CN104628895A - Method for thermally reversibly crosslinking styrenic thermoplastic elastomer material - Google Patents
Method for thermally reversibly crosslinking styrenic thermoplastic elastomer material Download PDFInfo
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- CN104628895A CN104628895A CN201510039748.7A CN201510039748A CN104628895A CN 104628895 A CN104628895 A CN 104628895A CN 201510039748 A CN201510039748 A CN 201510039748A CN 104628895 A CN104628895 A CN 104628895A
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Abstract
The invention discloses a method for thermally reversibly crosslinking a styrenic thermoplastic elastomer material. The method for thermally reversibly crosslinking the styrenic thermoplastic elastomer material comprises the following steps: firstly under the condition of ultraviolet light illumination, grafting sulfhydryl furan to a soft segment section of the styrenic thermoplastic elastomer SBC (TPE-S) by utilizing sulfhydryl-alkene click reaction, then adding a maleimide compound containing at least two maleimide groups, and carrying out reversible chemical crosslinking based on Diels-Alder reaction under the heating condition, so that the aim of reversibly crosslinking and modifying polystyrene-butadiene-styrene is achieved. The styrenic thermoplastic elastomer modifying method disclosed by the invention is simple, raw materials are available, and cost is low; and the styrenic thermoplastic elastomer modified by utilizing the method disclosed by the invention is improved in mechanical properties and solvent resistance and still has thermoplasticity.
Description
Technical field
The invention belongs to technical field of chemical material preparation, be specifically related to a kind of method of UV radiation modification styrene analog thermoplastic elastomer SBC (TPE-S) and the modified thermoplastic elastomer system of reversible crosslink.
Background technology
Styrene analog thermoplastic elastomer SBC (TPE-S), due to the physical crosslinking of PB phase, has the characteristic of plastics and rubber simultaneously, is therefore called as " third generation synthetic rubber "; On the one hand, it is excellent that SBC (TPE-S) material has tensile strength, skin friction coefficient is large, low-temperature performance is good, electrical property excellent and good processability, without the need to the feature such as crosslinked during use, is the maximum thermoplastic elastomer of current consumption, but then, the such as SBS (styrene-butadiene-vinylbenzene) in SBC (TPE-S) material and SIS (polystyrene-different propylene-styrene) etc. exist that intensity is lower, the easy shortcoming such as aging.
Summary of the invention
In order to overcome the deficiencies in the prior art, the object of the present invention is to provide a kind of method of modifying of simple styrene analog thermoplastic elastomer SBC (TPE-S) material.This method of modifying effectively can strengthen mechanical property, solvent resistance and the work-ing life of styrene analog thermoplastic elastomer material.
The present invention is first by UV light-induced graft modification, carry out mercapto alkene click-reaction, the furan nucleus being connected with sulfydryl is grafted to soft section of (i.e. isolated double bond) part of thermoplastic elastomer molecular chain, again thermoplastic elastomer after graft modification and the organic molecule or polymkeric substance containing polynary maleic anhydride (maleimide) are carried out, based on the reversible heat cross-linking of Di Ersi – Alder reaction (Diels – Alder reaction), obtaining the thermoplastic elastomer of reversible crosslink modification.In the thermoplastic elastomer of reversible crosslink modification, the ratio of furans grafting amount and furans and maleimide structure is all adjustable, and then can be used for the multiple performance regulating resulting materials, as mechanical property, and solvent resistance etc.
Technical solution of the present invention is specifically described below.
The invention provides a kind of method that styrene analog thermoplastic elastomer material thermal reversion is crosslinked, comprise the steps:
(1) styrene analog thermoplastic elastomer and sulfydryl furan compound are dissolved in organic solvent, after stirring, add light trigger, mercapto alkene click-reaction occurs under the condition of ultraviolet lighting, obtain the modified phenylethylene analog thermoplastic elastomer solution after grafting;
(2) in the modified phenylethylene analog thermoplastic elastomer solution after grafting, the compound containing maleimide base group is added, film forming under the condition of heating, crosslinked, obtain reversible crosslink modified styrenics thermoplastic elastic material; Wherein:
In step (1), containing isolated double bond in the molecular structure of described styrene analog thermoplastic elastomer, described sulfydryl furan compound is the compound simultaneously containing furan nucleus and sulfydryl in molecular structure; In described sulfydryl furan compound and styrene analog thermoplastic elastomer, the mol ratio of isolated double bond is (0.01-1): 1;
In step (2), on the thermoplastic elastomer after the maleimide compound added and furans grafting, the mol ratio of furans is (0.01-1): 1.
In the present invention, described styrene analog thermoplastic elastomer is SBS, SIS or SIBS; Described sulfydryl furan compound is furfurylmercaptan.The described maleimide compound containing at least two maleimide base groups is N, N'-(4,4'-methylenediphenyl) bismaleimides.
In the present invention, described organic solvent is tetrahydrofuran (THF), alcohols, chloroform, methylene dichloride, dimethyl sulfoxide (DMSO), 1,4-dioxane, N, N '-dimethyl methane amide, N, any one in N '-dimethyl ethanamide, N-methyl-pyrrolidon, benzene, toluene or dimethylbenzene; Described light trigger is free radical photo-initiation or cationic photoinitiator.
In the present invention, described free radical photo-initiation is the combination of one or more in st-yrax ethers, Dialkoxy acetophenones, Oxoxanthone, Sulfide-containing Hindered benzophenone, thioxanthone, anthraquinone and benzophenone and derivative thereof; Described cationic photoinitiator is any one in Diaryl iodonium compound, triaryl sulfide, Diaryl iodonium mantoquita or ferrocene salt.
Beneficial effect of the present invention is: the method for this modified phenylethylene analog thermoplastic elastomer SBC (TPE-S) by ultraviolet radiation graft and reversible crosslink is simple, and raw material is easy to get, cost is lower.The modified thermoplastic elastomer material mechanical performances obtained etc. do not lose thermoplasticity, again can process use while improving.Can be widely applied in daily life and industrial production.
Accompanying drawing explanation
Fig. 1 is the nuclear-magnetism of SBS after the furans grafting in embodiment 1 and infrared figure.
Fig. 2 is the stress-strain curve of the material of various ratio in embodiment 1.
Fig. 3 is the stress-strain curve of the material of various ratio in embodiment 2.
Fig. 4 is the stress-strain curve of the material after reinventing in embodiment 3.
Embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is further described.Following examples further illustrate of the present invention, instead of limit the scope of the invention.
Embodiment 1
SBS and furfurylmercaptan are dissolved in toluene by different ratios, add appropriate light trigger I907, and the graft ratio of the optional furfurylmercaptan of ratio is 2%, 5%, 10%, 15%, 20%, after stirring, and carry out click-reaction at ultraviolet lighting.Backward reacted solution in add the N with furans mole number half, N'-(4,4'-methylenediphenyl) bismaleimides (now the mol ratio of furans and maleimide structure is 1:1), after stirring, heats cross moulding under 80 DEG C of conditions.Table 1 be various ratio material extending test in elongation at break and breaking tenacity.Fig. 1 is the nuclear-magnetism of SBS after the furans grafting 20% in embodiment 1 and infrared figure.Fig. 2 is the stress-strain curve of the material of various ratio in embodiment 1.
Table 1
Embodiment 2
SBS and furfurylmercaptan are dissolved in dimethylbenzene, add appropriate light trigger I907, and ratio is set as that the graft ratio of furfurylmercaptan is 15%, after stirring, and carry out click-reaction at ultraviolet lighting.Backward reacted solution in add the N of different amount, N'-(4,4'-methylenediphenyl) bismaleimides, the mol ratio mole accounting for furans wherein selecting maleimide is respectively 0%, 20%, 40%, 60%, 80% and 100%, after stirring, heat cross moulding under 80 DEG C of conditions.Table 2 be various ratio material extending test in elongation at break and breaking tenacity.Fig. 3 is the stress-strain curve of the material of various ratio in embodiment 2.
Table 2
Maleimide accounts for the molar ratio of furans | Elongation at break (%) | Breaking tenacity (MPa) |
0 | 1127.56 | 7.14 |
20% | 914.54 | 10.07 |
40% | 922.54 | 12.02 |
60% | 933.89 | 11.54 |
80% | 843.21 | 14.96 |
100% | 751.99 | 9.45 |
Embodiment 3
Be 15% by furans grafting amount in embodiment 2, maleimide accounts for the sample that furans mol ratio is 80%, shred after film forming, at 150 DEG C, again film forming under the condition of 10MPa, repeat this process three times, test the stretching of the film of each gained, table 3 is elongation at break in each again obtained material extending test and breaking tenacity.Fig. 4 is the stress-strain curve of the material after reinventing in embodiment 3.
Table 3
Elongation at break (%) | Breaking tenacity (MPa) | |
Former state | 843.21 | 14.96 |
First time reinvents | 875.19 | 14.10 |
Second time is reinvented | 892.66 | 12.71 |
Third time reinvents | 885.71 | 12.03 |
Claims (5)
1. the method that styrene analog thermoplastic elastomer material thermal reversion is crosslinked, is characterized in that, comprise the steps:
(1) styrene analog thermoplastic elastomer and sulfydryl furan compound are dissolved in organic solvent, after stirring, add light trigger, mercapto alkene click-reaction occurs under the condition of ultraviolet lighting, obtain the modified phenylethylene analog thermoplastic elastomer solution after grafting;
(2), in the modified phenylethylene analog thermoplastic elastomer solution after grafting, maleimide compound is added, film forming at 60-120 DEG C of temperature, crosslinked, obtain reversible crosslink modified styrenics thermoplastic elastic material; Wherein:
In step (1), containing isolated double bond in the molecular structure of described styrene analog thermoplastic elastomer, described sulfydryl furan compound is the compound simultaneously containing furan nucleus and sulfydryl in molecular structure; In described sulfydryl furan compound and styrene analog thermoplastic elastomer, the mol ratio of isolated double bond is (0.01-1): 1;
In step (2), on the thermoplastic elastomer after the mole number of described maleimide and furans grafting, the mol ratio of furans is (0.01-1): 1.
2. method according to claim 1, is characterized in that: described styrene analog thermoplastic elastomer is SBS, SIS or SIBS; Described sulfydryl furan compound is furfurylmercaptan.
3. method according to claim 1, is characterized in that: described maleimide compound is N, N'-(4,4'-methylenediphenyl) bismaleimides.
4. method according to claim 1, it is characterized in that: described organic solvent is tetrahydrofuran (THF), alcohols, chloroform, methylene dichloride, dimethyl sulfoxide (DMSO), 1,4-dioxane, N, N '-dimethyl methane amide, N, any one in N '-dimethyl ethanamide, N-methyl-pyrrolidon, benzene, toluene or dimethylbenzene; Described light trigger is free radical photo-initiation or cationic photoinitiator.
5. method according to claim 4, is characterized in that: described free radical photo-initiation is the combination of one or more in st-yrax ethers, Dialkoxy acetophenones, Oxoxanthone, Sulfide-containing Hindered benzophenone, thioxanthone, anthraquinone and benzophenone and derivative thereof; Described cationic photoinitiator is any one in Diaryl iodonium compound, triaryl sulfide, Diaryl iodonium mantoquita or ferrocene salt.
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JP2017039877A (en) * | 2015-08-21 | 2017-02-23 | 日本ゼオン株式会社 | Crosslinkable rubber composition |
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CN104193852A (en) * | 2014-08-28 | 2014-12-10 | 上海交通大学 | Modified unsaturated rubber and preparation and use methods thereof |
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CN102391424A (en) * | 2011-09-01 | 2012-03-28 | 上海交通大学 | Method for modifying styrene-butadiene-styrene (SBS) block copolymer |
CN103788386A (en) * | 2014-01-26 | 2014-05-14 | 上海交通大学 | Method for modifying elastomer by using click reaction of thiol-ene |
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CN105602181A (en) * | 2015-12-28 | 2016-05-25 | 上海交通大学 | Carbon nanotube modified thermoplastic elastomer composite material with solvent resistance and preparing method thereof |
CN105949469A (en) * | 2016-06-23 | 2016-09-21 | 郑州大学 | High-polymer material interface modification method based on Diels-Alder reversible reaction |
CN105949469B (en) * | 2016-06-23 | 2019-03-01 | 郑州大学 | The interface modification method of high molecular material based on Diels-Alder reversible reaction |
CN106189040A (en) * | 2016-07-11 | 2016-12-07 | 上海交通大学 | A kind of method based on the schiff base reaction synthesis cross-linking modified elastomeric material of thermal reversion |
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