CN103709612B - Thermoplastic polyester elastomer of a kind of ultraviolet resistance and its preparation method and application - Google Patents
Thermoplastic polyester elastomer of a kind of ultraviolet resistance and its preparation method and application Download PDFInfo
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- CN103709612B CN103709612B CN201310628511.3A CN201310628511A CN103709612B CN 103709612 B CN103709612 B CN 103709612B CN 201310628511 A CN201310628511 A CN 201310628511A CN 103709612 B CN103709612 B CN 103709612B
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Abstract
The invention belongs to thermoplastic polyester elastomer technical field, disclose thermoplastic polyester elastomer of a kind of ultraviolet resistance and its preparation method and application.This thermoplastic polyester elastomer comprises the component of following parts by weight: thermoplastic polyester 100 parts; Phenolic antioxidant 0 ~ 0.4 part; Amine antioxidants 0 ~ 0.4 part; Sulphur compounds 0.1 ~ 0.4 part; Hindered amine UV stabilizer 0.1 ~ 0.3 part.The present invention utilizes the synergy of oxidation inhibitor and stablizer, utilizes sulphur compounds as auxiliary antioxidant, effectively can improve the color inhibition ability of material, thus reaches the effect of heat-resisting, resistance to ultraviolet, color inhibition.The present invention not only increases thermotolerance and the ultraviolet resistance ability of thermoplastic polyester elastomer, also can improve its heat-proof water ability and anti-yellowing property simultaneously.The present invention, under the prerequisite of not adding carbon black, obtains good uvioresistant ability effect, the thermoplastic polyester elastomer obtained be can be applicable in light-coloured prods.
Description
Technical field
The invention belongs to thermoplastic polyester elastomer technical field, particularly a kind of thermoplastic polyester elastomer and its preparation method and application of ultraviolet resistance.
Background technology
The over-all propertieies such as thermoplastic polyester elastomer has the elasticity of rubber, the use temperature of outstanding physical strength, excellent rebound resilience and broadness, are widely used in fields such as automotive part, flexible pipe, electric wire, stationery sports goodss.
Thermoplastic polyester elastomer is hard section with polybutylene terephthalate, and polytetrahydrofuran is the segmented copolymer of soft section.Easily aging under high temperature and uviolizing condition.Usually by adding the stability of phenols and/or amine antioxidants, UV light stabilizing agent and carbon black raising thermoplastic polyester elastomer.Adding of carbon black causes goods to be black, limits its application in light color article.If do not use carbon black, goods are under UV-irradiation, and surface color can deepen, and affect the outward appearance of goods.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art with not enough, primary and foremost purpose of the present invention is the thermoplastic polyester elastomer providing a kind of ultraviolet resistance.
Another object of the present invention is the preparation method of the thermoplastic polyester elastomer providing above-mentioned ultraviolet resistance.
Still a further object of the present invention is to provide the application of the thermoplastic polyester elastomer of above-mentioned ultraviolet resistance in automotive part, electric wire and stationery sports goods.
Object of the present invention is realized by following proposal:
A thermoplastic polyester elastomer for ultraviolet resistance, comprises the component of following parts by weight:
Described thermoplastic polyester refers to polybutylene terephthalate-co-polytetrahydrofuran multipolymer.
Preferably, in described polybutylene terephthalate-co-polytetrahydrofuran multipolymer, the content of polytetrahydrofuran is 25 ~ 60wt%.
More preferably, described polytetrahydrofuran refer to molecular weight be 1000 and molecular weight be at least one in the polytetrahydrofuran of 2000.
Described phenolic antioxidant refers to two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxybenzene propionic acid amide), 1,3,5-trimethylammonium-2,4,6-tri--(4 '-hydroxyl-3 ', 5 '-di-t-butyl benzyl) benzene, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) at least one in triketone and isocyanuric acid (3,5-di-tert-butyl-4-hydroxyl benzyl ester).
Described amine antioxidants refers to N, N '-two-betanaphthyl-Ursol D, N-phenyl-a-naphthylamine, 4,4 '-bis-(alpha, alpha-dimethylbenzyl) pentanoic, N, N ' at least one in-diphenyl-para-phenylene diamine.
Preferably, in the structure of described amine antioxidants, nitrogen-atoms is directly connected with phenyl ring.
Described sulphur compounds refers to the monothioester at least containing two propionic esters, as at least one in Tyox B, thio-2 acid two (13) ester, thio-2 acid two (14) ester, thio-2 acid two (18) ester.
In order to obtain better effect, preferably, in the structure of described sulphur compounds, the β-C atom of two propionic esters is connected by S atom.
Described hindered amine UV stabilizer refers at least one in TINUVIN144 and TINUVIN622.
Present invention also offers the preparation method of the thermoplastic polyester elastomer of above-mentioned ultraviolet resistance, comprise following concrete steps:
Dimethyl terephthalate (DMT), 1,4-butyleneglycol, polytetrahydrofuran, catalyst Ti acid esters mix, esterification, polycondensation obtain thermoplastic polyester, mix with phenolic antioxidant, amine antioxidants, sulphur compounds and hindered amine ultraviolet light stablizer again, obtain the thermoplastic polyester elastomer of ultraviolet resistance;
Or dimethyl terephthalate (DMT), 1,4-butyleneglycol, polytetrahydrofuran, catalyst Ti acid esters mix, esterification, then mix with phenolic antioxidant, amine antioxidants, sulphur compounds and hindered amine ultraviolet light stablizer, polycondensation, obtains the thermoplastic polyester elastomer of ultraviolet resistance.
The reaction conditions of described esterification is react 1 ~ 3h at 180 ~ 210 DEG C.
The reaction conditions of described polycondensation is react 2 ~ 4h at 220 ~ 250 DEG C.
The thermoplastic polyester elastomer of above-mentioned ultraviolet resistance can be used for the fields such as automotive part, electric wire and stationery sports goods.
Mechanism of the present invention is:
Be used alone phenols or amine antioxidants, can play heat-resisting effect, xanthochromia performance and resistance to ultraviolet ability can not improve; Use hindered amine ultraviolet light stablizer can improve uvioresistant ability, resistance toheat can not improve; The present invention utilizes the synergy of oxidation inhibitor and stablizer, utilizes sulphur compounds as auxiliary antioxidant, effectively can improve the color inhibition ability of material, thus reaches the effect of heat-resisting, resistance to ultraviolet, color inhibition.Can reach ideal role in the various performance parameters of amount ranges inner thermoplastic polyester elastomer of the present invention, when each amounts of components is prescribed a time limit lower than lower, then heat-resisting, the resistance to ultraviolet of the thermoplastic polyester elastomer obtained, anti-yellowing property do not reach desirable effect; When each amounts of components is prescribed a time limit higher than upper, system can be caused unstable, cause the precipitation as stablizer etc., and reduce the mechanical property of material.
The present invention, relative to prior art, has following advantage and beneficial effect:
(1) the present invention not only increases thermotolerance and the ultraviolet resistance ability of thermoplastic polyester elastomer, also can improve its heat-proof water ability and anti-yellowing property simultaneously.
(2) the present invention is under the prerequisite of not adding carbon black, obtains good uvioresistant ability effect, the thermoplastic polyester elastomer obtained be can be applicable in light-coloured prods.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Testing method:
Limiting viscosity: with phenol/orthodichlorobenzene (60/40wt/wt) for solvent, probe temperature is 25 DEG C, and Ubbelohde viscometer records;
Mechanical property is tested according to GB/T1040;
Yellowness index: produce ce7000 type color measurement instrument with X. Rite Inc. and measure.Get 140 DEG C of thermal ageing sample tests after 72 hours.B value is less, shows that anti-yellowing property is better.
Resistance toheat: mechanical stretch batten is placed in an oven, carries out thermal ageing at 140 DEG C.The time t of green strength 50% is dropped to by tensile strength
1represent resistance toheat.T
1be worth larger, show that resistance toheat is better.
Hydrolysis ability: be immersed in the distilled water of boiling by mechanical stretch batten, drops to the time t of 50% of green strength by tensile strength
2represent hydrolysis ability.T
2be worth larger, show that hydrolysis ability is stronger.
Ultraviolet-resistant performance: be placed on by mechanical stretch batten in ultraviolet ageing case, at 65 DEG C, relative humidity is 65%, and irradiance is 0.55W/m
2carry out ultraviolet light and aging under 340nm condition, declining by tensile strength causes the time t of green strength 50%
3represent ultraviolet-resistant performance.T
3be worth larger, show that ultraviolet-resistant performance is stronger
Material Source used in the following example can purchase available material on market, wherein:
Terephthalic acid: raise sub-petrochemical industry and produce, fibre-grade.
Dimethyl terephthalate (DMT): Japanese Supreme Being people produces, top grade product.
BDO: Shanxi three-dimensional is produced, top grade product.
Polytetrahydrofuran 1000:PTG company produces.
Polytetrahydrofuran 2000:PTG company produces.
Isopropyl titanate: commercially available analytical pure.
Phenolic antioxidant, amine antioxidants, sulphur compounds are commercially available analytical pure.
TINUVIN144, TINUVIN622 are BASF AG's product.
Embodiment 1: the preparation of the thermoplastic polyester elastomer of ultraviolet resistance
By dimethyl terephthalate (DMT) 1.94Kg, 1,4-butyleneglycol 1.8Kg, polytetrahydrofuran 20001.5Kg drop in reactor, fall the air in reactor with nitrogen replacement after, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 3g, be warming up to 180 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches 640g, add two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine 7g, Tyox B 3.5g, TINUVIN1447g, and be warming up to 250 DEG C gradually, at reacting kettle inner pressure lower than under 30Pa condition, polyase 13 h.In reactor, be filled with high pure nitrogen, obtain thermoplastic polyester elastomer through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as P1.
Embodiment 2: the preparation of the thermoplastic polyester elastomer of ultraviolet resistance
By dimethyl terephthalate (DMT) 1.94Kg, 1,4-butyleneglycol 1.8Kg, polytetrahydrofuran 10001.0Kg drop in reactor, fall the air in reactor with nitrogen replacement after, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 3g, be warming up to 210 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches 640g, and be warming up to 245 DEG C gradually, at reacting kettle inner pressure lower than under 30Pa condition, polyase 13 h.Add thio-2 acid two (18) ester 6g, N, N '-two-betanaphthyl-Ursol D 6g, TINUVIN6223g, in reactor, be filled with high pure nitrogen, obtain thermoplastic polyester elastomer through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as P2.
Embodiment 3: the preparation of the thermoplastic polyester elastomer of ultraviolet resistance
By thermoplastic polyester elastomer (wherein polytetrahydrofuran-1000 content is 25wt%) 10Kg, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxybenzene propionic acid amide) 40g, thio-2 acid two (13) ester 40g, TINUVIN14410g, TINUVIN62210g, mix in rear input twin screw extruder, 200 ~ 235 DEG C extrude, tie rod, polyester elastomer after pelletizing, be labeled as P3.
Embodiment 4: the preparation of the thermoplastic polyester elastomer of ultraviolet resistance
By thermoplastic polyester elastomer (wherein polytetrahydrofuran-2000 content is 60wt%) 10Kg, 4,4 '-bis-(α, α-dimethylbenzyl) pentanoic 40g, Tyox B 30g, TINUVIN62230g mixes in rear input twin screw extruder, 200 ~ 235 DEG C extrude, polyester elastomer after tie rod pelletizing, be labeled as P4.
Embodiment 5: the preparation of the thermoplastic polyester elastomer of ultraviolet resistance
Terephthalic acid 1.6Kg, BDO 2.7Kg are dropped in reactor, carries out esterification at 230 DEG C, after the current output that question response generates reaches 360g, add polytetrahydrofuran 1000500g, polytetrahydrofuran 2000500g, be warming up to 250 DEG C, under pressure is less than 30Pa condition, polycondensation 3h, adds 1,3,5-trimethylammonium-2,4,6-tri--(4 '-hydroxyl-3 ', 5 '-di-t-butyl benzyl) benzene 5g, thio-2 acid two (14) ester 12g, TINUVIN1449g.In reactor, be filled with high pure nitrogen, obtain polyester elastomer through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as P5.
Embodiment 6: the preparation of the thermoplastic polyester elastomer of ultraviolet resistance
By thermoplastic polyester elastomer (wherein polytetrahydrofuran-1000 content is 40wt%) 10Kg, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxybenzene propionic acid amide) 20g, two (α, α-dimethylbenzyl) pentanoic 20g, thio-2 acid two (13) ester 20g, TINUVIN62220g, mix in rear input twin screw extruder, 200 ~ 235 DEG C extrude, tie rod, polyester elastomer after pelletizing, be labeled as P6.
Comparative example 1
By dimethyl terephthalate (DMT) 1.94Kg, 1,4-butyleneglycol 1.8Kg, polytetrahydrofuran 20001.5Kg drop in reactor, fall the air in reactor with nitrogen replacement after, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 3g, be warming up to 210 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches 640g, and be warming up to 250 DEG C gradually, at reacting kettle inner pressure lower than under 30Pa condition, polyase 13 h.In reactor, be filled with high pure nitrogen, obtain polyester elastomer through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as Prf1.
Comparative example 2
By dimethyl terephthalate (DMT) 1.94Kg, 1,4-butyleneglycol 1.8Kg, polytetrahydrofuran 10001Kg drop in reactor, fall the air in reactor with nitrogen replacement after, be warming up to 170 DEG C, after dimethyl terephthalate (DMT) melts completely, add isopropyl titanate 3g, be warming up to 210 DEG C gradually and carry out esterification.After the methyl alcohol slipped out reaches 640g, add two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine 6g, N, N '-two-betanaphthyl-Ursol D 3.3g, TINUVIN1442g is also warming up to 250 DEG C gradually, at reacting kettle inner pressure lower than under 30Pa condition, polyase 13 h.In reactor, be filled with high pure nitrogen, obtain polyester elastomer through tie rod, pelletizing after the mold pressing of melt per os being gone out, be labeled as Prf2.
Comparative example 3
By thermoplastic polyester elastomer (wherein polytetrahydrofuran-1000 content is 20wt%, polytetrahydrofuran-2000 content is 15%) 10Kg, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxybenzene propionic acid amide) 20g, two (α, α-dimethylbenzyl) pentanoic 20g, thio-2 acid two (13) ester 20g mix in rear input twin screw extruder, 200 ~ 235 DEG C extrude, tie rod, polyester elastomer after pelletizing, be labeled as Prf3.
Performance measurement is carried out to the polyester elastomer that thermoplastic polyester elastomer and the comparative example 1 ~ 3 of the ultraviolet resistance that embodiment 1 ~ 6 prepares prepare, the results are shown in Table 1.
The performance index of the thermoplastic polyester elastomer of table 1 ultraviolet resistance
| Limiting viscosity/(dL/g) | B value | t 1/h | t 2/h | t 3/h | |
| P1 | 1.58 | 9 | 570 | 710 | 480 |
| P2 | 1.56 | 7 | 540 | 740 | 490 |
| P3 | 1.64 | 4 | 640 | 760 | 470 |
| P4 | 1.59 | 6 | 630 | 800 | 500 |
| P5 | 1.62 | 5 | 560 | 750 | 520 |
| P6 | 1.60 | 3 | 650 | 810 | 510 |
| Prf1 | 1.59 | 30 | 16 | 200 | 100 |
| Prf2 | 1.64 | 20 | 360 | 580 | 420 |
| Prf3 | 1.63 | 8 | 500 | 700 | 140 |
As can be seen from Table 1, after with the addition of the use of phenolic antioxidant, amine antioxidants, sulphur compounds and hindered amine ultraviolet light compound stabilizer, the thermotolerance of thermoplastic polyester elastomer and ultraviolet-resistant performance improve, and heat-proof water performance improves, and yellowness index (b value) declines.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a thermoplastic polyester elastomer for ultraviolet resistance, is characterized in that the component comprising following parts by weight:
The weight part sum of phenolic antioxidant and amine antioxidants is not 0;
Described phenolic antioxidant refers to two (3,5-di-tert-butyl-hydroxy phenyl propionyl) hydrazine, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxybenzene propionic acid amide), 1,3,5-trimethylammonium-2,4,6-tri--(4 '-hydroxyl-3 ', 5 '-di-t-butyl benzyl) benzene, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxyl benzyl) guanamine, 4,6-(1H, 3H, 5H) at least one in triketone and isocyanuric acid (3,5-di-tert-butyl-4-hydroxyl benzyl ester);
Described amine antioxidants refers to N, N '-two-betanaphthyl-Ursol D, N-phenyl-a-naphthylamine, 4,4 '-bis-(alpha, alpha-dimethylbenzyl) pentanoic and N, N ' at least one in-diphenyl-para-phenylene diamine;
Described sulphur compounds refers to the monothioester at least containing two propionic esters;
Described hindered amine UV stabilizer refers at least one in TINUVIN144 and TINUVIN622.
2. the thermoplastic polyester elastomer of ultraviolet resistance according to claim 1, is characterized in that: described thermoplastic polyester refers to polybutylene terephthalate-co-polytetrahydrofuran multipolymer.
3. the thermoplastic polyester elastomer of ultraviolet resistance according to claim 2, is characterized in that: in described polybutylene terephthalate-co-polytetrahydrofuran multipolymer, the content of polytetrahydrofuran is 25 ~ 60wt%.
4. the thermoplastic polyester elastomer of ultraviolet resistance according to claim 1, is characterized in that: described sulphur compounds refers at least one in Tyox B, thio-2 acid two (13) ester, thio-2 acid two (14) ester, thio-2 acid two (18) ester.
5. the thermoplastic polyester elastomer of ultraviolet resistance according to claim 1, is characterized in that: in the structure of described amine antioxidants, nitrogen-atoms is directly connected with phenyl ring; In the structure of described sulphur compounds, the β-C atom of two propionic esters is connected by S atom.
6. a preparation method for the thermoplastic polyester elastomer of the ultraviolet resistance according to any one of Claims 1 to 5, is characterized in that comprising following concrete steps:
Dimethyl terephthalate (DMT), 1,4-butyleneglycol, polytetrahydrofuran, catalyst Ti acid esters mix, esterification, polycondensation obtain thermoplastic polyester, mix with phenolic antioxidant, amine antioxidants, sulphur compounds and hindered amine ultraviolet light stablizer again, obtain the thermoplastic polyester elastomer of ultraviolet resistance;
Or dimethyl terephthalate (DMT), 1,4-butyleneglycol, polytetrahydrofuran, catalyst Ti acid esters mix, esterification, then mix with phenolic antioxidant, amine antioxidants, sulphur compounds and hindered amine ultraviolet light stablizer, polycondensation, obtains the thermoplastic polyester elastomer of ultraviolet resistance;
The reaction conditions of described esterification is react 1 ~ 3h at 180 ~ 210 DEG C;
The reaction conditions of described polycondensation is react 2 ~ 4h at 220 ~ 250 DEG C.
7. the application of thermoplastic polyester elastomer in automotive part, electric wire and stationery sports goods field of the ultraviolet resistance according to any one of Claims 1 to 5.
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| CN110452501B (en) * | 2019-07-29 | 2021-04-13 | 江阴爱科森博顿聚合体有限公司 | TPEE backing plate material for rail transit and preparation process thereof |
| CN113774507B (en) * | 2021-09-16 | 2023-07-11 | 东莞市博斯蒂新材料有限公司 | TPEE monofilament |
| CN114773798B (en) * | 2022-03-09 | 2024-03-15 | 上海金发科技发展有限公司 | High-impact long-acting yellowing-resistant PBT reinforced flame-retardant composite material and preparation method and application thereof |
| CN115926127B (en) * | 2022-12-13 | 2024-04-16 | 东莞市汇泽实业有限公司 | Thermoplastic polyester elastomer composition and preparation method thereof |
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| CN102532827A (en) * | 2011-12-22 | 2012-07-04 | 中纺投资发展股份有限公司 | White thermoplastic polyether ester elastomer composition with good heat stability |
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| CN102532827A (en) * | 2011-12-22 | 2012-07-04 | 中纺投资发展股份有限公司 | White thermoplastic polyether ester elastomer composition with good heat stability |
Non-Patent Citations (2)
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| "Recent Advances in the Photo-oxidation and Stabilization of Polymers";Norman S. Allen;《Chem. SOC.R ev.》;19861231;第373-404页 * |
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