CN101775198A - Polyester composition with oxygen absorbing function - Google Patents

Polyester composition with oxygen absorbing function Download PDF

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Publication number
CN101775198A
CN101775198A CN200910002239A CN200910002239A CN101775198A CN 101775198 A CN101775198 A CN 101775198A CN 200910002239 A CN200910002239 A CN 200910002239A CN 200910002239 A CN200910002239 A CN 200910002239A CN 101775198 A CN101775198 A CN 101775198A
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polymer blend
absorbing function
oxygen absorbing
acid
oxygen
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CN200910002239A
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吴汝瑜
刘邦锦
李淑珍
蔡翔秦
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Far Eastern New Century Corp
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Far Eastern New Century Corp
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Abstract

The invention discloses a polyester composition with oxygen absorbing function, which contains polyester, monomer containing aldehyde group and oxidation catalyst, wherein the monomer containing aldehyde group is shown in a formula (I) in the specification, and each substituted group in the formula (I) is limited in the specification and the claim range. The polyester composition with the oxygen absorbing function can be applied and manufactured into a packing material after processing, and the packing material has good oxygen barrier property. The technology of the invention can effectively block the external oxygen from entering the inside of the packing material, and can clear the original residual oxygen in loaded objects in the packing material at the same time.

Description

Polymer blend with oxygen absorbing function
Technical field
The present invention relates to a kind of polymer blend, particularly relate to a kind of polymer blend of making wrapping material that is applicable to oxygen absorbing function.
Background technology
Foods or drinks to oxygen sensitive, as fruit juice, vegetables and fruits, food flavouring etc., be to pack, so as to the infiltration of effective blocking oxygen with glass, metal tin (for example aluminium pot, can etc.) or aluminium foil layered material " for example Tetra Pak (Tetra Pak), Kang Meibao (Combibloc) etc. " etc. with high gas-barrier characteristic in the past.But these current packaging materials all exist some shortcomings in the use, and for example vial easily breaks because of collision, add that the higher shipment and delivery cost that causes of weight rises.In addition, the aluminium foil layered material causes it to be difficult for being recovered owing to be layered material that paper, polyethylene and aluminium foil constituted, adds and can't be burying or incineration process, thereby causes many environmental issues.Though metal tin does not have foregoing problems, the price problem of higher is arranged but.Just the someone proposes for this reason, if can use mass production, low price, safety and the Plastic Packaging Materials that is easy to reclaim such as polyethylene terephthalate (PET) to replace, can effectively solve existing problem in the aforementioned prior art.
General PET material has that appearance transparence is good, chemical property stable, physical strength is high and advantage such as recyclable utilization again, has been widely used in the various wrapping material at present.It is not excessive that (with beer is example when being applied to as splendid attire the PET material to the wrapping material of the Foods or drinks of oxygen sensitive, it is for oxygen, light and thermo-responsive, the oxygen of trace infiltrates will influence mouthfeel and freshness), PET (normal PET) the oxygen obstruction ability that wrapping material showed of general non-modified is but obviously not enough, must could improve its oxygen-barrier property by means of the PET material is carried out modification.
The general method that improves the obstruct gas-permeable ability of PET material mainly can be divided into following two big classes:
(1) passive type oxygen obstruction technology (Passive barrier technology):
This technology mainly by means of the resinous blending that will possess the gas-barrier ability to the PET material, or utilize multilayer bottle injection molding technology, will sandwich this high choke material resin layer in two pet layers.In addition, also the someone proposes to utilize gas phase deposition technology coating oxidation prevention material layer on the PET substrate surface.
Utilize the blending mode realize the lift gas obstructing capacity patent can referring to No. the 5th, 102,705, United States Patent (USP) for example with the 4th, 328, No. 374.In the blending mode of these patents, example as tool oxygen-barrier property ability resin, comprise: polyvinylidene dichloride (polyvinyl dichloride, PVDC), ethylene-vinyl alcohol copolymer (ethylene vinyl alcohol, EVOH), poly-m-xylene diamine (the meta-xylylene diamine of MXD6[, MXDA) with the product of hexanodioic acid (adipic acid)] and Polyethylene Naphthalate (polyethylene naphthalate, PEN).Though the resin that possesses higher gas-barrier ability by means of blending can promote the gas barrier property of general PET, but its shortcoming is the price of the resin of existing tool oxygen obstruction ability is height more than PET, when addition is higher, except that meeting improves manufacturing cost, also be easy to generate inconsistent problem during with the PET blending, this will cause the transparency of prepared wrapping material not good, and should with the not good resin of PET consistency also be unfavorable for after the PET material recovery with utilize again.
Utilize the patent of gas phase deposition technology then can be referring to United States Patent (USP) the 6th, 919, No. 114, the 6th, 827, No. 972 etc.This technology is to form decolorizing carbon (amorphous carbon) by means of under low pressure acetylene gas being intensified with the electricity slurry, then be deposited on the inwall of PET bottle, form the thick barrier layer of about 150nm,, keep the good transparency simultaneously so as to significantly promoting the barrier properties for gases of PET bottle.But, this low tension slurry needs the long cyclical operation time because intensifying technical process, it is not suitable for the moulding product with high surface area, and this gas phase deposition technology very easily produces the uneven problem of deposit thickness, more can't be applicable on the moulding product with different shapes and moulding.
Comprehensive above-mentioned patent documentation, the passive type gas-barrier principle of wrapping material mainly is by means of chemical molecular structure in the wrapping material and/or steric barrier that arrangement constituted, make the permeation pathway of gas elongated, so as to prolonging the time that gas enters wrapping material inside.Thereby these wrapping material in use for some time, and oxygen still can slowly penetrate into wrapping material inside, causes content rotten.
(2) active oxygen absorption technology (active oxygen scavenge technology):
This technology mainly is by means of blending oxygen absorption material in the PET material, and utilizes the active reaction base of oxygen absorption material and oxygen to produce oxygenizement, thereby reaches the oxygen absorption effect of initiative.
In such prior art, once be mentioned the example that can be provided as the oxygen absorption material, comprised iron powder (Japan's special permission 12-163481 number), iron powder+promotor (as sodium-chlor or silica gel, as United States Patent (USP) the 4th, 856, No. 650 and the 4th, 992, No. 410), xitix (ascorbic acid)+metal chloride (United States Patent (USP) the 5th, 629, No. 059), MXD6+ transition metal (United States Patent (USP) the 5th, 021, No. 515, the 5th, 049, No. 624 and the 5th, 639, No. 815) or the like.But above-mentioned prior art also exists some shortcomings when using, for example the iron powder material is subject to the carbonic acid gas influence and reduces its oxygen absorbing function, also there is opaque problem to be difficult to overcome in the time of in being applied to wrapping material, and also can causes the problem on the salvage material.In addition, when adding xitix and chlorination metallo-chelate (for example: iron(ic) chloride or copper sulfate) in the high molecular polymer, can only reach the purpose of of short duration oxygen uptake, not being suitable for needs long material packing of storage life, and this material catalyst is subject to the aqueous vapor influence and reduces its activity.In addition, use MXD6 then to have the problems such as transparency reduction that cause because of the incompatible material system, and be unfavorable for that also follow-up PET reclaims.
In addition, at United States Patent (USP) the 6th, 083, No. 585 and the 6th, 863, then disclosed a kind of oxygen absorption composition (oxygen scavenging composition) that comprises polyester copolymer in No. 988, this polyester copolymer is to be got through copolymerization by polyester and polyolefine oligopolymer, it contains with the polyester is the molecule segment that the molecule segment of main chain and being used to absorbs the polyolefine oligopolymer of oxygen, and wherein this polyolefine oligopolymer is to be selected from polypropylene, poly-(4-methyl)-1-amylene, unhydrided polyhutadiene or their combination.
In addition, United States Patent (USP) the 6th, 569, disclosed a kind of method that reduces acetaldehyde concentration in the polyester packaging material in No. 479, this method mainly is by means of adding oxide catalyst, make wrapping material based on polyester after manufacturing the residual rapid oxidation of acetaldehyde form acetate, ooze out so as to avoiding acetaldehyde residual in the wrapping material.This piece patent main purpose is to reduce acetaldehyde concentration, be not to be used to absorb oxygen, though having part oxygen in the oxidising process of acetaldehyde is consumed, but because based on the wrapping material of polyester after the manufacturing in wrapping material residual acetaldehyde amount limited, and acetaldehyde is gaseous substance and can't replenishes via outer addition manner, add that this mode is to be used for consuming fast residual acetaldehyde, even so can consume oxygen in the process of oxidation of acetaldehyde reaction, it also can only provide of short duration oxygen absorption effect.The method that this shows this patent only is used to reduce acetaldehyde concentration, and can't be used for effectively promoting the oxygen uptake usefulness of wrapping material.
In above-mentioned various prior aries, all still there are some shortcomings, therefore develop a kind of wrapping material that meet Financial cost, safety and possess good oxygen uptake usefulness and still have its desirability.
Summary of the invention
The objective of the invention is in that a kind of polymer blend with oxygen absorbing function is provided, to overcome aforementioned problems of the prior art.
Another object of the present invention provides a kind of polymer blend with oxygen absorbing function, for the material of packing to oxygen sensitive.
For this reason, pointed a kind of polymer blend according to the present invention with oxygen absorbing function, it comprises (a) polyester, and it gets through the condensation polymerization reaction for glycol and dicarboxylic acid; (b) by containing the aldehyde radical monomer shown in the following formula (I); And (c) oxide catalyst:
Figure G2009100022391D0000041
In the formula (I),
R 1Alkyl, the thiazolinyl of C2～C10 or the alkoxyl group of C1～C10 of expression (1) C1～C10; (2)-C nH 2nCOH, wherein n=0～10; (3)-COR 4, R wherein 4Alkyl, the thiazolinyl of C2～C5 or the alkoxyl group of C1～C5 of expression C1～C5; Or (4)-R 5OOH, wherein R 5Expression singly-bound, the alkyl of C1～C5, the thiazolinyl of C2～C5 or the alkoxyl group of C1～C5;
X represents the alkylidene group (alkylene) of arylidene (arylene), alkyl arylene (alkylarylene) or C1～C10;
R 2Expression singly-bound, the alkylidene group of C1～C4 or the alkenylene (alkenylene) of C2～C4; And
R 3Expression hydrogen, the alkyl of C1～C10, the thiazolinyl of C2～C10 or the alkoxyl group of C1～C10, its condition is to work as R 3When being not hydrogen, R 1Be necessary for-C nH 2nCOH, wherein n=0～10.
The present invention has the polymer blend of oxygen absorbing function, be by means of containing the aldehyde radical monomer under the catalysis of oxide catalyst, make this contain the aldehyde radical monomer and oxygen carries out oxidizing reaction and change into containing acid-based compound, reach the purpose of effective consumption oxygen simultaneously, so that polymer blend of the present invention possesses oxygen absorbing function.In addition, this contains the acid-based compound that contains that is produced after aldehyde radical monomer and the oxidation thereof, no matter all close on character or chemical structure with the employed acid compound of synthesizing polyester, and good consistency is arranged with polyester, and need not additionally to add compatilizer, can not destroy original character of polyester yet, therefore can possess the original transparency of polyester and mechanical properties.The polymer blend that the present invention has oxygen absorbing function is suitable for making wrapping material, particularly is applicable to make the wrapping material that possess good oxygen obstruction characteristic.
Description of drawings
Fig. 1 is the test result thermogravimetric loss analysis figure of the polymer blend of explanation embodiment 2 according to the oxygen absorption rate of oxidative stability testing standard method;
Fig. 2 is the thermogravimetric loss analysis figure of test result of the ability to take oxygen validation test of polymer blend under normal temperature of explanation embodiment 2.
Embodiment
In the present invention, should " containing the aldehyde radical monomer " expression have the monomer of aldehyde radical, preferably this to contain the aldehyde radical monomer be to represent the monomer with aldehyde radical that is solid-state at normal temperatures and pressures, more preferably have as shown in the formula the chemical structural formula shown in (I):
Figure G2009100022391D0000051
In the formula (I), R 1Alkyl, the thiazolinyl of C2～C10 or the alkoxyl group of C1～C10 of expression (1) C1～C10; (2)-C nH 2nCOH, wherein n=0～10; (3)-COR 4, R wherein 4Alkyl, the thiazolinyl of C2～C5 or the alkoxyl group of C1～C5 of expression C1～C5; Or (4)-R 5COOH, wherein R 5Expression singly-bound, the alkyl of C1～C5, the thiazolinyl of C2～C5 or the alkoxyl group of C1～C5; More preferably R 1Alkyl or the alkoxyl group of expression (1) C1～C5, or (2)-C nH 2nCOH, wherein n=0～5;
X represents the alkylidene group of arylidene, alkyl arylene or C1～C10; More preferably X represents arylidene or alkyl arylene.This X example more specifically is 1,4-phenylene, 1,3-phenylene, methylphenylene, dimethyl phenylene, ethyl phenylene;
R 2Expression singly-bound, the alkylidene group of C1～C4 or the alkenylene of C2～C4; More preferably R 2Expression singly-bound, methylene radical, ethylidene or vinylidene; And
R 3Expression hydrogen, the alkyl of C1～C10, the thiazolinyl of C2～C10 or the alkoxyl group of C1～C10, its condition is to work as R 3When being not hydrogen, R 1Be necessary for-C nH 2nCOH, wherein n=0～10.More preferably R 3Be hydrogen.
In concrete example of the present invention, the aldehyde radical monomer that contains shown in the formula (I) is to be selected from terephthalaldehyde (terephthalic aldehyde), m-terephthal aldehyde (isophthalic aldehyde), 3-formaldehyde methyl benzoate (3-methyl formylbenzoate), 4-formaldehyde methyl benzoate (4-methyl formylbenzoate), p-met hoxycinnamic aldehyde (4-methoxy-cinnamaldehyde) or their combination.
Polyester described in the present invention is so long as general any polyester that is made into wrapping material all can be applied among the present invention not special restriction among the present invention.Specifically, this polyester general reference is carried out the product that condensation polymerization is reacted by polyvalent alcohol and polyprotonic acid.Preferred this polyvalent alcohol is a glycol.As the concrete example of glycol of the present invention, it comprises ethylene glycol, 1, ammediol, naphthalene glycol, 1,2-propylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Diethylene Glycol, Resorcinol (hydroquinone), 1,3 butylene glycol, 1,5-pentanediol, 1,6-hexylene glycol, triethylene glycol, Resorcinol or their combination, but be not limited to this.In addition, this polyprotonic acid is more preferably the ester derivative that is selected from dicarboxylic acid, dicarboxylic acid, the acyl chloride derivative of dicarboxylic acid or their combination.As the concrete example of dicarboxylic acid of the present invention, it comprises terephthalic acid, m-phthalic acid, 2,6-naphthalic acid, 2,3-resorcylic acid (2,3-dihydrobenzoic acid), 1,4-dihydroxy naphthlene formic acid, cyclohexane cyclohexanedimethanodibasic, Succinic Acid, pentanedioic acid, hexanodioic acid, sebacic acid, 1,12-dodecandioic acid, methylene-succinic acid (itaconic acid) or their combination, but be not limited to this.
For the wrapping material that make gained have mechanical properties preferably, the melting range of preferred polyester of the present invention is 190～260 ℃, more preferably 210～230 ℃.In addition, this molecular weight of polyesters is preferably 1000～60000 dalton (Dalton), and more preferably 10000～50000 dalton most preferably are 15000～30000 dalton.In concrete example of the present invention, this polyester is the product that is carried out condensation polymerization reaction gained by terephthalic acid and/or m-phthalic acid and ethylene glycol.
Aforesaid oxide catalyst, as long as it is any catalyzer that can promote aldehyde compound to carry out oxidizing reaction can be applied among the present invention, also without particular limitation at this.Specifically, oxide catalyst of the present invention is a transition metal oxidation catalyst, and wherein this transition metal comprises iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, molybdenum, manganese and platinum etc., but is not limited to this.Preferred this oxide catalyst is to be selected from Cobaltous diacetate, new cobalt decanoate, iron(ic) chloride, cobaltous chloride (cobaltous chloride), single nickel salt, the inferior cobalt of sulfuric acid, manganous sulfate, Acetyl Acetone oxygen molybdenum (molybdenyl acetylacetonate), molybdenum carbide, hexacarbonylmolybdenum (molybdenum hexacarbonyl), molybdic oxide or their combination.
In polymer blend of the present invention, this polyester, the amount ranges that contains aldehyde radical monomer and oxide catalyst can be regulated according to actual needs, and wherein the amount ranges of oxide catalyst is according to containing the monomeric amount ranges of aldehyde radical and deciding basically.Preferably, be 100 listed as parts by weight with the consumption gross weight of this polyester, this contains the monomeric amount ranges of aldehyde radical is 0.01～20 weight part, 0.5～15 weight part more preferably, 1～10 weight part more preferably again.In addition, when containing the monomeric consumption gross weight of aldehyde radical and be 100 listed as parts by weight with this, the metal consumption scope of this catalyzer is 0.005～1 weight part, 0.075～0.5 weight part more preferably, 0.01～0.1 weight part more preferably again.
The preparation method of polymer blend of the present invention, so long as can be with polyester, contain any general method that aldehyde radical monomer and oxide catalyst mix and can be applied among the present invention, this and without particular limitation, for example do to mix, melting mixing or to mix after the dissolution with solvents.Integrated survey economic benefit, operation ease and mixing uniformity serve as better in the melting mixing mode in the aforementioned manner.Specifically, when preparing polymer blend of the present invention in the melting mixing mode, can by means of with polyester, contain the aldehyde radical monomer and oxide catalyst is mixed and heated to this temperature more than melting point polyester, make mixture be fluid-like state shape (molten state), mixed easily so as to impelling it.Those skilled in the art can recognize easily via the instruction of specification sheets of the present invention, can be with polyester, contain aldehyde radical monomer and oxide catalyst and mix the back in advance and feed or feed in the forcing machine respectively, extrude and granulation after mixing through heating and melting and in the chamber of forcing machine, so as to making polymer blend of the present invention, and just can make wrapping material such as bottle easily by means of general processing technology more afterwards.
In addition, because when containing the aldehyde radical monomer and at room temperature contact oxygen with oxide catalyst, will begin to produce oxidizing reaction, therefore in order to investigate the processing convenience of polymer blend of the present invention, and make stability in storage before the wrapping material such as bottle in reprocessing, preferably the preparation method of polymer blend can be changed to makes this polymer blend comprise first pre-composition and second pre-composition, and this polyester is divided into first part and second section, this first pre-composition contains the polyester of this first part and this contains the aldehyde radical monomer, and this second pre-composition contains polyester and this oxide catalyst of this second section.Aforementioned two kinds of pre-compositions are molten mixture more preferably, more preferably through further granulation, for example via the product of forcing machine extruding pelletization.When planning to make wrapping material, directly this first pre-composition is mixed with this second pre-composition that the back feeds or direct respectively feeding forcing machine in extruding pelletization, at last according to the in addition moulding of the required outward appearance kenel of subsequent applications.
In addition, if it is more even to plan that polymer blend is mixed, those skilled in the art can understand the technology that the present invention discloses via the instruction of specification sheets of the present invention also can be by means of the polymer blend that contains aldehyde radical monomer and oxide catalyst of preparing higher concentration in advance, add more this polyester afterwards again and be diluted to required concentration, more even so as to it is mixed.In like manner, the content ratio of this first pre-composition and this second pre-composition can be adjusted to high-content concentration according to process requirements in advance, and redilution is to desired concn afterwards.
Because the present invention contains the acid-based compound that contains that is produced after aldehyde radical monomer and the oxidation thereof, no matter all close on character or chemical structure with the employed acid compound of synthetic resins, so good consistency is arranged with polyester, this makes the polymer blend with oxygen absorbing function of the present invention to make the wrapping material that have high transparent and meet the mechanical properties of industry demand easily need not additionally to add under the compatilizer.In addition, the made wrapping material of polymer blend that the present invention has the oxygen absorbing function absorption usefulness that under room temperature environment, just can produce oxygen, can effectively stop the oxygen of wrapping material outside to enter its inside, and its time limit of keeping absorption oxygen ability can be regulated and control by means of containing the monomeric addition of aldehyde radical easily, and then can obtain the oxygen uptake lifetime that reaches the several months.As the specific examples of wrapping material of the present invention, be not limited to sealing bag, seal box (as crisper), beverage bottle (as juice bottle, Beer Bottle) but comprise ... etc.
The present invention will be described further with regard to following examples, but will be appreciated that, these embodiment are the purposes in order to illustrate just, and should not be interpreted as implementing restriction of the present invention.
Embodiment
Embodiment 1
Utilize the twin-screw mixer extrusion equipment (by the manufacturing of the great illuminate machinery in Taiwan company limited, model is the two-way twin screw extruder of PSM50, screw rod L/D=36), with (the Far East weaving of 20kg PET ester grain, model C B607), the 2kg terephthalaldehyde mixes the back adding with 1.2g Cobaltous diacetate (amount of cobalt accounts for the 24.9wt% of Cobaltous diacetate gross weight), and feed nitrogen (gas flow rate is 60mL/min) at the opening for feed place of screw rod simultaneously, screw speed is controlled to be 180rpm, and the temperature of the zone heating warm area of this equipment is controlled at 160～240 ℃.Extruding pelletization after the melting mixing in forcing machine just can make the ester grain (with the polyester total amount is 100 listed as parts by weight, and terephthaldehyde's aldehyde is 10 weight parts) that the present invention has the polymer blend of oxygen absorbing function whereby.
Embodiment 2
Technology of preparing with reference to general PET resin is pre-mixed terephthalic acid and m-phthalic acid according to part by weight at 9: 1, obtains the dicarboxylic acid mixture.Then make the ethylene glycol of this dicarboxylic acid mixture and 1.25 times of weight carry out the esterification condensation reaction again, the reaction final temp is 285 ℃, and then obtains to make by oneself polyester ester grain through extruding pelletizing.Utilize difference formula scanning calorimeter (DSC, by the manufacturing of U.S. TA Instrument company, model is DSC module 2910), detect this polyester ester grain, can learn that the fusing point of this polyester ester grain is about 223 ℃ with reference to its operational manual.
Utilize the twin-screw mixer extrusion equipment (by the manufacturing of the great illuminate machinery in Taiwan company limited, model is the two-way twin screw extruder of PSM50, screw rod L/D=36), the self-control polyester ester grain of aforementioned gained and the feeding rate of terephthalaldehyde are controlled at 40Kg/hr and 2Kg/hr respectively, feed nitrogen (gas flow rate is 60mL/min) simultaneously at screw feed mouth place, screw speed is controlled to be 180rpm, and the temperature of the zone heating warm area of this equipment is controlled at 160～240 ℃, make terephthalaldehyde carry out heat fusing and mix, to make first pre-composition with self-control polyester ester grain.
Be pre-mixed terephthalic acid and m-phthalic acid at 9: 1 according to part by weight, obtain the dicarboxylic acid mixture.Then make the ethylene glycol of this dicarboxylic acid mixture and 1.25 times of weight carry out the esterification condensation reaction again, and in the esterification condensation reaction process, add the oxide catalyst (Cobaltous diacetate) of 5000ppm, the reaction final temp is 285 ℃, and then obtains second pre-composition through extruding pelletizing.
Utilize the twin-screw mixer extrusion equipment, feed nitrogen (gas flow rate is 60mL/min) at screw feed mouth place, screw speed is controlled to be 200rpm, and the temperature of the zone heating warm area of this equipment is controlled at 160～210 ℃, again according to adding part by weight 9: 1, make first pre-composition and second pre-composition carry out heat fusing and mix, at last extruding pelletization again through solid-state polymerization, to make polymer blend (with the polyester total amount is 100 listed as parts by weight, and terephthaldehyde's aldehyde is 3 weight parts).
Embodiment 3
Step By Condition is with embodiment 2, but terephthalaldehyde changes m-terephthal aldehyde into, and compound concentration is for being 100 listed as parts by weight with the polyester total amount, and m-terephthal aldehyde content is 3 weight parts.
Embodiment 4
Step By Condition is with embodiment 2, but terephthalaldehyde changes p-met hoxycinnamic aldehyde into, and compound concentration is for being 100 listed as parts by weight with the polyester total amount, and p-met hoxycinnamic aldehyde content is 3 weight parts.
Embodiment 5
Step By Condition is with embodiment 2, but terephthalaldehyde changes 4-formaldehyde methyl benzoate into, and compound concentration is for being 100 listed as parts by weight with the polyester total amount, and 4-formaldehyde methyl benzoate content is 3 weight parts.
Test 1
For recording the oxygen uptake effect of polymer blend of the present invention between longer-term within a short period of time, carry out accelerated tests at this according to oxidative stability testing standard method ASTM D168, with embodiment 2 prepared polymer blends, (U.S. TA Instrument company makes to utilize thermal gravimetric analyzer, model is TGA2950), under mixed gas (nitrogen/dehumidified air) environment and gas flow rate 100mL/min, get the polymer blend of 40 milligrams embodiment 2, follow heating steps to be warming up to 80 ℃ by 30 ℃ of temperature rise rates with 2 ℃/min of temperature rise rate, and in 80 ℃ of constant temperature 120 minutes, observe the weight increase and decrease of this polymer blend again, end-result as shown in Figure 1.
Show that by analyzing the gained result among Fig. 1 the weight of polymer blend 100% increases to 102% when starting weight, weight distribution curve presents the trend that increases gradually.This is that the Sauerstoffatom number in this process in the compound molecule increases, and causes overall weight also can increase owing to can form acid compound behind polymer blend of the present invention and the oxygen reaction, so can confirm that polymer blend of the present invention can bring into play oxygen uptake usefulness.
Test 2
According to oxidation induction time standard method ASTM D3895, with embodiment 2 prepared polymer blends, utilize thermal gravimetric analyzer (model is TGA2950), under mixed gas (nitrogen/dehumidified air) environment and gas flow rate 100mL/min, and there be not (room temperature) under the situation of heat temperature raising, observe the weight increase and decrease that the polymer blend oxygen uptake forms oxide compound, with the oxygen uptake effect of checking polymer blend of the present invention under normal temperature environment.Gained the results are shown in Fig. 2.
Learn by gained result among Fig. 2, after 26 ℃ of air ambients of normal temperature continue to observe 50 minutes, (the Far East weaving of the control group of polymer blend of the present invention and commercially available unmodified PET, model C B607) begins to occur obvious changes in weight difference, the oxygen uptake reaction because take place in thing of the present invention, weight begins to increase, and the weight of contrast is then kept constant (not having any reaction takes place).Show that polymer blend of the present invention can carry out oxygen absorption reaction (weight increase) really.Confirm further that thus polymer blend of the present invention has oxygen absorption usefulness really.
Test 3
With embodiment 2～5 prepared polymer blends, respectively at carrying out the oxygen absorbed test under the normal temperature.In addition with commercially available unmodified PET resin (Far East weaving, model C B607) control group in contrast.
Utilize industrial trace oxygen supervisory system commonly used (to make by Japanese Iishima Electronic Industry Co., Ltd., model is MC-8G), respectively with the polymer blend of 10g embodiment 2～5, place the airtight sampling groove of trace oxygen supervisory system, be full of the oxygen concentration (oxygen concentration is 20.9% in the air, 26 ℃ of temperature, ambient relative humidity 60%RH) of fixed concentration in the sampling groove, then note down the oxygen concentration in the sampling groove, test result is as shown in table 1.
Table 1
Figure G2009100022391D0000111
In table 1, with the result of embodiment 2, after 120 days, the oxygen concentration in the sampling groove drops to 6.39% by 20.9%, and oxygen is consumed amplitude and reaches 69%, proves that the polymer blend of embodiment 2 can effectively be kept 120 days or above ability to take oxygen.By the result of embodiment 3～5, after 120 days, the oxygen concentration in the sampling groove also drops to 7.5%, 15.0% and 11.9% respectively by 20.9%, proves that equally also the polymer blend of embodiment 3～5 had 120 days or above ability to take oxygen.Provable by above result, the polymer blend that the present invention has oxygen absorbing function has good oxygen absorbing function really, and can keep 120 days or above oxygen uptake usefulness.
Test 4
With embodiment 1～5 prepared polymer blend, according to general bottle embryo injecting method, carry out a bottle embryo injection respectively with bottle embryo forming machine (Husky company, model Hypet90).
Then, the bottle embryo of injection according to general blow moulding, is carried out twin screw with bottle blowing machine (good bright machinery) and prolongs inferior blowfilm shaping.
The result shows that polymer blend of the present invention can be made bottle by means of prior art easily, and its outward appearance and unmodified PET are prepared as broad as long.
Test 5
Get the polymer blend of embodiment 2, prepared moulding product of 4 methods (bottle) after tested, (Haze meter, NIPPON DENSHOKU company, model NDH-2000) detects its haze change with the mist degree determinator.In addition make molding and organize in contrast to test 4 equally with commercially available unmodified PET resin (Far East weaving, model C B607).Test result is as shown in table 2 below.
Table 2
Figure G2009100022391D0000121
By mist degree test number in the table 2 as can be known, polymer blend of the present invention still has the excellent transparency after being processed into molding, and through 120 days deposit (oxygen uptake) after, still have the good transparency (haze value＜5%).
In sum, the present invention has the polymer blend of oxygen absorbing function, because of interpolation contains aldehyde radical monomer and oxide catalyst, and can obtain good oxygen absorbing function, and can keep long-time good oxygen uptake usefulness.The follow-up prepared wrapping material of polymer blend of the present invention also possess the good transparency and mechanical properties, meet the required wrapping material specification of industry fully, and prepared wrapping material are suitable for packing the material (as beer, fruit juice etc.) to oxygen sensitive very much.
The above is the preferred embodiments of the present invention; it should not be used to limit practical range of the present invention; that is to say that the simple equivalent of doing according to claim of the present invention and description changes and modifies, all belong in the protection domain that the present invention contains.

Claims (14)

1. polymer blend with oxygen absorbing function is characterized in that it comprises:
(a) polyester, it gets through the condensation polymerization reaction for glycol and dicarboxylic acid;
(b) by containing shown in the following formula (I)
Figure F2009100022391C0000011
In the formula (I),
R 1Alkyl, the thiazolinyl of C2～C10 or the alkoxyl group of C1～C10 of expression (1) C1～C10; (2)-C nH 2nCOH, wherein n=0～10; (3)-COR 4, R wherein 4Alkyl, the thiazolinyl of C2～C5 or the alkoxyl group of C1～C5 of expression C1～C5; Or (4)-R 5-COOH, wherein R 5Expression singly-bound, the alkyl of C1～C5, the thiazolinyl of C2～C5 or the alkoxyl group of C1～C5;
X represents the alkylidene group of arylidene, alkyl arylene or C1～C10;
R 2Expression singly-bound, the alkylidene group of C1～C4 or the alkenylene of C2～C4; And
R 3Expression hydrogen, the alkyl of C1～C10, the thiazolinyl of C2～C10 or the alkoxyl group of C1～C10, its condition is to work as R 3When being not hydrogen, R 1Be necessary for-C nH 2nCOH, wherein n=0～10; And
(c) oxide catalyst.
2. the polymer blend with oxygen absorbing function as claimed in claim 1 is characterized in that: the X of this formula (I) represents arylidene or alkyl arylene.
3. the polymer blend with oxygen absorbing function as claimed in claim 2 is characterized in that: the X of this formula (I) represents 1,4-phenylene, 1,3-phenylene, methylphenylene, dimethyl phenylene or ethyl phenylene.
4. the polymer blend with oxygen absorbing function as claimed in claim 1 is characterized in that: the R of this formula (I) 1The alkyl of expression (1)-C1～C5 or the alkoxyl group of C1～C5, or (2)-C nH 2nCOH, wherein n=0～5.
5. the polymer blend with oxygen absorbing function as claimed in claim 1 is characterized in that: the R of this formula (I) 2Expression singly-bound, methylene radical, ethylidene or vinylidene.
6. the polymer blend with oxygen absorbing function as claimed in claim 1 is characterized in that: the R of this formula (I) 3Expression hydrogen.
7. the polymer blend with oxygen absorbing function as claimed in claim 1 is characterized in that: the melting range of this polyester is 190 ℃～260 ℃.
8. the polymer blend with oxygen absorbing function as claimed in claim 1, it is characterized in that: this dicarboxylic acid is selected from terephthalic acid, m-phthalic acid, 2,6-naphthalic acid, 2,3-resorcylic acid, 1,4-dihydroxy naphthlene formic acid, cyclohexane cyclohexanedimethanodibasic, Succinic Acid, pentanedioic acid, hexanodioic acid, sebacic acid, 1,12-dodecandioic acid, methylene-succinic acid or their combination.
9. the polymer blend with oxygen absorbing function as claimed in claim 1, it is characterized in that: this glycol is selected from ethylene glycol, 1, ammediol, naphthalene glycol, 1,2-propylene glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, Diethylene Glycol, Resorcinol, 1,3-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, triethylene glycol, Resorcinol or their combination.
10. the polymer blend with oxygen absorbing function as claimed in claim 1 is characterized in that: this oxide catalyst is a transition metal oxidation catalyst.
11. the polymer blend with oxygen absorbing function as claimed in claim 1 is characterized in that: the consumption gross weight with this polyester is 100 listed as parts by weight, and this contains the monomeric amount ranges of aldehyde radical is 0.01～20 weight part.
12. the polymer blend with oxygen absorbing function as claimed in claim 11 is characterized in that: containing the monomeric consumption gross weight of aldehyde radical with this is 100 listed as parts by weight, and the metal consumption scope of this catalyzer is 0.005～1 weight part.
13. wrapping material is characterized in that: it is obtained by the polymer blend with oxygen absorbing function as claimed in claim 1.
14. wrapping material as claimed in claim 13 is characterized in that: these wrapping material are Beer Bottle.
CN200910002239A 2009-01-13 2009-01-13 Polyester composition with oxygen absorbing function Pending CN101775198A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102382429A (en) * 2011-10-24 2012-03-21 广州市信联智通实业有限公司 Polyethylene terephthalate barrier composite material and preparation technology of same
WO2015135244A1 (en) * 2014-03-12 2015-09-17 北京崇高纳米科技有限公司 Material composition for producing beer bottle and method of producing beer bottle
CN106046648A (en) * 2016-05-30 2016-10-26 南京禾宇化工有限公司 Corrosion-resistant and high-temperature-resistant resin and preparing method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102382429A (en) * 2011-10-24 2012-03-21 广州市信联智通实业有限公司 Polyethylene terephthalate barrier composite material and preparation technology of same
CN102382429B (en) * 2011-10-24 2013-11-06 广州信联智通实业股份有限公司 Polyethylene terephthalate barrier composite material and preparation technology of same
WO2015135244A1 (en) * 2014-03-12 2015-09-17 北京崇高纳米科技有限公司 Material composition for producing beer bottle and method of producing beer bottle
CN106046648A (en) * 2016-05-30 2016-10-26 南京禾宇化工有限公司 Corrosion-resistant and high-temperature-resistant resin and preparing method thereof

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