CN102060984B - Composition for preparing amorphous copolyester - Google Patents
Composition for preparing amorphous copolyester Download PDFInfo
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- CN102060984B CN102060984B CN201010593531.8A CN201010593531A CN102060984B CN 102060984 B CN102060984 B CN 102060984B CN 201010593531 A CN201010593531 A CN 201010593531A CN 102060984 B CN102060984 B CN 102060984B
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Abstract
The invention discloses a composition for preparing amorphous copolyester. The composition consists of a diacid monomer and a diol monomer. The diacid monomer comprises terephthalic acid (TPA), and the diol monomer comprises ethylene glycol (EG). Moreover, the diol monomer also comprises 1,3/1,4-cyclohexanedimethanol (1,3/1,4-CHDM), so that when the adding amount of the 1,3/1,4-CHDM is 20 to 100 mole percent of the equivalent weight of the diol, the amorphous copolyester can be obtained.
Description
Technical field
The present invention relates to a kind of amorphous copolyester (amorphous copolyester) and application thereof, more specifically, the present invention relates to a kind of amorphous copolyester and the application thereof with quite broad amorphous domain.
Background technology
Polyethylene terephthalate (polyethylene terephthalate, PET) be by diacid (diacid) and glycol (diol) fat polymerization after thermoplastic polyester engineering plastics.This material because have strong in mechanical characteristics and electrical specification obstruct power that is quite broad, gas, light transmission is good, hardness, handling ease, the advantage such as inexpensive, be therefore widely used in many industries.But because of its molecular structure tool systematicness, easily pile up and form crystalline texture, and then affect its light transmission, shock-resistance and dyeability etc.So the applied research of visible amorphous copolyester everywhere in many high level industries.
Current most of amorphous copolyester mainly synthesize with Yi Shi Man of the U.S. (Eastman Kodak company) 1,4-cyclohexanedimethanol (1,4-cyclohexanedimethanol, be abbreviated as 1,4-CHDM) the copolyesters polymer (being also called PETG) of monomer polymerization is main, or to import m-phthalic acid (isophthalic acid, IPA) polymerizable, amorphous copolyesters; And suitable narrow in the former its pars amorpha, being only present in Isosorbide-5-Nitrae-CHDM monomer addition is 20 ~ 40%.Latter causes easily crisp and then affect its machinery and working properties owing to importing the cause of IPA.
Summary of the invention
The invention provides a kind of amorphous copolyester, to obtain the simple and easy and material of amorphous domain broadness of synthesis.
The present invention also provides a kind of amorphous copolyester, has broad amorphous domain, applies in order to various forming process.
Container, flap and film that it is material that the present invention also provides with this amorphous copolyester.
The present invention proposes a kind of amorphous copolyester, and it is synthesized by diacid monomer and diol monomer, and this amorphous copolyester comprises the structure shown in formula (1):
Wherein, diacid monomer comprises terephthalic acid (terephthalic acid, is abbreviated as TPA), and diol monomer comprises ethylene glycol (ethylene glycol is abbreviated as EG) and 1,3/1,4-cyclohexanedimethanol (1,3/1,4-cyclohexanedimethanol, be abbreviated as 1,3/1,4-CHDM), wherein 1, the add-on of 3/1,4-cyclohexanedimethanol is 20 ~ 100 % by mole of glycol equivalent.
In one of embodiments of the invention, also comprise in the building-up reactions of diacid monomer and diol monomer and add polycondensation catalyst.And this polycondensation catalyst is 25 ~ 500ppm, and for being selected from one or more metal catalyst in antimony system, titanium system, germanium system, tin system, gallium system, aluminium system and combination thereof.
In one of embodiments of the invention, the intrinsic viscosity of described amorphous copolyester is greater than 0.5dL/g.
The present invention also proposes a kind of amorphous copolyester, and it is synthesized by diacid monomer and diol monomer, and this amorphous copolyester comprises the structure shown in formula (2):
Wherein, diacid monomer comprises terephthalic acid (TPA) and 5-tert-butyl isophthalic acid (5-tert-butylisophthalic acid, 5tBIA); Diol monomer comprises ethylene glycol (EG) and 1,3/1,4-cyclohexanedimethanol (1,3/1,4-CHDM), and work as 1 of gauge with the add-on of the 5tBIA of two acid equivalent basis with glycol, the add-on of 3/1,4-cyclohexanedimethanol adds up to 20 ~ 100 % by mole.
In another embodiment of the invention, also comprise in the building-up reactions of described diacid monomer and diol monomer and add polycondensation catalyst.And this polycondensation catalyst is 25 ~ 500ppm, it is be selected from one or more metal catalyst in antimony system, titanium system, germanium system, tin system, gallium system, aluminium system and combination thereof.
In another embodiment of the invention, the intrinsic viscosity of described amorphous copolyester is greater than 0.5dL/g.
The present invention also proposes a kind of container, and it comprises using one of above-mentioned two kinds of amorphous copolyesters as material.And said vesse can be food product containers, cosmetics containers or drug container.
The present invention also proposes a kind of flap, and it comprises using above-mentioned two kinds of amorphous copolyesters as material.And above-mentioned flap can be sheet material or sheet material.
The present invention also proposes a kind of film, and it comprises using above-mentioned two kinds of amorphous copolyesters as material.And above-mentioned film can be wrapping material or shrink film.
The present invention is because adopting 1, and 3/1,4 cyclohexanedimethanols (1,3/1,4-CHDM), as one of monomer synthesizing amorphous copolyester, therefore can obtain the copolyesters with quite broad amorphous domain.In addition, the present invention, outside above-mentioned 1,3/1,4 cyclohexanedimethanols, also can add 5-tert-butyl isophthalic acid (5tBIA) monomer again to prepare amorphous copolyester, also thus effectively be prevented the effect that glass transition temp declines.And amorphous copolyester of the present invention can be widely used in various industry, be especially applicable to making container, film and flap.
Accompanying drawing explanation
Fig. 1 is the graph of relation of amorphous copolyester 1,3/1,4-cyclohexanedimethanol (1,3/1,4-CHDM) add-on according to first embodiment of the invention and temperature of fusion.
Embodiment
In order to make above-mentioned feature and advantage of the present invention become apparent, preferred embodiment cited below particularly, and coordinate institute's accompanying drawings, be described in detail below.
First embodiment:
The amorphous copolyester of the first embodiment is synthesized by a kind of diacid monomer and two kinds of diol monomers, and its structural formula is as shown in the formula shown in (1):
Wherein, diacid monomer comprises terephthalic acid (terephthalic acid, is abbreviated as TPA), and diol monomer comprises ethylene glycol (ethylene glycol is abbreviated as EG) and 1,3/1,4-cyclohexanedimethanol (1,3/1,4-cyclohexanedimethanol, be abbreviated as 1,3/1,4-CHDM), wherein 1, the add-on of 3/1,4-cyclohexanedimethanol is 20 ~ 100 % by mole of glycol equivalent.In addition, above-mentioned diacid monomer and diol monomer generally through two benches esterification, polycondensation and synthesizing, and need need to add polycondensation catalyst in reaction process, and its content about 25 ~ 500ppm is not etc.And at this polycondensation catalyst adopted such as being selected from one or more metal catalyst in antimony system, titanium system, germanium system, tin system, gallium system, aluminium system and combination thereof; Be preferably antimony acetate and titanium antimony alloy catalyzer.Be then addition according to diacid monomer and diol monomer as A and C in formula (1) and determine.
In addition, above-mentioned 1,3/1, the 4-cyclohexanedimethanol UNOXOL that can provide purchased from DOW Chemical international corporation (Dow Chemical Company)
tM34Diol, its composition is composed as follows:
UNOXOL
tM34Diol component list:
About in the first embodiment with the amorphous copolyester that formula (1) represents, its route of synthesis is as follows:
Following table is the intrinsic viscosity (intrinsic viscosity) and thermal properties thereof that obtain with the amorphous copolyester synthesized by different monomers proportion of composing first, wherein T represents terephthalic acid (TPA), E represents ethylene glycol (EG), C represents 1,3/1,4-cyclohexanedimethanol (1,3/1,4-CHDM).And with " PETG
1.3/1.4" represent the amorphous copolyester synthesized with terephthalic acid, ethylene glycol and 1,3/1,4-cyclohexanedimethanol.
Table one
Intrinsic viscosity in table one is the solution utilizing tetrachloroethane (tetrachloroethane) to mix with phenol (phenol) weight ratio 40: 60, carries out testing obtained value at 25 DEG C with Ubbelohde viscometer (Ubbelohde viscometer).From table one, the intrinsic viscosity (intrinsic viscosity) of amorphous copolyester under difference composition of the first embodiment is all greater than 0.5dL/g.
The measurement of relevant temperature aspect is then utilize elementary errors calorimeter, with per minute 20 DEG C of its thermal propertiess of rate analysis, as the temperature of fusion (T in table one
m).From table one, the T when % by mole (the representing with C) of 1,3/1,4-cyclohexanedimethanol is 20
mbe 196 DEG C, the amount increasing by 1,3/1,4-cyclohexanedimethanol afterwards more just cannot measure its melting temperature (Tm); That is, the add-on of 1,3/1,4-cyclohexanedimethanol is more than 20 % by mole of glycol equivalent, can synthesize the copolyesters of the non-crystalline state of first embodiment of the invention.
In addition, by 1,3/1,4-cyclohexanedimethanol (1,3/1, the 4-CHDM) add-on of table one and melting temperature (Tm) (T
m) relation be made graphic representation, then clearlyer can find out that amorphous copolyester of the present invention gathers and has broad amorphous domain (as Fig. 1).
Second embodiment:
The amorphous copolyester of the second embodiment is synthesized by two kinds of diacid monomer and two kinds of diol monomers, and its structural formula is as shown in the formula shown in (2):
Wherein, diacid monomer comprises terephthalic acid (TPA) and 5-tert-butyl isophthalic acid (5tBIA), diol monomer comprises ethylene glycol (EG) and 1, 3/1, 4-cyclohexanedimethanol (1, 3/1, 4-CHDM), wherein work as 1 of gauge with the add-on of the 5tBIA of two acid equivalent basis with glycol, 3/1, the add-on of 4-cyclohexanedimethanol adds up to 20 ~ 100 % by mole, if and above-mentioned diacid monomer and diol monomer are through two benches esterification, polycondensation is synthesized, then need to add polycondensation catalyst in reaction process, its content about 25 ~ 500ppm is not etc.And at this polycondensation catalyst adopted such as being selected from one or more metal catalyst in antimony system, titanium system, germanium system, tin system, gallium system, aluminium system and combination thereof; Be preferably antimony acetate and titanium antimony alloy catalyzer.And A, B, C and D in formula (2) are addition according to diacid monomer and diol monomer and determine.And above-mentioned 1,3/1,4-cyclohexanedimethanol is the UNOXOL provided purchased from DOW Chemical international corporation (Dow Chemical Company) equally
tM34Diol.
Route of synthesis about the amorphous copolyester represented with formula (2) in the second embodiment is as follows:
Following table two is the intrinsic viscosity and thermal properties thereof that obtain with the amorphous copolyester synthesized by different monomers proportion of composing, wherein T represents terephthalic acid (TPA), tBI represents 5-tert-butyl isophthalic acid (5tBIA), E represents ethylene glycol (EG), C represents 1,3/1,4-cyclohexanedimethanol (1,3/1,4-CHDM).And with " PETG
1.3/1.4b " the representative amorphous copolyester of above four kinds of monomer synthesize.And intrinsic viscosity in table two and melting temperature (Tm) (T
m) be record by the mode identical with the first embodiment.
Table two
From table two, intrinsic viscosity wherein is all greater than 0.5dL/g.And when % by mole (representing with C) of 1,3/1,4-cyclohexanedimethanol be 10,5-tert-butyl isophthalic acid % by mole (representing with tBI) when being 10, just cannot measure T
m; That is, when the summation of C and tBI is more than or equal to 20 % by mole, the amorphous copolyester of second embodiment of the invention can be synthesized.
As for the glass transition temperature (T in table two
g), elementary errors calorimeter also can be utilized to obtain with per minute 20 DEG C of rate analysis.From table two, when the summation of C and tBI is more than or equal to 20 % by mole, the glass transition temperature of amorphous copolyester can't reduce.
Because the amorphous copolyester of first and second embodiment above-mentioned can be processed with traditional forming method, therefore container, flap, thin-film material etc. can be widely used in.
With container, amorphous copolyester of the present invention can improve the toughness of conventional polyester container, especially be applicable to manufacturing the thick transparent vessel of Large Copacity thickness, and because of its high-clarity, not easily broken, be easy to the advantages such as surface working, and high by 1, have more the advantage such as endurance and gamma ray resistant under 3/1,4-cyclohexanedimethanol content, therefore can be applicable to the field of containers such as food, medicine or makeup.Even can add various additive in amorphous copolyester of the present invention, as releasing agent, dyestuff etc., adopt different upgrading formulas according to the requirement in different application field.
With flap (sheet), because amorphous copolyester of the present invention poly-has that toughness is better, transparency is high, the not easily advantage such as broken, make sheet material or sheet material so also can be applicable to.
With film, because amorphous copolyester of the present invention has high plastic uptake power, high-clarity, high gloss, low haze, be easy to printing, difficult drop-off and the advantage such as when storing natural shrinking rate is low, make as the flap such as wrapping material or shrink film so can be widely used in.
In sum, the present invention is because with 1, and 3/1,4 cyclohexanedimethanols (1,3/1,4-CHDM), as one of monomer synthesizing amorphous copolyester, therefore can obtain the copolyesters with quite broad amorphous domain.Meanwhile, the present invention also can add 5-tert-butyl isophthalic acid (5tBIA) monomer again to prepare amorphous copolyester, so the effect that also can effectively be prevented glass transition temp from declining.And amorphous copolyester of the present invention is because this has multiple advantages in material aspect, therefore can be used for making various container or the flap as wrapping material or shrink film etc.
Although the present invention discloses as above with preferred embodiment; so itself and be not used to limit the present invention; any those skilled in the art; without departing from the spirit and scope of the invention; when doing a little change and retouching, the scope that the protection domain of therefore the present invention ought define with claims is as the criterion.
Claims (8)
1., for the preparation of a composition for amorphous copolyester, comprise diacid monomer and diol monomer, it is characterized in that:
This diacid monomer comprises terephthalic acid (TPA), and the add-on of terephthalic acid is 100 % by mole;
This diol monomer comprises ethylene glycol (EG) and 1, 3/1, 4-cyclohexanedimethanol (1, 3/1, mixture 4-CHDM), ethylene glycol (EG) and 1, 3/1, 4-cyclohexanedimethanol (1, 3/1, add-on 4-CHDM) adds up to 100 % by mole, wherein 1, 3/1, the add-on of the mixture of 4-cyclohexanedimethanol is 20 ~ 100 % by mole of glycol equivalent, 1, 3/1, the mixture of 4-cyclohexanedimethanol is by suitable 1, 3-cyclohexanedimethanol 32.8%, anti-1, 3-cyclohexanedimethanol 24%, along 1, 4-cyclohexanedimethanol 13% and anti-1, 4-cyclohexanedimethanol 30.2% forms, above-mentioned 1, 3/1, the UNOXOL that the mixture of 4-cyclohexanedimethanol provides for DOW Chemical international corporation
tM34D iol,
Wherein said composition also comprises polycondensation catalyst, and this polycondensation catalyst is 25 ~ 500ppm, and this polycondensation catalyst is be selected from more than one metal catalyst in antimony system, titanium system, germanium system, tin system, gallium system, aluminium system and combination thereof,
The structural formula of described amorphous copolyester is as shown in the formula shown in (1):
A and C in formula (1) is addition according to diacid monomer and diol monomer and determines.
2. the composition for the preparation of amorphous copolyester according to claim 1, is characterized in that: the intrinsic viscosity of prepared amorphous copolyester is greater than 0.5dL/g.
3. a container, is characterized in that:
Use described in claim 1 or 2 for the preparation of amorphous copolyester composition prepared by amorphous copolyester be material.
4. container according to claim 3, it is food product containers, cosmetics containers or drug container.
5. a film, is characterized in that:
Use described in claim 1 or 2 for the preparation of amorphous copolyester composition prepared by amorphous copolyester be material.
6. film according to claim 5, it is wrapping material or shrink film.
7. a flap, is characterized in that:
Use described in claim 1 or 2 for the preparation of amorphous copolyester composition prepared by amorphous copolyester be material.
8. flap according to claim 7, it is sheet material or sheet material.
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| CN201010593531.8A CN102060984B (en) | 2006-12-29 | 2006-12-29 | Composition for preparing amorphous copolyester |
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| CNA2006101725418A Division CN101210067A (en) | 2006-12-29 | 2006-12-29 | Amorphous copolyester and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121727A (en) * | 1993-04-27 | 1996-05-01 | 伊斯曼化学公司 | Copolyester of cyclohexanedimethanol and process for producing such polyester |
| US6025069A (en) * | 1998-06-19 | 2000-02-15 | Eastman Chemical Company | Thermoplastic article having high-relief surface |
| CN1285881A (en) * | 1997-11-06 | 2001-02-28 | 伊斯曼化学公司 | Copolyester binder fibers |
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2006
- 2006-12-29 CN CN201010593531.8A patent/CN102060984B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1121727A (en) * | 1993-04-27 | 1996-05-01 | 伊斯曼化学公司 | Copolyester of cyclohexanedimethanol and process for producing such polyester |
| CN1285881A (en) * | 1997-11-06 | 2001-02-28 | 伊斯曼化学公司 | Copolyester binder fibers |
| US6025069A (en) * | 1998-06-19 | 2000-02-15 | Eastman Chemical Company | Thermoplastic article having high-relief surface |
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