CN105131266A - Polyester copolymer with hindered amine group-containing main chain and preparation method thereof - Google Patents
Polyester copolymer with hindered amine group-containing main chain and preparation method thereof Download PDFInfo
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- CN105131266A CN105131266A CN201510564185.3A CN201510564185A CN105131266A CN 105131266 A CN105131266 A CN 105131266A CN 201510564185 A CN201510564185 A CN 201510564185A CN 105131266 A CN105131266 A CN 105131266A
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Abstract
The invention provides a polyester copolymer with hindered amine group-containing main chain, polycondensation is carried out for aromatic acids, aliphatic diols and 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-pipradrol, wherein, the mol ratio between 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl-4-pipradrol and aliphatic diols is (0.1:99.9)-(20:80). The aromatic acids contain terephthalic acid and 2,6-naphthalenedicarboxylic acid, and the aliphatic diols contain glycol, propylene glycol, butylene glycol or cyclohexanediol. Compared with the prior art, the invention has the advantages that the polyester copolymer of the present invention has excellent ultraviolet light stability of the hindered amine compound, simultaneously has excellent mechanical properties, and overcomes the disadvantage that in the prior art after the polyester is added with the hindered amine light stabilizing agent, the mechanical properties decrease.
Description
Technical field
The present invention relates to a kind of polyester copolymer of main chain containing hindered amine group with high ultraviolet light stability.
Background technology
Hindered amine as light stabilizer (HALS) is the compound with 2,2,6,6-tetramethyl piperidine group in a kind of molecular structure, and the UV light stabilizing agent as excellent performance obtains a wide range of applications in macromolecular material industry.Meanwhile, hindered amine as light stabilizer adds in macromolecular material together with ultraviolet absorbers, can produce significant synergistic effect, thus increases substantially the UV Aging Resistance of macromolecular material.Common hindered amine as light stabilizer has micromolecular compound and polymer two class.
following formulagive the molecular structural formula of some conventional hindered amine as light stabilizer.Wherein, the hindered amine as light stabilizer of small molecules type, as GW-770 and GW-540 etc., has thermotolerance poor, easily volatilizees when processing temperature is higher, produces irritating smell, is easily extracted, and in use easily the shortcomings such as migration occurs.Polymer hindered amine stabilizer comprises the kinds such as GW-622 and GW-944.Wherein, GW-622 is by succinic acid and 1-(2'-hydroxyethyl)-2,2,6, the polycondensation of 6-tetramethyl--4-piperidine alcohols, be characterized in that molecular weight is large, volatility is low, do not produce irritating smell in the course of processing, resistance to migration, resistance to extraction etc. when using, the ultraviolet light stability that polymkeric substance is permanent can be given.
But, above-mentioned hindered amine as light stabilizer be used for polyester, as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), time, there is distinct disadvantage.Such as, the hindered amine as light stabilizer (as photostabilizer 770,944 etc.) containing active hydrogen easily causes the remarkable degraded of polyester in the course of processing; GW-540 and GW-622 does not contain active hydrogen, but not good with polyester consistency, and when addition is higher (as weight percent is greater than 1%), the mechanical property of polyester article can obviously reduce.Although GW-622 belongs to polyester polymer, but because it is with aliphatic dibasic acid and 1-(2'-hydroxyethyl)-2,2,6, the oligopolymer of 6-tetramethyl--4-piperidine alcohols polycondensation, molecular weight ratio lower (3000-4000), undesirable with the consistency of PET, cause polyester mechanical properties decrease, and be easy to hydrolysis.Meanwhile, GW-622 thermotolerance is poor, such as, can produce the thermal weight loss of about 3% when being heated to 280 degree.Therefore, GW-622 is difficult to the service requirements meeting PET.
Summary of the invention
The object of the invention is to the shortcoming overcoming prior art, main chain is provided to contain the polyester copolymer of hindered amine group, not only show the outstanding ultraviolet light stability of hindered amine compound, both can film forming also can add in conventional polyester material as additive separately, not only show the outstanding ultraviolet light stability of hindered amine compound, and with general purpose polyester material, there is good consistency, thus make polyester have excellent mechanical performances and ultraviolet light stability concurrently, in addition, also there is the advantages such as resistant to hydrolysis performance is good, volatility is low, resistance to migration.
The technical solution adopted for the present invention to solve the technical problems is:
Main chain is containing a polyester copolymer for hindered amine group, and its molecular structural formula is as follows:
Wherein, R
1phenyl ring or naphthalene nucleus, R
2ethyl, propyl group, butyl or cyclohexyl;
Wherein, m:n=0.1-80:99.9-20.
Particularly, the intrinsic viscosity scope of described polyester copolymer is 0.2-1.2dL/g.
Main chain, containing a preparation method for the polyester copolymer of hindered amine group, comprises the steps:
1) esterification: by terephthalic acid or to naphthalic acid, aliphatic dihydroxy alcohol and hindered amine monomer 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl--4-piperidine alcohols and catalyzer add in reactor, are heated to 245-265 DEG C of reaction 2-12 hour;
2) polycondensation: add stablizer in reactor is 265-295 DEG C in temperature, and vacuum tightness is carry out polycondensation under 50-150Pa condition, and reaction 2-12 hour, obtains polyester copolymer;
3) cool, discharging pelletizing, obtains polyester copolymer.
Particularly, described catalyzer is tetrabutyl titanate, antimonous oxide, antimony acetate or antimony glycol.
Particularly, described stablizer is trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester or triphenylphosphate.
Particularly, described terephthalic acid or the mol ratio to naphthalic acid, aliphatic dihydroxy alcohol and hindered amine monomer 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl--4-piperidine alcohols are 100:(0.1-20): (99.9-80).
Particularly, the total mole number of described aliphatic dihydroxy alcohol and hindered amine monomer 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl--4-piperidine alcohols is (100-130) with the ratio of the mole number of aromatic acid: 100.
Particularly, described catalyzer be terephthalic acid or to naphthalic acid quality 0.01% ~ 0.5%.
Particularly, the addition of described stablizer is 0.001% ~ 0.05% of reactant total mass.
Containing the polyester material of main chain containing the polyester copolymer of hindered amine group, comprise in mass ratio: the polyester slice of 0-95 part, 5-100 part main chain contain polyester copolymer and 0.05-3 part ultraviolet absorbers of hindered amine group.
Particularly, described ultraviolet absorbers is one or more in Tinuvin329, Tinuvin234, Tinuvin326, Tinuvin350, Tinuvin320, Tinuvin328, Tinuvin360, Tinuvin327, TinuvinUV-P, UV-3638F, UV-1577, UV-1164 and triazine-425.
The invention has the beneficial effects as follows:
1) be connected on polyester backbone by histamine group by copolymerization mode in polyester copolymer of the present invention, make itself and conventional polyester have good consistency, so can more be evenly dispersed in polyester by histamine group.Even if only have 0.1% polyester also can be made to have good ultraviolet light stability by the content of histamine group in polyester material; Meanwhile, when by histamine group content height, polyester not only has excellent uvioresistant performance but also does not sacrifice the mechanical property of polyester.
2) polyester copolymer containing hindered amine group of the present invention has good processing stability, its 5% thermal weight loss temperatures as high 380 DEG C, in polyester extrusion (280-290 DEG C) volatility extremely low, do not produce irritating smell.
3) polyester copolymer containing hindered amine group of the present invention has excellent resistance to migration and resistance to extractibility, washes its uvioresistant performance substantially without impact.
Embodiment
The present invention is further detailed explanation in conjunction with the embodiments now.
The technical solution adopted for the present invention to solve the technical problems is:
Main chain is containing a polyester copolymer for hindered amine group, and its molecular structural formula is as follows:
Wherein, R
1phenyl ring or naphthalene nucleus, R
2ethyl, propyl group, butyl or cyclohexyl;
Wherein, m:n=0.1-80:99.9-20.
Particularly, the intrinsic viscosity scope of polyester copolymer is 0.2-1.2dL/g.
Main chain, containing a preparation method for the polyester copolymer of hindered amine group, comprises the steps:
1) esterification: by terephthalic acid or to naphthalic acid, aliphatic dihydroxy alcohol and hindered amine monomer 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl--4-piperidine alcohols and catalyzer add in reactor, are heated to 245-265 DEG C of reaction 2-12 hour; Terephthalic acid or be 100:(0.1-20 to the mol ratio of naphthalic acid, aliphatic dihydroxy alcohol and hindered amine monomer 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl--4-piperidine alcohols): (99.9-80); The total mole number of aliphatic dihydroxy alcohol and hindered amine monomer 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl--4-piperidine alcohols is (100-130) with the ratio of the mole number of aromatic acid: 100; Catalyzer be terephthalic acid or to naphthalic acid quality 0.01% ~ 0.5%;
2) polycondensation: add stablizer in reactor is 265-295 DEG C in temperature, and vacuum tightness is carry out polycondensation under 50-150Pa condition, and reaction 2-12 hour, obtains polyester copolymer; The addition of stablizer is 0.001% ~ 0.05% of reactant total mass;
3) cool, discharging pelletizing, obtains polyester copolymer.
Particularly, described catalyzer is tetrabutyl titanate, antimonous oxide, antimony acetate or antimony glycol.
Particularly, described stablizer is trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester or triphenylphosphate.
Massfraction, the intrinsic viscosity of 1-embodiment 10 each component are implemented in the synthesis of polyester copolymer of the present invention
as table 1shown in.
table 1:
By main chain obtained for the embodiment of the present invention 1 ~ 10 of different content containing the polyester copolymer of hindered amine group and polyester slice, thermo-stabilizer four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, ultraviolet absorbers triazine-425, i.e. 2-(2 '-hydroxyl-4 '-octyloxyphenyl)-4,6-bis-(2 "; 4 "-xylyl)-1,3,5-triazine, obtains embodiment 11-30 compound through mixing, forcing machine granulation.
By the commodity hindered amine as light stabilizer of different content and polyester slice, thermo-stabilizer four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, ultraviolet absorbers Tinuvin360, obtain compound through mixing, forcing machine granulation, obtain comparative example 1-13 compound.Concrete component is shown in by massfraction
table 2.
table 2:
Note: polyester slice type: (A) polyethylene terephthalate; (B) Poly(Trimethylene Terephthalate); (C) polybutylene terephthalate; (D) cyclohexanedimethanol's diol ester; (E) polyethylene naphthalate.
Compound being added forcing machine, after melting, extrude slab by die head shaping, through two-way stretch (stretch ratio=3.4) heat setting type, cooling, rolling obtain the biaxial stretching polyester film of embodiment 11 to embodiment 20, and the thickness of film is 188 ± 5 μm, fabric width is 3.4 meters.Test with the tensile property of electronic universal tester to the polyester film of embodiment 7 to embodiment 20; Ultraviolet light stability reference standard IEC61215-2005 before and after polyester film washing measure ultraviolet light irradiation (wavelength is 5kWhm-2 at the uv-radiation of 280nm to 385nm scope) afterwards the elongation at break conservation rate of polyester film and yellowness index Δ YI evaluate, concrete data are shown in
table 3.The method of washing is soaked by polyester film to take out 60 degree of dryings 2 hours after 2 hours in deionized water.
table 3:
By
table 3visible, the polyester copolymer ratio commodity hindered amine as light stabilizer obtained with the present invention can improve mechanical property and the ultraviolet light stability of polyester bistretched film better, has a significant effect.Meanwhile, work in-process also finds, the polyester copolymer that the present invention obtains has excellent processing stability, does not produce irritating smell in the course of processing.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must
according to claimscope determines its technical scope.
Claims (11)
1. main chain is containing a polyester copolymer for hindered amine group, and its molecular structural formula is as follows:
Wherein, R
1phenyl ring or naphthalene nucleus, R
2ethyl, propyl group, butyl or cyclohexyl;
Wherein, m:n=0.1-80:99.9-20.
2. a kind of main chain as claimed in claim 1 is containing the polyester copolymer of hindered amine group, it is characterized in that: the intrinsic viscosity scope of described polyester copolymer is 0.2-1.2dL/g.
3. main chain is containing a preparation method for the polyester copolymer of hindered amine group, comprises the steps:
1) esterification: by terephthalic acid or to naphthalic acid, aliphatic dihydroxy alcohol and hindered amine monomer 1-(2'-hydroxyethyl)-2,2,6,6-tetramethyl--4-piperidine alcohols and catalyzer add in reactor, are heated to 245-265 DEG C of reaction 2-12 hour;
2) polycondensation: add stablizer in reactor is 265-295 DEG C in temperature, and vacuum tightness is carry out polycondensation under 50-150Pa condition, and reaction 2-12 hour, obtains polyester copolymer;
3) cool, discharging pelletizing, obtains polyester copolymer.
4. a kind of main chain as claimed in claim 3 is containing the preparation method of the polyester copolymer of hindered amine group, it is characterized in that: described catalyzer is tetrabutyl titanate, antimonous oxide, antimony acetate or antimony glycol.
5. a kind of main chain as claimed in claim 3 is containing the preparation method of the polyester copolymer of hindered amine group, it is characterized in that: described stablizer is trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester or triphenylphosphate.
6. a kind of main chain as claimed in claim 3 is containing the preparation method of the polyester copolymer of hindered amine group, it is characterized in that: described terephthalic acid or to naphthalic acid, aliphatic dihydroxy alcohol and hindered amine monomer 1-(2'-hydroxyethyl)-2,2, the mol ratio of 6,6-tetramethyl--4-piperidine alcohols is 100:(0.1-20): (99.9-80).
7. a kind of main chain as claimed in claim 3 is containing the preparation method of the polyester copolymer of hindered amine group, it is characterized in that: described aliphatic dihydroxy alcohol and hindered amine monomer 1-(2'-hydroxyethyl)-2,2, the total mole number of 6,6-tetramethyl--4-piperidine alcohols is (100-130) with the ratio of the mole number of aromatic acid: 100.
8. a kind of main chain as claimed in claim 3 is containing the preparation method of polyester copolymer of hindered amine group, it is characterized in that: described catalyzer be terephthalic acid or to naphthalic acid quality 0.01% ~ 0.5%.
9. a kind of main chain as claimed in claim 3 is containing the preparation method of the polyester copolymer of hindered amine group, it is characterized in that: the addition of described stablizer is 0.001% ~ 0.05% of reactant total mass.
10. containing the polyester material of the main chain described in claim 1 or 2 containing the polyester copolymer of hindered amine group, comprise in mass ratio: the polyester slice of 0-95 part, 5-100 part main chain contain polyester copolymer and 0.05-3 part ultraviolet absorbers of hindered amine group.
11. is a kind of containing the polyester material of polyester copolymer of main chain containing hindered amine group as claimed in claim 10, it is characterized in that: described ultraviolet absorbers is one or more in Tinuvin329, Tinuvin234, Tinuvin326, Tinuvin350, Tinuvin320, Tinuvin328, Tinuvin360, Tinuvin327, TinuvinUV-P, UV-3638F, UV-1577, UV-1164 and triazine-425.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110392718A (en) * | 2017-03-30 | 2019-10-29 | 富士胶片株式会社 | Light curable inks composition and image forming method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4609698A (en) * | 1983-03-21 | 1986-09-02 | Ciba-Geigy Corporation | Oligoesters containing polyalkylpiperidine groups |
| JPH07252435A (en) * | 1985-12-06 | 1995-10-03 | Ciba Geigy Ag | Dispersion coating composition containing microparticle of light stabilized polymer |
| CN104479122A (en) * | 2014-12-01 | 2015-04-01 | 金发科技股份有限公司 | Stable-color fatty-aromatic copolyester and preparation method thereof |
| CN104592504A (en) * | 2015-01-21 | 2015-05-06 | 苏州飞翔新材料研究院有限公司 | Method for preparing light stabilizer 622 |
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2015
- 2015-09-07 CN CN201510564185.3A patent/CN105131266B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4609698A (en) * | 1983-03-21 | 1986-09-02 | Ciba-Geigy Corporation | Oligoesters containing polyalkylpiperidine groups |
| JPH07252435A (en) * | 1985-12-06 | 1995-10-03 | Ciba Geigy Ag | Dispersion coating composition containing microparticle of light stabilized polymer |
| CN104479122A (en) * | 2014-12-01 | 2015-04-01 | 金发科技股份有限公司 | Stable-color fatty-aromatic copolyester and preparation method thereof |
| CN104592504A (en) * | 2015-01-21 | 2015-05-06 | 苏州飞翔新材料研究院有限公司 | Method for preparing light stabilizer 622 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110392718A (en) * | 2017-03-30 | 2019-10-29 | 富士胶片株式会社 | Light curable inks composition and image forming method |
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