CN1824703A - Manufacturing method of high baffer modified polyester - Google Patents
Manufacturing method of high baffer modified polyester Download PDFInfo
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- CN1824703A CN1824703A CN 200510024022 CN200510024022A CN1824703A CN 1824703 A CN1824703 A CN 1824703A CN 200510024022 CN200510024022 CN 200510024022 CN 200510024022 A CN200510024022 A CN 200510024022A CN 1824703 A CN1824703 A CN 1824703A
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Abstract
The present invention relates to a method for preparing high-barrier modified polyester resin. Said method includes the following processes: (1), uniformly mixing polyethylene glycol terephthatate resin PET, polyethylene naphthalate resin PEN, dihydrogen-like oxazole compound and antioxidant according to the following proportion: PET:PEN=100:(5-30); PET:dihydrogen-like oxazole compound=100:(0.01-8); PET:antioxidant=100:(0.1-8), said invention also provides the structure formula of said dihydrogen-like oxazole; and (2), making the above-mentioned mixture undergo the processes of melting extrusion and granulating by using screw extruding machine, its melting temperature is 265-300deg.C and screw rotating speed is 15-80rpm.
Description
Technical field
The present invention relates to a kind of manufacture method of high baffer modified polyester resin, particularly adopt the method for PEN resin by melt blending in addition modification of pet resin, to improve its barrier property to gas.
Background technology
Pet resin (hereinafter to be referred as PET) is a kind of crystalline thermoplastic resin, make the synthon except that being used as, also be widely used in making wrapping material such as bottle type container and film, and the application quantity growth in the wrapping material field is exceedingly fast in recent years.But there is a very big defective in PET as wrapping material, be that it is relatively poor to the stronger material barrier of various perviousness such as gas, grease, in the application scenario that barrier is had particular requirement, the wrapping material made from general PET just can't satisfy service requirements.
In the prior art, in order to remedy the relatively poor defective of general PET wrapping material barrier, the way of mainly taking has:
1) MULTILAYER COMPOSITE: when the PET wrapping material are made, when making, wall of container is made three layers or multilayered structure, make to have a kind of intermediate barrier layer that forms by the better macromolecular material of barrier property in the pet layer at interval as containers such as PET bottles.The better macromolecular material of barrier property mainly contains nylon 6, EVOH (ethylene/vinyl alcohol copolymer), LCP (liquid crystalline polymers) etc.But because the material manufacturing process complexity of multilayer mechanism, cost is higher.This in addition technology also is not suitable for the PET film of making high barrier.
2) surface-coated: adopt silicon oxide, carbon etc. some for the lower coated materials of material adsorptive poweies such as gas and grease in common PET package material surface as barrier layer, by reducing these materials improve material at the solubility coefficient of material surface barrier property.But the surface-coated method is owing to can cause transparency to descend behind other material of spraying on the PET material, and the occasion of its application is also very limited.
3) blending and modifying: adopt the polymkeric substance of high obstructing performance and PET to make a kind of PET of modification by melt blending usually, this modified PET has reduced the spread coefficient in material body when reducing the solubility coefficients of material at material surface such as gas and grease, improved the barrier property of material from two aspects.
Comprehensively, blending and modifying is to improve comparatively ideal method of PET barrier property, and its manufacturing process is fairly simple, and is very little to the physicals influence of PET material others, the material of making can be used for making various wrapping material, and finished product also are easy to reclaim.
In the prior art, be used for the high barrier polymkeric substance of modification proper be PEN resin (hereinafter to be referred as PEN).It is usually by 2,6-naphthalic acid or 2, and 6-naphthalene diformic acid dimethyl ester and ethylene glycol polycondensation form.Compare with PET, because the polyester molecule chain has replaced phenyl ring by the bigger naphthalene nucleus of rigidity, make it have unique physicals, show that especially its barrier property is very excellent, and with other most of barrier properties preferably superpolymer compare, PEN and PET have better consistency.
But there is a defective in the melt blending modified PET of existing P ET/PEN, and promptly as will reach enough barriering effects, the consumption of PEN is very high, and the ratio of mixture that requires both usually is PET: PEN=100: 70, or to require the amount of PEN at least be 0.5 times of PET.Because the price of PEN will be far above PET, this has caused the manufacturing cost of this high baffer modified PET very high.
Summary of the invention
The invention provides a kind of manufacture method of high baffer modified polyester, it adopts PET and PEN to make by the method for melt blending, technical problem to be solved is to reduce the consumption of PEN, but can obtain excellent barrier property equally, thereby overcomes the defective that prior art exists.
Below be the technical scheme that the present invention solves the problems of the technologies described above:
A kind of manufacture method of high baffer modified polyester resin, this method comprises following process:
1) pet resin PET, PEN resin PEN, dihydro class oxazoline compound and oxidation inhibitor is even by following mixed:
PET∶PEN＝100∶(5～30)；
PET: dihydro class oxazoline compound=100: (0.01～8);
PET: oxidation inhibitor=100: (0.1～8),
The limiting viscosity of above-mentioned PET [η] is 0.6～0.8dl/g; The limiting viscosity of PEN [η] is 0.4～0.7dl/g; Dihydro class oxazoline compound has structural formula:
R is the alkyl or phenyl of C1～C6 in the formula; Oxidation inhibitor is the mixture of polynary resistance phenol oxidation inhibitor and phosphite antioxidant, wherein polynary resistance phenol oxidation inhibitor: phosphite antioxidant=1: 1～10,
2) said mixture melt extrudes granulation with screw extrusion press, and melt processing temperature is 265～300 ℃, and screw speed is 15～80 rev/mins, and the residence time of mixture in screw extrusion press is 75～400 seconds.
Above-mentioned polynary resistance phenol oxidation inhibitor generally can be to take from four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] defend tetrol ester, 3-(3 season, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, it is two that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] triethyleneglycol ester or β-(3, the 5-di-tert-butyl-hydroxy phenyl) a kind of in propionic acid ten caprylates, but be preferably four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] and defend the tetrol ester season; Phosphite antioxidant can be to take from three (2, the 4-di-tert-butyl-phenyl) a kind of in phosphorous acid ester, diisooctyl phenyl phosphite, alkyl alcohol pentaerythritol phosphite or three (nonyl phenyl) phosphorous acid ester, but be preferably three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
The adding of oxidation inhibitor is known by the present technique field in the prior art, and the present invention also there is no special requirement to the selection of oxidation inhibitor, and the proportioning of its consumption and two kinds of oxidation inhibitor is also basic identical with prior art.
Said process 1 described PET: PEN is preferably 100: (8～18); PET: dihydro class oxazoline compound is preferably 100: (0.5～5); PET: oxidation inhibitor is preferably 100: (0.5～5).
2 residence time of described mixture in screw extrusion press of said process are preferably 100～200 seconds.
Two kinds of superpolymer make a kind of high molecule alloy material by melt blending, and both consistencies are crucial.Following reaction can take place in PET and PEN in the course of processing of melt blending:
PET and PEN have generated product (I) after transesterification reaction, product (I) all has good consistency to PET and PEN, and why the melt blending of PET and PEN has good consistency, and the existence of product (I) is one of important reasons very.Content yet the contriver finds product (I) too much is not to be the part good thing, and this can make the almost whole external phase that becomes a kind of PET-PEN of PET and PEN, and has only pure PEN external phase just can offer the material good barrier performance in fact.Certainly, if exist too much in the material PET and PEN separately independently disperse phase the physicals of material is descended.The contriver found through experiments, and optimal state is that PET is external phase, and PEN is disperse phase, and like this, material can rely on the external phase of PET to obtain due physicals; And pure particulate state PEN disperse phase forms thin layer owing to material drawn in the manufacturing processed of finished product, and the PEN thin layer of intersecting can make material obtain good barrier performance in this PET of the being scattered in external phase.Because PET is an external phase in the material, PEN is a disperse phase, so the consumption of PEN obviously can significantly reduce.
Technical scheme provided by the invention forms according to above discovery, and wherein most important key problem in technology is to have added dihydro class oxazoline compound in the process of PET and PEN melt blending, and it will following reaction take place with PET and PEN:
And:
Because the molecular volume of dihydro class oxazole is less, contact than the end of the chain that is easier to and twine mutually, therefore the occurrence probability of above-mentioned reaction is greater than the reaction that takes place between PEN and the PET.By the add-on of control dihydro class oxazole and the processing condition of melt blending, so the technical program has been controlled at the content of above-mentioned product (I) in the suitable scope.The contriver finds by test, the PET/PEN melt blending modified PET that obtains like this, and PET presents external phase, and PEN presents uniform disperse phase.And find that by a series of follow-up test this modified PET is made film by stretching or made container such as PET bottle, its barrier property is very good.
Compared with prior art, advantage of the present invention is the consumption that can significantly reduce PEN, usually PET: PEN can be below 100: 30, and the PET/PEN melt blending modified PET that obtains can obtain good barrier property equally, and other physicals is also very good.
Below will the invention will be further described by specific embodiment, the testing method of each index is as described below in an embodiment.
Tensile strength, tensile modulus, elongation at break, flexural strength and modulus in flexure:
The Z010 type universal electrical puller system that uses German Zwick company to produce press the GB1040-79 regulation and is tested.
The barrier property test:
Utilize two-way stretch to become the testing film sample, adopt the oxygen flow tester of MOCON company that the barrier of barrier material is tested, testing standard is ASTM D-3985-1988.This testing method mainly is by measure film under unit surface, unit time, the oxygen volume that passes through under the condition of determining air pressure.
Embodiment
Because the present invention is basic identical to selecting for use with prior art of oxidation inhibitor, this is that those skilled in the art is known, thus embodiment this is not done too much for example, but this does not mean limitation of the scope of the invention.
[embodiment 1～10]
It is even that PET, PEN, dihydro class oxazoline compound and oxidation inhibitor are pressed the described mixed of table 1, and wherein dihydro class oxazoline compound has structural formula:
It is 2 listed that the concrete dihydro class oxazoline compound that uses of each embodiment sees Table, and oxidation inhibitor is the mixture that four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] defend tetrol ester and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester season.
The limiting viscosity of PET is [η] 0.6～0.8dl/g; The limiting viscosity of PEN [η] is 0.4～0.7dl/g.
Said mixture melt extrudes granulation with screw extrusion press, and concrete melt processing temperature, screw speed, the residence time of mixture in screw extrusion press of adopting of each embodiment sees Table 2 listed.
The PET/PEN melt blending modified PET product that makes carries out performance test, the results are shown in Table 3.
[comparative example 1～4]
Do not add dihydro class oxazoline compound when PET and PEN melt blending, all the other are with embodiment 1～10, and relevant data are with listing in table 1～table 3.
Table 1.
| PEN | Dihydro class oxazole | Oxidation inhibitor | A∶B | |
| Embodiment 1 | 5 | 0.5 | 0.1 | 1∶2 |
| Embodiment 2 | 8 | 0.01 | 0.5 | 1∶8 |
| Embodiment 3 | 8 | 3 | 1 | 1∶4 |
| Embodiment 4 | 8 | 1 | 1 | 1∶4 |
| Embodiment 5 | 12 | 3 | 3 | 1∶3 |
| Embodiment 6 | 15 | 3 | 3 | 1∶6 |
| Embodiment 7 | 18 | 5 | 5 | 1∶2 |
| Embodiment 8 | 24 | 5 | 3 | 1∶4 |
| Embodiment 9 | 24 | 8 | 5 | 1∶5 |
| Embodiment 10 | 30 | 8 | 8 | 1∶1 |
| Comparative example 1 | 8 | - | 1 | 1∶4 |
| Comparative example 2 | 12 | - | 3 | 1∶3 |
| Comparative example 3 | 18 | - | 5 | 1∶2 |
| Comparative example 4 | 24 | - | 5 | 1∶4 |
Data in the table are except that A: B is both weight ratios of A, B, and being with PET is 100 weight ratio.Defend the tetrol ester season and A is four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid], B is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
Table 2.
Table 3.
| Tensile strength (MPa) | Tensile modulus (MPa) | Extension at break (%) | Flexural strength (MPa) | Modulus in flexure (MPa) | Barrier (cm 3/m 2 ·d·bar) | |
| Embodiment 1 | 2741.72 | 69.715 | 3.08 | 1478.82 | 33.09 | 60.5 |
| Embodiment 2 | 2573.85 | 50.488 | 2.188 | 1439.32 | 32.45 | 53.7 |
| Embodiment 3 | 2633.87 | 64.124 | 2.962 | 1421.80 | 30.81 | 51.2 |
| Embodiment 4 | 2650.65 | 63.874 | 3.402 | 1428.26 | 31.04 | 42.3 |
| Embodiment 5 | 2608.94 | 59.326 | 2.916 | 1377.67 | 28.51 | 41.1 |
| Embodiment 6 | 2583.42 | 55.532 | 2.498 | 1346.48 | 29.13 | 40.5 |
| Embodiment 7 | 2602.43 | 63.600 | 3.075 | 1352.28 | 28.06 | 40.2 |
| Embodiment 8 | 2521.53 | 42.4 | 1.818 | 1354.50 | 28.50 | 40.0 |
| Embodiment 9 | 2458.26 | 63.736 | 3.128 | 1300.40 | 29.17 | 39.9 |
| Embodiment 10 | 2483.41 | 65.532 | 2.498 | 1246.48 | 29.13 | 39.6 |
| Comparative example 1 | 2512.37 | 52.171 | 2.187 | 1354.504 | 31.502 | 60.7 |
| Comparative example 2 | 2497.74 | 50.759 | 1.863 | 1300.402 | 29.17 | 58.4 |
| Comparative example 3 | 2507.33 | 51.296 | 1.908 | 1251.188 | 28.784 | 56.9 |
| Comparative example 4 | 2532.76 | 55.043 | 1.914 | 1321.802 | 30.806 | 55.0 |
Claims (9)
1, a kind of manufacture method of high baffer modified polyester resin, this method comprises following process:
1) pet resin PET, PEN resin PEN, dihydro class oxazoline compound and oxidation inhibitor is even by following mixed:
PET∶PEN＝100∶(5～30)；
PET: dihydro class oxazoline compound=100: (0.01～8);
PET: oxidation inhibitor=100: (0.1～8),
The limiting viscosity of above-mentioned PET is [η] 0.6～0.8dl/g; The limiting viscosity of PEN [η] is 0.4～0.7dl/g; Dihydro class oxazoline compound has structural formula:
R is the alkyl or phenyl of C1～C6 in the formula; Oxidation inhibitor is the mixture of polynary resistance phenol oxidation inhibitor and phosphite antioxidant, wherein polynary resistance phenol oxidation inhibitor: phosphite antioxidant=1: 1～10,
2) said mixture melt extrudes granulation with screw extrusion press, and melt processing temperature is 265～300 ℃, and screw speed is 15～80 rev/mins, and the residence time of mixture in screw extrusion press is 75～400 seconds.
2, the manufacture method of high baffer modified polyester according to claim 1, it is characterized in that described polynary resistance phenol oxidation inhibitor takes from four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] defend tetrol ester, 3-(3 season, the 5-di-tert-butyl-hydroxy phenyl) methyl propionate, it is two that [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] a kind of in triethyleneglycol ester or β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid ten caprylates.
3, the manufacture method of high baffer modified polyester according to claim 1, it is characterized in that described phosphite antioxidant takes from a kind of in three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, diisooctyl phenyl phosphite, alkyl alcohol pentaerythritol phosphite or three (nonyl phenyl) phosphorous acid ester.
4, the manufacture method of high baffer modified polyester according to claim 1 is characterized in that process 1 described PET: PEN=100: (8～18).
5, the manufacture method of high baffer modified polyester according to claim 1 is characterized in that process 1 described PET: dihydro class oxazoline compound=100: (0.5～5).
6, the manufacture method of high baffer modified polyester according to claim 1 is characterized in that process 1 described PET: oxidation inhibitor=100: (0.5～5).
7, the manufacture method of high baffer modified polyester according to claim 1 is characterized in that 2 residence time of described mixture in screw extrusion press of process are 100～200 seconds.
8, the manufacture method of high baffer modified polyester according to claim 2 is characterized in that described polynary resistance phenol oxidation inhibitor is that four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] defend the tetrol ester season.
9, the manufacture method of high baffer modified polyester according to claim 3 is characterized in that described phosphite antioxidant is three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
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| CNB2005100240222A CN100460457C (en) | 2005-02-23 | 2005-02-23 | Manufacturing method of high baffer modified polyester |
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| CNB2005100240222A CN100460457C (en) | 2005-02-23 | 2005-02-23 | Manufacturing method of high baffer modified polyester |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504501A (en) * | 2011-11-09 | 2012-06-20 | 华润包装材料有限公司 | High-barrier polyester composite material and preparation method thereof |
| CN102875980A (en) * | 2012-09-29 | 2013-01-16 | 四川东方绝缘材料股份有限公司 | Preparation method of heat-resistant oxygen-resistant polyester film |
| CN114031840A (en) * | 2021-12-01 | 2022-02-11 | 江苏弘奇金属科技有限公司 | High-temperature-resistant anti-puncture winding film and production process thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6767951B2 (en) * | 2001-11-13 | 2004-07-27 | Eastman Kodak Company | Polyester nanocomposites |
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- 2005-02-23 CN CNB2005100240222A patent/CN100460457C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504501A (en) * | 2011-11-09 | 2012-06-20 | 华润包装材料有限公司 | High-barrier polyester composite material and preparation method thereof |
| CN102875980A (en) * | 2012-09-29 | 2013-01-16 | 四川东方绝缘材料股份有限公司 | Preparation method of heat-resistant oxygen-resistant polyester film |
| CN102875980B (en) * | 2012-09-29 | 2014-07-23 | 四川东方绝缘材料股份有限公司 | Preparation method of heat-resistant oxygen-resistant polyester film |
| CN114031840A (en) * | 2021-12-01 | 2022-02-11 | 江苏弘奇金属科技有限公司 | High-temperature-resistant anti-puncture winding film and production process thereof |
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| CN100460457C (en) | 2009-02-11 |
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