CN101469057B - Atactic amorphous copolyester as well as preparation method and application thereof - Google Patents
Atactic amorphous copolyester as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an irregular amorphous copolymerized ester, which comprises diacid monomer and diol monomer, and has a structure shown as formula (I), wherein R1 and R2 are aromatic or aliphatic groups, A is 0 to 0.8, B is 0 to 0.8, C is 0 to 1, D is 0 to 1, E is 0 to 0.8, F is 0 to 0.8, wherein the sum of the C and the D is more than 0.2, and the sum of the A, the B, the E and the F is less than 0.8; wherein the diacid monomer comprises terephthalic acid and aromatic or aliphatic diacid monomer, and the diol monomer comprises glycol, 1, 3/1, 4-cyclohexane dimethanol and aromatic or aliphatic diol monomer, wherein the 1, 3/1, 4-cyclohexane dimethanol accounts for 20 to 100 mol percent in 100 mol percent of diol, the aromatic or aliphatic diacid monomer accounts for 0 to 100 mol percent in 100 mol percent of diacid, and the aromatic or aliphatic diol monomer accounts for 0 to 80 mol percent in 100 mol percent of diol.
Description
[technical field]
The present invention relates to a kind of amorphous copolyester (amorphous copolyester), particularly relate to a kind of amorphous copolyester with broad second-order transition temperature.
[background technology]
Heat-shrinkable film be widely used in bottle, box, container and the tubing string of glass, metal, pottery or plastic material label, protect, tie up and parcel etc.For example, heat-shrinkable film can be used as the label of food or medicine, promptly shows at the enterprising rower of plastic containers (like beverages can).In general, shrink film can be divided into two kinds: (1) is used for the Biaxially oriented film (biaxially oriented film) of wrapping material, and this Biaxially oriented film can shrink on x and y direction of principal axis; (2) non-Biaxially oriented film (unbiaxially oriented film), this non-Biaxially oriented film itself can shrink according to stretching or compression direction, and the contraction on non-stretching or compression direction is less.
Though materials such as shrink film can PS (OPS), Vilaterm, Vestolen PP 7052 and polyester prepare, general shrink film is all SE (PVC) material.Though PVC has good heat shrinkability characteristic, PVC also is not suitable for the low temperature contraction, and PVC meeting generation hydrogenchloride after burning, and then corrosion incinerator and contaminate environment.In addition, the proportion of PVC and polyethyleneterephthalate (PET) therefore is difficult in removal process both separated all near 1.33, amorphous polyester to replace PVC so develop.
At present; Amorphous copolyester is mainly with 1 of U.S. Yi Shi Man (Eastman Kodak company); 4-cyclohexanedimethanol (1; 4-cyclohexanedimethanol) the copolyesters polymer of monomer polymerization (being called PETG again) is main, but also can't shrink down in comparatively high temps effectively at present, so industry is needed a kind of novel amorphous copolyester and method of manufacture thereof with broad heat shrink temperature badly.
[summary of the invention]
The invention provides a kind of atactic amorphous copolyester, it is to use diacid monomer and diol monomer synthetic, has suc as formula the structure shown in (I):
(formula I)
R
1Be aromatic series or aliphatic group, R
2Be aromatic series or aliphatic group; A is 0-0.8, and B is 0-0.8, and C is 0-1, and D is 0-1, and E is 0-0.8, and F is 0-0.8, wherein C+D>0.2 and A+B+E+F<0.8; Wherein this diacid monomer comprises terephthalic acid and aromatic series or aliphatic diacid monomer, and this diol monomer comprises terepthaloyl moietie, 1,3/1,4-cyclohexanedimethanol and aromatic series or aliphatic diol monomer.Here, A-F representes the mole fraction of each unit in polymer molecular chain respectively.
In one embodiment of the present invention, R
1For contain 6 above carbon atoms, such as the aromatic group of phenyl ring, naphthalene nucleus etc., perhaps contain aliphatic group 2 above carbon atoms, straight or branched.
In one embodiment of the present invention, R
2For contain 6 above carbon atoms, such as the aromatic group of phenyl ring, naphthalene nucleus etc., perhaps contain aliphatic group 2 above carbon atoms, straight or branched or oligomer etc.
The present invention provides a kind of film in addition, comprises amorphous copolyester, and wherein this amorphous copolyester is synthesized by diacid monomer and diol monomer, has suc as formula the structure shown in (I):
(I)
R
1, R
2Be aromatic series or aliphatic group; A is 0-0.8, and B is 0-0.8, and C is 0-1, and D is 0-1, and E is 0-0.8, and F is 0-0.8, wherein C+D>0.2 and A+B+E+F<0.8; Wherein this diacid monomer comprises terephthalic acid and aromatic series or aliphatic monomer, and this diol monomer comprises terepthaloyl moietie and 1,3/1,4-cyclohexanedimethanol and aromatic series or aliphatic monomer.
The present invention also provides a kind of method of manufacture of atactic amorphous copolyester, comprising: terephthalic acid, terepthaloyl moietie and 1,3/1 are provided, the 4-cyclohexanedimethanol; Aromatic monomer or aliphatic monomer are provided, and wherein this aromatic monomer comprises aromatic diacid monomer or aromatic diol monomer, and this aliphatic monomer comprises aliphatic diacid monomer or aliphatic diol monomer; Mix this terephthalic acid, terepthaloyl moietie and 1; 3/1; 4-cyclohexanedimethanol and this aromatic monomer or aliphatic monomer carry out esterification and polycondensation to form this amorphous copolyester, and wherein this terephthalic acid, aromatic diacid monomer and aliphatic diacid monomer are diacid monomer, this terepthaloyl moietie, 1; 3/1,4-cyclohexanedimethanol, aromatic diol monomer and aliphatic diol monomer are diol monomer.
In order to let the present invention non-above-mentioned and other purpose, characteristic and the advantage can be more obviously understandable, hereinafter is special lifts preferred embodiment, and cooperates appended diagram, elaborates as follows.
[description of drawings]
Fig. 1 shows the shrinkage temperature and the shrinking percentage of the amorphous copolyester of embodiment 1,2.
[embodiment]
The present invention has disclosed a kind of atactic amorphous copolyester with broad second-order transition temperature and heat shrink temperature, and it has suc as formula the structure shown in (I):
and
(I)
Atactic amorphous copolyester of the present invention is to use glycol and diacid monomer synthetic, R
1, R
2Be respectively aromatic series or aliphatic group, (I) can know by formula, R
1Connect two carboxyls, R
2Connect two alcohol radicals.The ratio of A, B, C, D, E and F is decided according to the addition of each diacid and diol monomer, and preferable A can be 0-0.8, and B can be 0-0.8, and C can be 0-1, and D can be 0-1, and E can be 0-0.8, and F can be 0-0.8, wherein C+D>0.2 and A+B+E+F < 0.8.
Diol monomer comprises terepthaloyl moietie (EG), 1,3/1,4-cyclohexanedimethanol and aromatic series or aliphatic diol monomer.In this diol monomer of 100 molar percentages, contain the 0-80 molar percentage terepthaloyl moietie, 20-100 molar percentage 1,3/1, the aromatic series of 4-cyclohexanedimethanol and 0-80 molar percentage or aliphatic diol monomer.The aromatic diol monomer can be 2, and two (4-hydroxy phenyl) propane of 2-(2,2-Bis (4-hydroxyphenyl) propane; Be called dihydroxyphenyl propane again), 1, the 1-bis(4-hydroxyphenyl) cyclohexane (1,1-Bis (4-hydroxyphenyl) cyclohexane; Be called bisphenol Z again) or 4, the 4-xenol (4,4-Biphenol).The aliphatic diol monomer can be Ucar 35, butyleneglycol, polyoxyethylene glycol (PEG) or polytetramethylene ether (polytetramethylene oxide, PTMO).
In one embodiment, diacid monomer comprises terephthalic acid (TPA) and aromatic diacid monomer, and this aromatic diacid monomer includes, but are not limited to; 2,6-naphthalene diformic acid dimethyl ester, 2,6-naphthalic acid, 2; 7-naphthalic acid, 1,4-naphthalic acid, 2,7-naphthalene diformic acid dimethyl ester, 2; 3-naphthalene diformic acid dimethyl ester or m-phthalic acid (IPA) etc., and in the diacid monomer of 100 molar percentages, contain the aromatic diacid monomer of 0-100 molar percentage.
In another embodiment; Diacid monomer comprises terephthalic acid (TPA) and aliphatic diacid monomer; This aliphatic diacid monomer includes, but not limited to succsinic acid, propanedioic acid or hexanodioic acid etc.; And in the diacid monomer of 100 molar percentages, contain the aliphatic diacid monomer of 0-100 or 0-40 molar percentage.
Atactic amorphous copolyester of the present invention has broad second-order transition temperature and heat shrink temperature; For example, its second-order transition temperature can reach-20 ℃ to 150 ℃, is preferably 40 ℃ to 120 ℃; Its limiting viscosity is preferably 0.6-0.75dL/g greater than 0.5dL/g.
Amorphous copolyester of the present invention can be used to prepare container, food product containers, cosmetics containers, drug container, sheet material, wrapping material or film; And, therefore can promote the range of application of said vesse, sheet material or film because amorphous copolyester of the present invention has broad second-order transition temperature.
The present invention discloses a kind of film in addition, and it comprises amorphous copolyester, and this amorphous copolyester has suc as formula the structure shown in (I):
(formula I)
R wherein
1, R
2Be aromatic series or aliphatic group, define same as described above.The ratio of A, B, C, D, E and F can be decided according to the addition of each diacid and diol monomer equally, and preferable A can be 0-0.8, and B can be 0-0.8, and C can be 0-1, and D can be 0-1, and E can be 0-0.8, and F can be 0-0.8, wherein C+D>0.2 and A+B+E+F < 0.8.This film can be wrapping material or shrink film.
The present invention more provides a kind of method of manufacture of atactic amorphous copolyester, and comprising provides terephthalic acid, terepthaloyl moietie and 1,3/1,4-cyclohexanedimethanol; Aromatic series or aliphatic monomer are provided; Carry out esterification and polycondensation to form amorphous copolyester of the present invention.
Diacid monomer of the present invention comprises phthalic acid, aromatic diacid monomer and aliphatic diacid monomer, and diol monomer comprises terepthaloyl moietie, 1,3/1,4-cyclohexanedimethanol, aromatic diol monomer and aliphatic diol monomer.In the diacid monomer of 100 molar percentages, contain this aromatic series or the aliphatic diacid monomer of 0-100 molar percentage; In this diol monomer of 100 molar percentages, contain this aromatic series or the aliphatic diol monomer of 0-80 molar percentage.
As stated, aromatic monomer comprises aromatic diacid monomer and aromatic diol monomer.Aromatic diacid monomer comprises 2,6-naphthalene diformic acid dimethyl ester, 2,6-naphthalic acid, 2,7-naphthalic acid, 1,4-naphthalic acid, 2,7-naphthalene diformic acid dimethyl ester, 2,3-naphthalene diformic acid dimethyl ester or m-phthalic acid (IPA).The aromatic diol monomer can be 2, and two (4-hydroxy phenyl) propane of 2-(2,2-Bis (4-hydroxyphenyl) propane; Be called dihydroxyphenyl propane again), 1, the 1-bis(4-hydroxyphenyl) cyclohexane (1,1-Bis (4-hydroxyphenyl) cyclohexane; Be called bisphenol Z again) or 4, the 4-xenol (4,4-Biphenol).
Aliphatic monomer comprises aliphatic diacid monomer and aliphatic diol monomer.Aliphatic diacid monomer comprises succsinic acid, propanedioic acid or hexanodioic acid.The aliphatic diol monomer can be Ucar 35, butyleneglycol, polyoxyethylene glycol (PEG) or polytetramethylene ether (polytetramethylene oxide, PTMO).
The temperature of esterification can be 220-250 ℃, and the temperature of polycondensation can be 250-280 ℃.In the present invention, can when polycondensation reaction, add polycondensation catalyst, this polycondensation catalyst can be the metal catalyst of antimony system, germanium system, tin system, gallium system, aluminium system or its aforesaid combination, is preferably antimony acetate or titanium antimony alloy catalyzer.With respect to total feed weight, the consumption of polycondensation catalyst can be about 25-500ppm.
In one embodiment, the employed catalyzer of esterification and polycondensation is identical; In another embodiment, the employed catalyzer of esterification and polycondensation is different.Catalyzer in esterification of the present invention and the polycondensation, temperature, time are identical with general known technology, do not have special restriction, and those skilled in the art can select different reaction parameters according to different needs.
[embodiment]
The structural formula of this amorphous copolyester is as shown in the formula shown in (II):
The amorphous copolyester of this embodiment is synthetic by two kinds of diacid monomer and two kinds of diol monomers, and diacid monomer comprises terephthalic acid (TPA) and 2,6-naphthalene diformic acid dimethyl ester (NDC); Diol monomer comprises terepthaloyl moietie (EG) and 1,3/1, and the 4-cyclohexanedimethanol (1,3/1,4-CHDM) (Dow Chemical Company, UNOXOL
TM34 Diol).Terephthalic acid (TPA), 2,6-naphthalene diformic acid dimethyl ester (NDC), terepthaloyl moietie (EG) and 1,3/1, the molar percentage of 4-cyclohexanedimethanol is as shown in table 1.Can know by table 1, can be through regulating 2, the content of 6-naphthalene diformic acid dimethyl ester changes the second-order transition temperature of copolyesters, for example, and 2, the content of 6-naphthalene diformic acid dimethyl ester is high more, and second-order transition temperature is then high more.Diacid monomer and diol monomer are to form via the esterification of two stages, polycondensation, and in polycondensation process, add tetrabutyl titanate ester or the antimony acetate catalyzer of the about 350ppm of content.
The amorphous copolyester route of synthesis of embodiment 1 is following:
The characteristic of the amorphous copolyester of table 1. embodiment 1
T: terephthalic acid (TPA)
N:2,6-naphthalene diformic acid dimethyl ester (NDC)
G
1,3/1,4: 1,3/1, the 4-cyclohexanedimethanol
E: terepthaloyl moietie (EG)
Tg: second-order transition temperature
Tm: melting temperature (Tm)
Embodiment 2, PETG
xS
y
The structural formula of this amorphous copolyester is as shown in the formula shown in (III):
The amorphous copolyester of this embodiment is by two kinds of diacid monomer and two kinds of diol monomer synthetic, and diacid monomer comprises terephthalic acid (TPA) and succsinic acid (SA); Diol monomer comprises terepthaloyl moietie (EG) and 1,3/1, and the 4-cyclohexanedimethanol (1,3/1,4-CHDM) (Dow Chemical Company, UNOXOL
TM34 Diol), wherein terephthalic acid (TPA), succsinic acid (SA), terepthaloyl moietie (EG) and 1,3/1, the molar percentage of 4-cyclohexanedimethanol is as shown in table 2.Can be known that by table 2 can change the second-order transition temperature of copolyesters through the content of regulation and control succsinic acid, for example, the content of succsinic acid is higher, second-order transition temperature is then lower.Diacid monomer and diol monomer form via the esterification of two stages, polycondensation, in polycondensation process, add tetrabutyl titanate ester or the antimony acetate catalyzer of the about 350ppm of content.
The amorphous copolyester route of synthesis of embodiment 2 is following:
The characteristic of the amorphous copolyester of table 2. embodiment 2
T: terephthalic acid (TPA)
S: succsinic acid (SA)
G
1,3/1,4: 1,3/1, the 4-cyclohexanedimethanol
E: terepthaloyl moietie (EG)
Tg: second-order transition temperature
Tm: melting temperature (Tm)
Embodiment 3, contraction test
The amorphous copolyester of embodiment 1,2 is cut into suitable size; Extend being higher than under 10～20 ℃ of the second-order transition temperatures; Extension ratio is a twice, and the amorphous copolyester with extend through places the baking oven of differing temps to calculate its shrinking percentage in five minutes again, and it is defined as:
L is that sample is long after oven, l
0Former length for sample
With reference to Fig. 1, the succsinic acid of different concns and 2,6-naphthalene diformic acid dimethyl ester can change the shrinkage temperature of the amorphous copolyester of embodiment 1,2.
Though the present invention discloses as above with preferred embodiment; Right its is not in order to limiting the present invention, anyly has the knack of this art, do not breaking away from the spirit and scope of the present invention; When can doing a little change and retouching, so protection scope of the present invention is when being as the criterion with claim institute restricted portion.
Claims (7)
1. atactic amorphous copolyester, it is to use two kinds of diol monomers and terephthalic acid and is selected from 2,6-naphthalene diformic acid dimethyl ester, 2; 6-naphthalic acid, 2; 7-naphthalic acid, 1,4-naphthalic acid, 2,7-naphthalene diformic acid dimethyl ester, 2; A kind of monomer synthetic of 3-naphthalene diformic acid dimethyl ester or m-phthalic acid (IPA), succsinic acid, propanedioic acid or hexanodioic acid has suc as formula the structure shown in (I):
R
1, R
2Be aromatic series or aliphatic group;
A is 0-0.8, and B is 0-0.8, and C is 0-1, and D is 0-1, and E is 0, and F is 0, wherein C+D＞0.2 and A+B+E+F＜0.8;
Wherein this diol monomer comprises terepthaloyl moietie, 1,3/1,4-cyclohexanedimethanol mixture; This terepthaloyl moietie and 1,3/1, the ratio of 4-cyclohexanedimethanol mixture is 0: 100-70: 30, said 1,3/1,4-cyclohexanedimethanol mixture is the UNOXOL that Dow Chemical Company produces
TM34Diol;
Wherein the limiting viscosity of this amorphous copolyester is greater than 0.5dL/g.
2. atactic amorphous copolyester as claimed in claim 1, wherein the second-order transition temperature of this amorphous copolyester is between-20 to 150 ℃.
3. a film comprises atactic amorphous copolyester, wherein this amorphous copolyester by two kinds of diol monomers and terephthalic acid be selected from 2; 6-naphthalene diformic acid dimethyl ester, 2,6-naphthalic acid, 2,7-naphthalic acid, 1; 4-naphthalic acid, 2; 7-naphthalene diformic acid dimethyl ester, 2, a kind of monomer of 3-naphthalene diformic acid dimethyl ester or m-phthalic acid (IPA), succsinic acid, propanedioic acid or hexanodioic acid synthesizes, and has suc as formula the structure shown in (I):
R
1, R
2Be aromatic series or aliphatic group;
A is 0-0.8, and B is 0-0.8, and C is 0-1, and D is 0-1, and E is 0, and F is 0, wherein C+D＞0.2 and A+B+E+F＜0.8;
Wherein this diol monomer comprises terepthaloyl moietie, 1,3/1,4-cyclohexanedimethanol mixture; This terepthaloyl moietie and 1,3/1, the ratio of 4-cyclohexanedimethanol mixture is 0: 100-70: 30, said 1,3/1,4-cyclohexanedimethanol mixture is the UNOXOL that Dow Chemical Company produces
TM34Diol;
Wherein the limiting viscosity of this amorphous copolyester is greater than 0.5dL/g.
4. film as claimed in claim 3, wherein this film is shrink film or wrapping material.
5. the preparation method of an atactic amorphous copolyester comprises:
Terephthalic acid, terepthaloyl moietie and 1,3/1 are provided, 4-cyclohexanedimethanol mixture;
Provide to be selected from 2 6-naphthalene diformic acid dimethyl ester, 2,6-naphthalic acid, 2; 7-naphthalic acid, 1; 4-naphthalic acid, 2,7-naphthalene diformic acid dimethyl ester, 2, a kind of monomer of 3-naphthalene diformic acid dimethyl ester or m-phthalic acid (IPA), succsinic acid, propanedioic acid or hexanodioic acid; And
Mix this terephthalic acid, terepthaloyl moietie and 1,3/1,4-cyclohexanedimethanol mixture be selected from 2; 6-naphthalene diformic acid dimethyl ester, 2,6-naphthalic acid, 2,7-naphthalic acid, 1; 4-naphthalic acid, 2,7-naphthalene diformic acid dimethyl ester, 2, a kind of monomer of 3-naphthalene diformic acid dimethyl ester or m-phthalic acid (IPA), succsinic acid, propanedioic acid or hexanodioic acid carries out esterification and polycondensation; To form this amorphous copolyester; This terepthaloyl moietie, 1,3/1 wherein, 4-cyclohexanedimethanol mixture is a diol monomer; This terepthaloyl moietie and 1,3/1, the ratio of 4-cyclohexanedimethanol mixture is 0: 100-70: 30; Wherein, said 1,3/1,4-cyclohexanedimethanol mixture is the UNOXOL that Dow Chemical Company produces
TM34Diol,
Wherein the limiting viscosity of this amorphous copolyester is greater than 0.5dL/g.
6. preparation method as claimed in claim 5 wherein also comprises the adding polycondensation catalyst in this polycondensation.
7. preparation method as claimed in claim 6, wherein this polycondensation catalyst comprises the metal catalyst of antimony system, germanium system, tin system, gallium system, aluminium system or its above-mentioned combination.
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| CN103483569B (en) * | 2013-09-29 | 2015-12-09 | 太仓东能环保设备有限公司 | Polyester thermal contraction film of a kind of high flexibility and preparation method thereof |
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