CN103059279B - A kind of barrier polyester and preparation method thereof - Google Patents
A kind of barrier polyester and preparation method thereof Download PDFInfo
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- CN103059279B CN103059279B CN201110320992.2A CN201110320992A CN103059279B CN 103059279 B CN103059279 B CN 103059279B CN 201110320992 A CN201110320992 A CN 201110320992A CN 103059279 B CN103059279 B CN 103059279B
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Abstract
A kind of barrier polyester, including terephthalic acid (TPA), ethylene glycol and barrier comonomer, described barrier comonomer is hydroxy carboxylic acid compound or the benzoic acid derivative of at least two substituents, and described substituent is selected from hydroxyl or carboxyl, but can not be carboxyl simultaneously.Described barrier polyester is nontoxic, good mechanical performance, particularly the good barrier property to oxygen, and OTR oxygen transmission rate is low.
Description
Technical field
The present invention is a kind of barrier polyester and preparation method thereof, specifically, is a kind of poly- to benzene with barrier
Naphthalate.
Background technology
Polyethylene terephthalate (PET) is a kind of crystalline thermoplastic resin of function admirable, with preferable
Chemical stability, mechanical property, heat resistance, sanitation performance and environmental-protecting performance, except be widely used as manufacture synthetic fibers it
Outside, production bottle class and film based packaging material are also extensively used for, and in recent years, PET is rapid in the application of packaging field
Increase.But, PET but existed as packaging material one it is clearly disadvantageous, i.e., it is to O2、CO2Small point stronger etc. permeability
The barrier property of sub- gas is not ideal, especially O2, because molecular dimension is smaller, PET packaging materials to its barrier property more
Difference, is often easily caused packaging products taste and declines, or even rotten.Therefore, people are directed to by various technologies way always
PET gas barrier property is improved in footpath, is especially desirable to improve its O2Barrier property.
In the prior art, in order to make up the defect that PET packaging material barrier properties are poor, the measure of use mainly has many
Layer is compound, blending and modifying and nano material are compound etc. several.
CN101172525A, CN1174847C, CN2897642Y etc. disclose a kind of by the raising of double-deck or multiple-layer stacked
The method of produced polyester packaging material barrier property.Choose PET resin and do the basic unit of packaging material, at the same choose it is another kind of or
A few class high barrier polyester resin do barrier layer, then using extra quality/double coloured plastic injection machine or double-deck co-injection machine, coordinate double-deck
Preform mould, injection or synchronous co-injection be into after double-deck base in two times, then by the preheating of bottle parison heating machinery and two-way drawing
Stretch blowing machinery and produce double-layer polyester bottle.Its essence replaces with other high barrier polyester equivalent to by a part of PET resin
Resin, the improvement to PET resin barrier property is not related to.
CN1817609A, CN100503237C disclose the method that polyester barrier property is improved by coating.From PET
Resin, by being coated with one or more layers thermoplastic or high resistant oxygen glue for having good trapping characteristic at least one surface thereof
The aqueous solution, improves the barrier property of polyester article.It is preferred that barrier material to oxygen and carbon dioxide have the infiltration low compared with PET
Rate, while its Main physical performance is approached with PET.The polyester of coating can be used for the bag of soft drink, beer or fruit juice etc beverage
Dress.Obviously, the technology is also not involved with the improvement to PET resin barrier property.
CN100460457C discloses a kind of preparation method of high baffer modified polyester.By PET, gather to naphthalenedicarboxylic acid second
Diol ester (PEN resins), two hydrogen species oxazole compounds and antioxidant are mixed in proportion, and use screw extruder extruding pelletization
Form.Be characterized in after PET has been produced, by with other polyester or auxiliary agent blending extrusion, improve PET resin resistance
Separating performance.
CN101200575A discloses a kind of montmorillonite modified polyester and preparation method thereof.By montmorillonite, ethylene glycol and right
Rutgers is mixed by proper proportion, is polymerize in 160~290 DEG C, obtains imvite modified polyester.Feature is
In PET production processes, add inorganic cover and hold in the palm native filler, pass through the barrier property that polycondensation improves PET.
On the whole, the method for multiple-layer stacked and the method for coating do not change the barrier properties of PET in itself, blending
It is that reheating, melting extrusion have technological process after PET production shapings although modified method technique is simple
The higher deficiency of long, energy consumption.The illiteracy support soil of support soil, the especially thinner nanoscale of particle diameter is covered by adding in polymerization,
PET barrier property is improved to a certain extent, and work flow is short, energy consumption is relatively low, but the inorganic filler of addition may influence PET
Other physicochemical properties.
The content of the invention
It is an object of the invention to provide a kind of barrier polyester and preparation method, described barrier polyester is nontoxic, mechanics
Function admirable, the particularly good barrier property to oxygen, OTR oxygen transmission rate are low.
The barrier polyester that the present invention is provided, including terephthalic acid (TPA), ethylene glycol and barrier comonomer, described resistance
Every the hydroxy carboxylic acid compound or benzoic acid derivative that property comonomer is at least two substituents, described substituent is selected from
Hydroxyl or carboxyl, but can not be carboxyl simultaneously.
The present invention adds the hydroxyl carboxylic of at least two substituents in the synthesis material of polyethylene terephthalate
Acid compound or benzoic acid derivative can increase degree of cross linking when terephthalic acid (TPA) and ethylene glycol polymerization as barrier monomer,
So that polymer forms more network structures, and then reduce the OTR oxygen transmission rate of polyester.
Embodiment
The present invention is barrier comonomer using the benzoic acid derivative of hydroxy carboxylic acid compound or hydroxyl, by itself plus
Enter and reacted in terephthalic acid (TPA) and ethylene glycol raw material, the hydroxyl on barrier comonomer can be better than ethylene glycol and to benzene two
The carboxyl of formic acid is reacted, so as to improve the degree of cross linking of polyester, reduces the transmitance of oxygen.The polyester that the present invention is provided without
Poison, and good mechanical performance, can be widely used for producing various beverages, food and pharmaceutical packing container.Described barrier gathers
Ester preparation method flow is short, energy consumption is low, is more suitable for large-scale industrial production.
Barrier comonomer used is the hydroxycarboxylic acid or benzene first at least containing two substituents in polyester of the present invention
Acid derivative, described substituent is hydroxyl or carboxyl, but is asynchronously carboxyl, i.e., carboxylic acid of the present invention is to contain hydroxyl
Carboxylic acid, also contain hydroxyl in benzoic acid derivative.Should at least it contain in described hydroxy carboxylic acid compound or benzoic acid derivative
There are three reactive groups, described reactive group is hydroxyl or carboxyl, and the number of reactive group is alternatively 4 or 5, hydroxycarboxylic acid
The number of compound reactive group is also greater than 5, but described reactive group it is different when be carboxyl.
The preferred dihydroxy carboxylic acids of described hydroxy carboxylic acid compound or the dicarboxylic acids for having a hydroxyl, the carbon of the carboxylic acid
Atomicity preferably 4~8.The preferred dihydroxy-benzoic acid of described benzoic acid derivative or monohydroxy phthalic acid.
The barrier that 0.2~10 mass %, more preferably 0.3~8.0 mass % is preferably included in polyester of the present invention is total to
Polycondensation monomer.
The preparation method for the polyester that the present invention is provided, including terephthalic acid (TPA), ethylene glycol and barrier comonomer are mixed
Close, esterification is first carried out in the presence of a catalyst, polycondensation reaction is carried out after heating again.
In the above method in terephthalic acid (TPA), ethylene glycol and barrier comonomer carboxyl and hydroxyl mol ratio, i.e., it is anti-
The mol ratio for answering the total carboxyl and total hydroxyl contained in thing is 1: 1.0~1.8, preferably 1: 1.1~1.5.
Hydroxyl and carboxyl (sum of the two) and the total hydroxyl of reactant and total carboxyl (two that the barrier comonomer is provided
Person's sum) molar percentage be 0.5~10mol%, preferably 0.5~5mol%.
In two steps, the first step is anti-for the esterification carried out between small molecule for the preparation method for the barrier polyester that the present invention is provided
Should, carry out at ambient pressure, reaction temperature is 180~250 DEG C, preferably 200~250 DEG C.Second step is formed greatly for product after esterification
The polycondensation reaction of molecule, described polycondensation reaction is carried out under reduced pressure, and reaction temperature is 260~300 DEG C.
The catalyst used in above-mentioned preparation process of polyester is antimony acetate or antimony oxide, preferably antimony acetate.Catalyst
Consumption be reaction raw materials total amount 0.01~0.10 mass %, preferably 0.02~0.05 mass %.
The barrier polyester that the present invention is provided is applied to produce various beverages, food and pharmaceutical packing container.
The present invention is further illustrated below by example, but the present invention is not limited thereto.
In example, the gas permeability of polyester product is tested by GB/T1038-2000, and inherent viscosity presses GB/T22235-2008 methods
Determine, glass transition temperature (Tg) and crystallization temperature (Tm) are determined with Differential scanning calorimetry respectively.
Example 1
By 415.0g (2.50mol) terephthalic acid (TPA), 184.1g (2.97mol) ethylene glycol, 4.44g (0.03mol) 3,5-
Dihydroxy caproic acid and 0.2g catalyst acetic acids antimony are added in autoclave, with nitrogen displacement gas reactor twice.0.1MPa is pressed
Under power and stirring esterification is carried out in 230 DEG C 2 hours.Temperature is risen to 280 DEG C, polycondensation reaction 2 hours is carried out under reduced pressure.
Polyester product is collected, its property is shown in Table 3, the 5- dihydroxy caproic acids for containing 0.8 mass % in 1, polyester.
Example 2
By 415.0g (2.50mol) terephthalic acid (TPA), 180.4g (2.91mol) ethylene glycol, 13.32g (0.09mol) 3,5-
Dihydroxy caproic acid and 0.2g catalyst acetic acids antimony are added in autoclave, with nitrogen displacement gas reactor twice.0.1MPa is pressed
Under power and stirring esterification is carried out in 230 DEG C 1 hour.Temperature is risen to 280 DEG C, polycondensation reaction 1 hour is carried out under reduced pressure.
Polyester product is collected, its property is shown in Table 3, the 5- dihydroxy caproic acids for containing 2.2 mass % in 1, polyester.
Example 3
By 415.0g (2.50mol) terephthalic acid (TPA), 176.7g (2.85mol) ethylene glycol, 22.2g (0.15mol) 3,5-
Dihydroxy caproic acid and 0.2g catalyst acetic acids antimony are added in autoclave, with nitrogen displacement gas reactor twice.0.1MPa is pressed
Under power and stirring esterification is carried out at 230 DEG C 2 hours.Temperature is risen to 280 DEG C, polycondensation reaction 1 hour is carried out under reduced pressure.
Polyester product is collected, its property is shown in Table 3, the 5- dihydroxy caproic acids for containing 3.6 mass % in 1, polyester.
Example 4
By 410.0g (2.47mol) terephthalic acid (TPA), 182.3g (2.94mol) ethylene glycol, 4.62g (0.03mol) 3,5-
Dihydroxy-benzoic acid and 0.2g catalyst acetic acids antimony are added in autoclave, with nitrogen displacement gas reactor twice.0.1MPa
Under pressure and stirring esterification is carried out at 230 DEG C 2 hours.Temperature is risen to 280 DEG C, polycondensation reaction 2 is carried out under reduced pressure small
When.Polyester product is collected, its property is shown in Table 3, the 5- dihydroxy-benzoic acids for containing 0.8 mass % in 1, polyester.
Example 5
By 400.0g (2.41mol) terephthalic acid (TPA), 174.8g (2.82mol) ethylene glycol, 13.86g (0.09mol) 3,
5- dihydroxy-benzoic acids and 0.2g catalyst acetic acids antimony are added in autoclave, with nitrogen displacement gas reactor twice.
Under 0.1MPa pressure and stirring esterification is carried out in 230 DEG C 1 hour.Temperature is risen to 280 DEG C, carries out being condensed instead under reduced pressure
Answer 2 hours.Polyester product is collected, its property is shown in Table 3, the 5- dihydroxy-benzoic acids for containing 2.3 mass % in 1, polyester.
Example 6
By 390.1g (2.35mol) terephthalic acid (TPA), 167.4g (2.70mol) ethylene glycol, 23.1g (0.15mol) 3,
5- dihydroxy-benzoic acids and 0.2g catalyst acetic acids antimony are added in autoclave, with nitrogen displacement gas reactor twice.
Under 0.1MPa pressure and stirring esterification is carried out at 230 DEG C 2 hours.Temperature is risen to 280 DEG C, polycondensation is carried out under reduced pressure anti-
Answer 1 hour.Polyester product is collected, its property is shown in Table 3, the 5- dihydroxy-benzoic acids for containing 3.7 mass % in 1, polyester.
Comparative example 1
415.0g (2.50mol) terephthalic acid (TPA), 186.0g (3.6mol) ethylene glycol and 0.2g catalyst acetic acid antimony are added
Enter in autoclave, with nitrogen displacement gas reactor twice.Under 0.1MPa pressure and stirring esterification 2 is carried out at 230 DEG C
Hour.Temperature is risen to 280 DEG C, polycondensation reaction 2 hours is carried out under reduced pressure.Polyester product is collected, its property is shown in Table 1.
Table 1
Claims (8)
1. a kind of barrier polyester, is made up of terephthalic acid (TPA), ethylene glycol and barrier comonomer, described barrier copolymerization
Monomer is hydroxy carboxylic acid compound or the benzoic acid derivative of at least two substituents, described at least two substituents
Hydroxy carboxylic acid compound is dihydroxy carboxylic acids or has the dicarboxylic acids of a hydroxyl, the benzene first of described at least two substituents
The substituent of acid derivative is selected from hydroxyl or carboxyl, but can not be carboxyl simultaneously, and the polyester includes 0.2~10 mass %'s
Barrier comonomer.
2. according to the polyester described in claim 1, it is characterised in that the benzoic acid derivative of at least two described substituents
For dihydroxy-benzoic acid or monohydroxy phthalic acid.
3. the preparation method of polyester described in a kind of claim 1, including by terephthalic acid (TPA), ethylene glycol and barrier comonomer
Mixing, first carries out esterifications at 180~250 DEG C in the presence of a catalyst, is warming up to after 260~300 DEG C that to carry out polycondensation again anti-
Should, the hydroxy carboxylic acid compound or benzoic acid derivative of described barrier comonomer at least two substituents are described
At least two substituents hydroxy carboxylic acid compound is dihydroxy carboxylic acids or has the dicarboxylic acids of a hydroxyl.
4. in accordance with the method for claim 3, it is characterised in that contain in terephthalic acid (TPA), ethylene glycol and barrier comonomer
The mol ratio of some carboxyl and hydroxyl is 1: 1.0~1.8.
5. in accordance with the method for claim 4, it is characterised in that contain in terephthalic acid (TPA), ethylene glycol and barrier comonomer
The mol ratio of some carboxyl and hydroxyl is 1: 1.1~1.5.
6. in accordance with the method for claim 3, it is characterised in that hydroxyl and carboxyl and reaction that barrier comonomer is provided
The molar percentage of the total hydroxyl of thing and total carboxyl is 0.5~10mol%.
7. in accordance with the method for claim 3, it is characterised in that described esterification is carried out at ambient pressure, described polycondensation
Reaction is carried out under reduced pressure.
8. in accordance with the method for claim 3, it is characterised in that described catalyst is antimony acetate or antimony oxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10280254B2 (en) * | 2016-04-20 | 2019-05-07 | Elevance Renewable Sciences, Inc. | Renewably derived polyesters and methods of making and using the same |
| CN109054007A (en) * | 2018-08-30 | 2018-12-21 | 中国科学院宁波材料技术与工程研究所 | Biology base furandicarboxylic acid polyester and preparation method thereof |
| CN115011085B (en) * | 2022-07-15 | 2023-08-22 | 华润化学材料科技股份有限公司 | Barrier polyester and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1312304A (en) * | 2000-03-08 | 2001-09-12 | 财团法人工业技术研究院 | Composite for preparing high molecular weight polyester and the prepn process of the high molecular weight polyester |
| CN101130626A (en) * | 2006-08-25 | 2008-02-27 | 中国科学院合肥物质科学研究院 | Copolyester flame-retardant material containing Lewis acid and preparation method thereof |
| CN101134810A (en) * | 2006-09-01 | 2008-03-05 | 远东纺织股份有限公司 | Modified copolyester, thermal shrinkage polyester film produced thereby and method for preparing same |
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| CN101412804B (en) * | 2008-11-23 | 2011-01-19 | 浙江大学宁波理工学院 | Method for preparing aromatic-aliphatic copolyester |
| CN102718955B (en) * | 2012-07-03 | 2014-07-23 | 常州大学 | Poly(terephthalate glycol ester-CO-glycolate) copolyester and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312304A (en) * | 2000-03-08 | 2001-09-12 | 财团法人工业技术研究院 | Composite for preparing high molecular weight polyester and the prepn process of the high molecular weight polyester |
| CN101130626A (en) * | 2006-08-25 | 2008-02-27 | 中国科学院合肥物质科学研究院 | Copolyester flame-retardant material containing Lewis acid and preparation method thereof |
| CN101134810A (en) * | 2006-09-01 | 2008-03-05 | 远东纺织股份有限公司 | Modified copolyester, thermal shrinkage polyester film produced thereby and method for preparing same |
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