (en) * | 2020-01-16 | 2021-07-22 | 北京化工大学 | Butenediol-based polyester elastomer and preparation method |
| CN115028817A (en) * | 2022-04-26 | 2022-09-09 | 华润化学材料科技股份有限公司 | Barrier polyester material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187206A (en) * | 1995-06-07 | 1998-07-08 | 切夫里昂化学公司 | Compositions having ethylenic backbone and benzylic, allylic, or ether-containing side-chains, oxygen scavenging compositions containing the same, and polymer |
| CN1515608A (en) * | 1998-03-25 | 2004-07-28 | �з��ﰺ�����ջ�ѧ�������ι�˾ | Oxygen scavenger for reducing oxidation products of plastic film and beverage and food container |
| CN101137719A (en) * | 2005-03-08 | 2008-03-05 | 威士伯资源公司 | Oxygen scavenging polymers |
| US20080171169A1 (en) * | 2005-04-13 | 2008-07-17 | Invista North America S.A.R.L. | Oxygen Scavenging Compositions and Method of Preparation |
| CN101423601A (en) * | 2007-10-30 | 2009-05-06 | 远东纺织股份有限公司 | Polyester copolymer with oxygen inhalation and gas barrier properties and preparation method thereof |
| CN101466761A (en) * | 2006-04-12 | 2009-06-24 | 东洋制罐株式会社 | Oxygen-absorbing resin, oxygen-absorbing resin compositions and oxygen-absorbing containers |
-
2018
- 2018-12-29 CN CN201811653095.1A patent/CN109705321A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1187206A (en) * | 1995-06-07 | 1998-07-08 | 切夫里昂化学公司 | Compositions having ethylenic backbone and benzylic, allylic, or ether-containing side-chains, oxygen scavenging compositions containing the same, and polymer |
| CN1515608A (en) * | 1998-03-25 | 2004-07-28 | �з��ﰺ�����ջ�ѧ�������ι�˾ | Oxygen scavenger for reducing oxidation products of plastic film and beverage and food container |
| CN101137719A (en) * | 2005-03-08 | 2008-03-05 | 威士伯资源公司 | Oxygen scavenging polymers |
| US20080171169A1 (en) * | 2005-04-13 | 2008-07-17 | Invista North America S.A.R.L. | Oxygen Scavenging Compositions and Method of Preparation |
| CN101466761A (en) * | 2006-04-12 | 2009-06-24 | 东洋制罐株式会社 | Oxygen-absorbing resin, oxygen-absorbing resin compositions and oxygen-absorbing containers |
| CN101423601A (en) * | 2007-10-30 | 2009-05-06 | 远东纺织股份有限公司 | Polyester copolymer with oxygen inhalation and gas barrier properties and preparation method thereof |
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| WO2021143435A1 (en) * | 2020-01-16 | 2021-07-22 | 北京化工大学 | Butenediol-based polyester elastomer and preparation method |
| CN115028817A (en) * | 2022-04-26 | 2022-09-09 | 华润化学材料科技股份有限公司 | Barrier polyester material and preparation method and application thereof |
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