CN105131266B - The polyester copolymer of a kind of main chain containing hindered amine group and preparation method thereof - Google Patents
The polyester copolymer of a kind of main chain containing hindered amine group and preparation method thereof Download PDFInfo
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- CN105131266B CN105131266B CN201510564185.3A CN201510564185A CN105131266B CN 105131266 B CN105131266 B CN 105131266B CN 201510564185 A CN201510564185 A CN 201510564185A CN 105131266 B CN105131266 B CN 105131266B
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Abstract
The invention provides a kind of polyester copolymer of main chain containing hindered amine group, with aromatic acid and aliphatic dihydroxy alcohol and 1 (2' ethoxys) 2,2,6, the piperidine alcohols of 6 tetramethyl 4 carry out polycondensation, wherein 1 (2' ethoxys) 2,2, the mol ratio of the piperidine alcohols of 6,6 tetramethyl 4 and aliphatic dihydroxy alcohol is (0.1:99.9)‑(20:80).Described aromatic acid is terephthalic acid (TPA), 2, and 6 naphthalene diacid, described aliphatic dihydroxy alcohol is ethylene glycol, propane diols, butanediol or cyclohexanediol.Compared with prior art, the advantage of the invention is that：The polyester copolymer of the present invention has the excellent ultraviolet light stability of hindered amine compound, while having excellent mechanical property, overcomes the shortcoming of mechanical properties decrease after polyester addition hindered amine as light stabilizer of the prior art.
Description
Technical field
The present invention relates to a kind of polyester copolymer of the main chain containing hindered amine group with high ultraviolet light stability.
Background technology
Hindered amine as light stabilizer (HALS) is the chemical combination with 2,2,6,6- tetramethyl piperidine groups in a kind of molecular structure
Thing, is obtained a wide range of applications as the UV light stabilizing agent of excellent performance in high polymer material industry.Meanwhile, hindered amine light
Stabilizer is added in high polymer material together with UV absorbers, can produce significant cooperative effect, so that significantly
Improve the UV Aging Resistance of high polymer material.Common hindered amine as light stabilizer has micromolecular compound and polymer electrolyte two
Class.The molecular structural formula of some conventional hindered amine as light stabilizer given below.Wherein, the hindered amine light stabilizer of small molecule type
Agent such as GW-770 and GW-540 etc., it is poor with heat resistance, it is readily volatilized when processing temperature is higher, produce excitant gas
Taste, is easily extracted, and in use easily the shortcomings of migrate.Polymer electrolyte hindered amine stabilizer includes GW-622
With the kind such as GW-944.Wherein, GW-622 is contracted by succinic acid and the tetramethyl -4- piperidine alcohols of 1- (2'- ethoxys) -2,2,6,6-
It is poly-, it is resistance to migration when being characterized in that molecular weight is big, volatility is low, penetrating odor is not produced in process, is used, resistance to
Extraction etc., can assign polymer permanent ultraviolet light stability.
It is such as polyethylene terephthalate (PET), poly- to benzene two however, above-mentioned hindered amine as light stabilizer is used for polyester
Formic acid butanediol ester (PBT), when, there is distinct disadvantage.For example, hindered amine as light stabilizer (such as light stabilizer containing reactive hydrogen
770th, 944 etc.) the notable degraded of polyester is easily caused in process；GW-540 and GW-622 is free of reactive hydrogen, but with gathering
Ester compatibility is not good, and when addition is higher (such as percentage by weight is more than 1%), the mechanical property of polyester article can substantially drop
It is low.Although GW-622 belongs to polyester-based polymer, due to it be with aliphatic dibasic acid and 1- (2'- ethoxys) -2,2,6,
The oligomer of 6- tetramethyl -4- piperidine alcohols polycondensations, molecular weight is paid no attention to than relatively low (3000-4000) with PET compatibility
Think, cause polyester mechanical properties decrease, and it is susceptible to hydrolysis.Meanwhile, GW-622 heat resistances are poor, for example, when being heated to 280 degree
About 3% thermal weight loss can be produced.Therefore, GW-622 is difficult to the use requirement for meeting PET.
The content of the invention
It is an object of the invention to overcome the shortcoming of prior art there is provided polyester copolymer of the main chain containing hindered amine group,
Not only show the outstanding ultraviolet light stability of hindered amine compound, both can individually film forming can also as additive add it is general
In logical polyester material, the outstanding ultraviolet light stability of hindered amine compound is not only shown, and have with general purpose polyester material
There is good compatibility, so that polyester has excellent mechanical performances and ultraviolet light stability concurrently, in addition, also having hydrolytic Resistance
The advantages of good, low volatility, resistance to migration.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of polyester copolymer of main chain containing hindered amine group, its molecular structural formula is as follows：
Wherein, R1It is phenyl ring or naphthalene nucleus, R2It is ethyl, propyl group, butyl or cyclohexyl；
Wherein, m:N=0.1-80:99.9-20.
Specifically, the intrinsic viscosity scope of the polyester copolymer is 0.2-1.2dL/g.
A kind of preparation method of polyester copolymer of main chain containing hindered amine group, comprises the following steps：
1) esterification：By terephthalic acid (TPA) or to naphthalenedicarboxylic acid, aliphatic dihydroxy alcohol and the amine monomers 1- (2'- that are obstructed
Ethoxy) -2,2,6,6- tetramethyl -4- piperidine alcohols and catalyst added in reactor, is heated to 245-265 DEG C of reaction 2-12 small
When；
2) polycondensation reaction：Stabilizer is added in reactor, is 265-295 DEG C in temperature, vacuum is 50-150Pa bars
Polycondensation reaction is carried out under part, reacts 2-12 hours, obtains polyester copolymer；
3) cool down, discharge pelletizing, produces polyester copolymer.
Specifically, the catalyst is tetrabutyl titanate, antimony oxide, antimony acetate or antimony glycol.
Specifically, the stabilizer is trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester or triphenyl phosphate.
Specifically, the terephthalic acid (TPA) or to naphthalenedicarboxylic acid, aliphatic dihydroxy alcohol and amine monomers 1- (the 2'- hydroxyls that are obstructed
Ethyl) -2,2,6,6- tetramethyl -4- piperidine alcohols mol ratio be 100:(0.1-20):(99.9-80).
Specifically, the aliphatic dihydroxy alcohol and the tetramethyl -4- piperazines of amine monomers 1- (2'- ethoxys) -2,2,6,6- that are obstructed
The ratio between the total mole number of pyridine alcohol and the molal quantity of aromatic acid are (100-130):100.
Specifically, the catalyst be terephthalic acid (TPA) or to naphthalenedicarboxylic acid quality 0.01%~0.5%.
Specifically, the addition of the stabilizer is the 0.001%~0.05% of reactant gross mass.
A kind of polyester material of the polyester copolymer containing hindered amine group containing main chain, includes in mass ratio：0-95 parts poly-
Ester section, polyester copolymer and 0.05-3 part UV absorbers of the 5-100 parts of main chains containing hindered amine group.
Specifically, the UV absorbers are Tinuvin 329, Tinuvin 234, Tinuvin 326, Tinuvin
350、Tinuvin 320、Tinuvin328、Tinuvin 360、Tinuvin 327、Tinuvin UV-P、UV-3638F、UV-
1577th, the one or more in UV-1164 and triazine -425.
The beneficial effects of the invention are as follows：
1) be connected in polyester copolymer of the invention by histamine group by copolymerization mode on polyester backbone, make its with it is general
Logical polyester has good compatibility, so can more uniformly be disperseed in the polyester by histamine group.Even if by histamine base
Content only 0.1% of the group in polyester material also can make polyester have good ultraviolet light stability；Meanwhile, when by histamine base
When mass contg is high, 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 invention has good processing stability, its 5% thermal weight loss
Temperature is up to 380 DEG C, and (280-290 DEG C) volatility is extremely low in polyester extrusion, do not produce penetrating odor.
3) polyester copolymer containing hindered amine group of the invention has excellent resistance to migration and resistance to extractibility, washes to it
Uvioresistant performance is substantially without influence.
Embodiment
Presently in connection with embodiment, the present invention is further detailed explanation.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of polyester copolymer of main chain containing hindered amine group, its molecular structural formula is as follows：
Wherein, R1It is phenyl ring or naphthalene nucleus, R2It is ethyl, propyl group, butyl or cyclohexyl；
Wherein, m:N=0.1-80:99.9-20.
Specifically, the intrinsic viscosity scope of polyester copolymer is 0.2-1.2dL/g.
A kind of preparation method of polyester copolymer of main chain containing hindered amine group, comprises the following steps：
1) esterification：By terephthalic acid (TPA) or to naphthalenedicarboxylic acid, aliphatic dihydroxy alcohol and the amine monomers 1- (2'- that are obstructed
Ethoxy) -2,2,6,6- tetramethyl -4- piperidine alcohols and catalyst added in reactor, is heated to 245-265 DEG C of reaction 2-12 small
When；Terephthalic acid (TPA) or to naphthalenedicarboxylic acid, aliphatic dihydroxy alcohol and the amine monomers 1- that is obstructed (2'- ethoxys) -2,2,6,6- four
The mol ratio of methyl -4- piperidine alcohols is 100:(0.1-20):(99.9-80)；Aliphatic dihydroxy alcohol and the amine monomers 1- (2'- that are obstructed
Ethoxy) total mole number of -2,2,6,6- tetramethyl -4- piperidine alcohols and the ratio between the molal quantity of aromatic acid be (100-
130):100；Catalyst be terephthalic acid (TPA) or to naphthalenedicarboxylic acid quality 0.01%~0.5%；
2) polycondensation reaction：Stabilizer is added in reactor, is 265-295 DEG C in temperature, vacuum is 50-150Pa bars
Polycondensation reaction is carried out under part, reacts 2-12 hours, obtains polyester copolymer；The addition of stabilizer is reactant gross mass
0.001%~0.05%；
3) cool down, discharge pelletizing, produces polyester copolymer.
Specifically, the catalyst is tetrabutyl titanate, antimony oxide, antimony acetate or antimony glycol.
Specifically, the stabilizer is trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester or triphenyl phosphate.
The mass fraction of each component of 1- embodiments 10, the intrinsic viscosity such as institute of table 1 are implemented in the synthesis of polyester copolymer of the present invention
Show.
Table 1：
By polyester copolymer and polyester of the main chain made from the embodiment of the present invention 1~10 of different content containing hindered amine group
Section, heat stabilizer four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, UV absorbers triazine-
425, i.e. 2- (2 '-hydroxyl -4 '-octyloxyphenyl) -4,6- bis- (2 ", 4 "-xylyl) -1,3,5-triazines, blended, extrusion
Machine granulation obtains embodiment 11-30 compounds.
By the commodity hindered amine as light stabilizer of different content and polyester slice, heat stabilizer four [β-(3,5- di-t-butyls-
4- hydroxy phenyls) propionic acid] pentaerythritol ester, UV absorbers Tinuvin360, blended, extruder granulation mixed
Material, obtains comparative example 1-13 compounds.Specific component is shown in Table 2 as mass fraction.
Table 2：
Note：Polyester slice type：(A) polyethylene terephthalate；(B) PTT；(C) gather
Mutual-phenenyl two acid bromide two alcohol ester；(D) cyclohexanedimethanol's diol ester；(E) polyethylene naphthalate.
Add mixture into extruder after melting by die head extrude slab be molded, through biaxial tension (draw ratio=
3.4) embodiment 11 is made to the biaxial stretching polyester film of embodiment 20 in thermal finalization, cooling, winding, and the thickness of film is 188 ± 5 μ
M, breadth are 3.4 meters.Embodiment 7 to the tensile property of the polyester film of embodiment 20 is tested with electronic universal tester；
(wavelength is arrived ultraviolet light stability reference standard IEC61215-2005 measurements ultraviolet light irradiation before and after polyester film washing in 280nm
The ultraviolet radioactive of 385nm scopes is 5kWhm-2) the elongation at break conservation rate of polyester film and yellowness index Δ YI evaluations afterwards,
Specific data are shown in Table 3.The method of washing is to take out polyester film immersion after 2 hours in deionized water to dry 2 hours at 60 degree.
Table 3：
From table 3, can preferably it be carried with commodity hindered amine as light stabilizer with polyester copolymer ratio produced by the present invention
The mechanical property and ultraviolet light stability of superpolyester biaxial stretching film, have a significant effect.Meanwhile, work in-process also found,
Polyester copolymer produced by the present invention, which has in excellent processing stability, process, does not produce penetrating odor.
Using the above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to its technical scope is determined according to right.
Claims (10)
1. a kind of preparation method of polyester copolymer of main chain containing hindered amine group, comprises the following steps：
1) esterification：By terephthalic acid (TPA) or to naphthalenedicarboxylic acid, aliphatic dihydroxy alcohol and the amine monomers 1- that is obstructed (2'- hydroxyl second
Base) -2,2,6,6- tetramethyl -4- piperidine alcohols and catalyst add in reactor, be heated to 245-265 DEG C and react 2-12 hours；
2) polycondensation reaction：Stabilizer is added in reactor, is 265-295 DEG C in temperature, vacuum is under the conditions of 50-150Pa
Polycondensation reaction is carried out, reacts 2-12 hours, obtains polyester copolymer；
3) cool down, discharge pelletizing, produces polyester copolymer,
The stabilizer is trimethyl phosphate, triethyl phosphate, tricresyl phosphate propyl ester or triphenyl phosphate.
2. a kind of preparation method of polyester copolymer of main chain containing hindered amine group as claimed in claim 1, it is characterised in that：
The molecular structural formula of polyester copolymer of the main chain containing hindered amine group is as follows：
Wherein, R1It is phenyl ring or naphthalene nucleus, R2It is ethyl, propyl group, butyl or cyclohexyl；
Wherein, m:N=0.1-80:99.9-20.
3. a kind of preparation method of polyester copolymer of main chain containing hindered amine group as claimed in claim 2, it is characterised in that：
The intrinsic viscosity scope of the polyester copolymer is 0.2-1.2dL/g.
4. a kind of preparation method of polyester copolymer of main chain containing hindered amine group as claimed in claim 1, it is characterised in that：
The catalyst is tetrabutyl titanate, antimony oxide, antimony acetate or antimony glycol.
5. a kind of preparation method of polyester copolymer of main chain containing hindered amine group as claimed in claim 1, it is characterised in that：
The terephthalic acid (TPA) or to naphthalenedicarboxylic acid, aliphatic dihydroxy alcohol and the amine monomers 1- that is obstructed (2'- ethoxys) -2,2,6,6- four
The mol ratio of methyl -4- piperidine alcohols is 100:(0.1-20):(99.9-80).
6. a kind of preparation method of polyester copolymer of main chain containing hindered amine group as claimed in claim 1, it is characterised in that：
The total mole number of the aliphatic dihydroxy alcohol and the amine monomers 1- that is obstructed (2'- ethoxys) -2,2,6,6- tetramethyl -4- piperidine alcohols with
The ratio between molal quantity of aromatic acid is (100-130):100.
7. a kind of preparation method of polyester copolymer of main chain containing hindered amine group as claimed in claim 1, it is characterised in that：
The catalyst be terephthalic acid (TPA) or to naphthalenedicarboxylic acid quality 0.01%~0.5%.
8. a kind of preparation method of polyester copolymer of main chain containing hindered amine group as claimed in claim 1, it is characterised in that：
The addition of the stabilizer is the 0.001%~0.05% of reactant gross mass.
9. a kind of polyester material of the polyester copolymer containing hindered amine group containing main chain, includes in mass ratio：0-95 parts of polyester
Section, polyester copolymer and 0.05-3 part UV absorbers of the 5-100 parts of main chains containing hindered amine group, the main chain, which contains, to be obstructed
The polyester copolymer of amine groups is polyethylene terephthalate copolymer of a kind of main chain containing hindered amine group according to claim any one of 1-8
Obtained by the preparation method of thing.
10. a kind of polyester material of the polyester copolymer containing hindered amine group containing main chain as claimed in claim 9, its feature exists
In：The UV absorbers are Tinuvin 329, Tinuvin 234, Tinuvin 326, Tinuvin 350, Tinuvin
320、Tinuvin328、Tinuvin 360、Tinuvin 327、Tinuvin UV-P、UV-3638F、UV-1577、UV-1164
With the one or more in triazine -425.
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| CN201510564185.3A CN105131266B (en) | 2015-09-07 | 2015-09-07 | The polyester copolymer of a kind of main chain containing hindered amine group and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4609698A (en) * | 1983-03-21 | 1986-09-02 | Ciba-Geigy Corporation | Oligoesters containing polyalkylpiperidine groups |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0226538B1 (en) * | 1985-12-06 | 1991-09-11 | Ciba SC Holding AG | Light stabilized polymer microparticles |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4609698A (en) * | 1983-03-21 | 1986-09-02 | Ciba-Geigy Corporation | Oligoesters containing polyalkylpiperidine groups |
| 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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