CN107501554A - A kind of superhigh intensity thermoplastic elastomer (TPE) and preparation method thereof - Google Patents
A kind of superhigh intensity thermoplastic elastomer (TPE) and preparation method thereof Download PDFInfo
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000004952 Polyamide Substances 0.000 claims abstract description 104
- 229920002647 polyamide Polymers 0.000 claims abstract description 104
- 229920001971 elastomer Polymers 0.000 claims abstract description 25
- 239000000806 elastomer Substances 0.000 claims abstract description 25
- 238000012545 processing Methods 0.000 claims description 23
- 239000013067 intermediate product Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 abstract description 5
- 238000013459 approach Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000005445 natural material Substances 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 description 27
- 239000002028 Biomass Substances 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- -1 hydrogen furans Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000003673 urethanes Chemical class 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- ANLABNUUYWRCRP-UHFFFAOYSA-N 1-(4-nitrophenyl)cyclopentane-1-carbonitrile Chemical compound C1=CC([N+](=O)[O-])=CC=C1C1(C#N)CCCC1 ANLABNUUYWRCRP-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- DXRFZHILMCWCNG-UHFFFAOYSA-N N,N-dimethyl-1,8-naphthyridin-2-amine Chemical class C1=CC=NC2=NC(N(C)C)=CC=C21 DXRFZHILMCWCNG-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical class [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- ZXKINMCYCKHYFR-UHFFFAOYSA-N aminooxidanide Chemical compound [O-]N ZXKINMCYCKHYFR-UHFFFAOYSA-N 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000034303 cell budding Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000010010 raising Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XPQPWPZFBULGKT-UHFFFAOYSA-N undecanoic acid methyl ester Natural products CCCCCCCCCCC(=O)OC XPQPWPZFBULGKT-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
Abstract
The present invention relates to a kind of superhigh intensity thermoplastic elastomer (TPE) and preparation method thereof.Superhigh intensity thermoplastic elastomer (TPE) is made up of function polyamide, the structural formula of the function polyamide：The function polyamide structure formula includes the first constitutional repeating unit and the second constitutional repeating unit, works as R1To be first constitutional repeating unit during OH, work as R1ForWhen be second constitutional repeating unit, wherein 5≤n≤5000.The elastomer is stretched by the function polyamide, relaxation cycles mechanical treatment obtains.The structure for the function polyamide that the present invention selects provides support for its outstanding mechanical property, the function polyamide simultaneously forms superhigh intensity thermoplastic elastomer (TPE) by multiple cyclic tension mechanical treatment, the elastomer can reach preferable mechanical performance, function polyamide selected by the present invention can be synthesized by natural material, sustainable to make, green society provides favourable approach.
Description
Technical field
The invention belongs to biomass-based polymeric material field, be specifically related to a kind of superhigh intensity thermoplastic elastomer (TPE) and
Its preparation method.
Background technology
Nowadays the every aspect that we live all is flooded with the figure of thermoplastic elastomer (TPE), such as adhesive, coating, manages,
Tire and fiber.However, most of elastomers are prepared by non-renewable resources now, recyclable organism matrix thermoplastic elastomehc
Property body is still in the budding stage.Scientists also develop many by biomass-based thermoplastic elastomer (TPE), for example, biological poly
Urethane class elastomer (Donglin Tang, ChristopherW.Macosko, Polym.Chem., 2014,5,3231-3237),
Protein-based thermoplastic elastomer (TPE) (Karthik Nagapudi, William T.Brinkman, Macromolecules, 2005,
38 (2), pp345-354), poly ester urethane analog thermoplastic elastomer (Janneand Jukka V.
Macromolecules, 1997,30 (10), pp 2876-2882), come from aliphatic acid biomass-based elastomer (Shu Wang,
Sameer Vajjala Kesava,Enrique D.And Megan L.Robertson, Macromolecules,
2013,46(18),pp 7202–7212).But from mechanical property, these elastomers are also difficult to practical application.Then, it is
The reinforcing above mechanical property is carried out, researchers have carried out substantial amounts of trial, for example introduce silica nanometer
Grain enhancing elastomer performance (By Tao Wei, Li juan Lei, Hailan Kang, Bo Qiao, Zhao Wang, Liqun
Zhang, Phil Coates, Kuo-Chih Hua and Joseph Kulig, ADVANCED ENGINEERING
MATERIALS 2012,14,No.1-2)；Addition nano clay enhancing elastomer performance (Lin Zhu, Richard P.Wool,
Polymer 47 (2006) 8106-8115) etc..
Due to social demand constantly expands, conventional petroleum resource peter out and it is the environmental consciousness of people, sustainable
The consciousness of development constantly strengthens, and explores new reproducible biomass-based thermoplastic elastomer (TPE) and is spread out to replacement is traditional with oil
The non-renewable resources such as biology are imperative for the thermoplastic elastomer (TPE) of raw material.
So far, the main raw material(s) of biomass-based elastomer includes：Oleic acid, castor oil acid, PLA, protein,
Lactone, aliphatic acid and its derivative etc..These raw material all have the characteristics of renewable, source is wide, and contain functional group in itself
Reaction easy to process.But most of mechanics of elastic bodies poor-performings prepared by these raw material, even if adding nanometer afterwards
The nano particles such as silica, its mechanical property are still unable to reach preferable situation.
The content of the invention
In order to solve the above-mentioned technical problem, the present invention provides a kind of superhigh intensity thermoplastic elastomer (TPE) and preparation method thereof.
In order to realize the purpose of the present invention, present invention employs following technical scheme：
A kind of superhigh intensity thermoplastic elastomer (TPE), the elastomer are made up of function polyamide, the function polyamide
Structural formula is as follows：
The function polyamide structure formula includes the first constitutional repeating unit and the second constitutional repeating unit, works as R1For-
It is first constitutional repeating unit during OH, works as R1ForWhen be second constitutional repeating unit, wherein 5≤n
≤5000。
Further, the mechanical property parameters of the elastomer are：40~700Mpa of initial elastic modulus, fracture strength 30~
1000Mpa, elongation at break 5~100%, rebound degree 60~100%.
A kind of method for producing elastomers, the function polyamide is stretched, relaxation cycles mechanical treatment.
Further, the preparation method comprises the following steps：
S1, at room temperature, function polyamide is subjected to first round stretching, relaxation cycles mechanical treatment and obtains middle production
Product：The first round stretching, relaxation cycles mechanical treatment include multi-drawing, relaxation cycles process, gradually improve stretch processing
Shi Suoshu functions polyamide needs the function polyamide during setting strain value, wherein last time stretch processing reached to need
The maximum strain value ε that sets strain value and can reach in stretch processing first as the function polyamide reached1；Draw every time
After the function polyamide reaches setting strain value when stretching processing, stop stretching and the relaxation of function polyamide is replied until should
Force value is reduced to zero；
S2, at room temperature, the intermediate products are subjected to the second wheel stretching, relaxation cycles mechanical treatment and obtain elastomer
Product：The second wheel stretching, relaxation cycles mechanical treatment include multi-drawing, relaxation cycles process, gradually improve at stretching
The intermediate products need to reach during the setting strain value, wherein last time stretch processing that the intermediate products need to reach during reason
To the maximum strain value ε that sets strain value and can reach in stretch processing first as the intermediate products2；At each stretching
After the intermediate products reach setting strain value during reason, stop stretching and intermediate products relaxation is replied until stress value reduces
It is zero.
Further, the rate of extension of the sample is 10mm/min.
The beneficial effects of the present invention are：
(1) structure for the function polyamide that the present invention selects provides support, the function for its outstanding mechanical property
Polyamide simultaneously forms superhigh intensity thermoplastic elastomer (TPE) by multiple cyclic tension mechanical treatment, and the elastomer can reach reason
The mechanical performance thought, the function polyamide selected by the present invention can be synthesized by natural material castor oil derivative, can held to make
Continuous, green society provides favourable approach.
(2) because first round stretching, relaxation cycles mechanical treatment can not fully change sample collection state knot in the present invention
Structure and mechanical performance, so the second wheel stretching, relaxation cycles mechanical treatment need to be carried out, it is allowed to possess excellent elasticity.The sample
Product stretch, after relaxation cycles mechanical treatment by two-wheeled, and internal crystallization orientation is complete, and elasticity is optimized.
(3) present invention realizes the various of elastomer application to obtain the biomass-based thermoplastic elastomer (TPE) of excellent performance
Change, the present invention realizes the fine of rational Molecular Design and aggregated structure by stretching, relaxation cycles mechanical treatment
Regulation and control, its unique structure and intermolecular active force make function polyamide possess excellent performance.Work(of the present invention
Energy polyamide macromolecule is become with excellent mechanical strength and good elastic very-high performance heat by a series of post processings
Thermoplastic elastic.
Brief description of the drawings
Fig. 1 is the nucleus magnetic hydrogen spectrum of monomer of polyamide 1 in embodiment 1.
Fig. 2 is the nucleus magnetic hydrogen spectrum of monomer of polyamide 2 in embodiment 1.
Fig. 3 is the nucleus magnetic hydrogen spectrum of function polyamide in embodiment 3.
Fig. 4 is the microstructure (atomic force micrograph) of function polyamide in embodiment 3.
Fig. 5 is the stress-strain curve during the first round is handled of function polyamide 1 in embodiment 4.
Fig. 6 is the stress-strain curve during the processing of the second wheel of function polyamide 1 in embodiment 4.
Fig. 7 is that function polyamide 1 handles Posterior circle tensile stress-strain curve figures in two wheels in embodiment 4.
Fig. 8 is the stress-strain curve during the first round is handled of function polyamide 2 in embodiment 5.
Fig. 9 is the stress-strain curve during the processing of the second wheel of function polyamide 2 in embodiment 5.
Figure 10 is that function polyamide 2 handles Posterior circle tensile stress-strain curve figures in two wheels in embodiment 5.
Figure 11 is function kymene stress-strain curve during the first round is handled in embodiment 6.
Figure 12 is function kymene stress-strain curve during the processing of the second wheel in embodiment 6.
Figure 13 is that function kymene handles Posterior circle tensile stress-strain curve figures in two wheels in embodiment 6.
Figure 14 is the simple tension stress-strain curve before circular treatment of function polyamide 1,2,3.
Figure 15 is the simple tension stress-strain curve after circular treatment of function polyamide 1,2,3.
Embodiment
The reagent used in following examples is bought from market, and the solvent must be done through anhydrous magnesium sulfate before the use
It is evaporated under reduced pressure after dry, azodiisobutyronitrile need to pass through recrystallization purifying.
The preparation of the biomass-based function polyamide 1 of embodiment 1
It is following to prepare function monomer of polyamide 1：Methyl undecylenate 100g, 1,3- diaminourea-propyl alcohol 1g is taken to add 4ml tetra-
In hydrogen furans.After being passed through argon gas half an hour, it is positioned in 40 DEG C of oil bath pans, after adding 10ml sodium methoxides, 40 DEG C are reacted 20 hours,
Again by being recrystallized to give white powdery solids, as hydroxy amide base monomer.
The 1HNMR spectrograms of the function monomer of polyamide 1 as shown in figure 1, from figure f at e peaks and 3.8 at 3.38ppm
Peak, which can be seen that, contains amide groups and hydroxyl in monomer；At 4.85ppm, tri- peaks of a, b, c at 5.0ppm and at 5.8ppm
Displaying monomer contains double bond, it was demonstrated that is successfully prepared function monomer of polyamide 1.
The structural formula of the function monomer of polyamide 1 is as follows：
Wherein R1For-OH (hydroxyl).
It is following to prepare function monomer of polyamide 2：Take function monomer of polyamide 1 prepared in 54g embodiments 1,12g butyric acid
Acid anhydride, 40mg dimethylamino naphthyridines are placed in the flask of bottom, are added the mixing of 3ml tetrahydrofurans, are reacted 10 hours, clarified at 50 DEG C
Solution, purified obtained function monomer of polyamide 2.
The 1HNMR spectrograms of the function monomer of polyamide 2 are as shown in Fig. 2 comparison diagram 1 can be seen that, former f peaks disappear at 3.8ppm
Lose, appearance of the 4.8ppm places new f peaks and e peaks of appearance at 2.18ppm shows hydroxyl on function monomer of polyamide 1 by ester
Change, obtain function monomer of polyamide 2.
The structural formula of the function monomer of polyamide 2 is as follows：
Wherein R1For
Biomass-based function polyamide 1 is prepared as follows：By 1350mg function monomer of polyamide 2,150mg function polyamide
Monomer 1, the mercaptan of 200mg oxa-s two, and 10mg azodiisobutyronitriles catalyst and 10ml tetrahydrofurans are added in reaction vessel.
It is passed through argon gas 15 minutes, mixture is positioned over 36 hours of reaction in 100 DEG C of oil bath pans afterwards.Purify afterwards, obtain function
Polyamide 1.
The function polyamide 1 to prepare equation as follows：
As above shown in equation, high-strength thermoplastic elastomer is made up of product functionality polyamide, and it is by function
Monomer of polyamide and the mercaptan of oxa- two are formed by sulfydryl-alkenyl reactive polymeric.
The function polyamide structure formula includes the first constitutional repeating unit and the second constitutional repeating unit, works as R1
To be first constitutional repeating unit during-OH, work as R1ForWhen be second constitutional repeating unit.
The preparation of the biomass-based function polyamide 2 of embodiment 2
Biomass-based function polyamide 2 is prepared as follows：Its preparation method gathers with embodiment 1 except that adding function
The mass of amide monomer 2 is 1200mg, and the quality of function monomer of polyamide 1 is 300mg, obtains function polyamide 2.
The preparation of the biomass-based function kymene of embodiment 3
Biomass-based function kymene is prepared as follows：Its preparation method gathers with embodiment 1 except that adding function
The mass of amide monomer 2 is 750, and function monomer of polyamide 1 is 750mg, obtains function kymene.
The nucleus magnetic hydrogen spectrum of function kymene is as shown in figure 3, comparison diagram 1, Fig. 2,1.7ppm, 2.3ppm, 3.8ppm and
Peak at 4.8ppm illustrates in the copolymer of embodiment 3 while has function monomer of polyamide 1 and a function monomer of polyamide 2.Say
Bright function monomer of polyamide 1 and function monomer of polyamide 2 can be copolymerized by the method, entered function polyamide.
Fig. 4 is the atomic force microscope observation of function kymene, as can be seen from Figure containing a large amount of in function kymene
Nano crystals, the product for illustrating the present invention be those semi-crystalline materials, and this is the preparation of superhigh intensity thermoplastic elastomer (TPE) below
Provide possibility.
It is high-strength thermoplastic method for producing elastomers below：Operated the function polyamide for convenience in embodiment
Membrane structure is made in the sample of composition, and specific method is：The function polyamide is dissolved to form solution by tetrahydrofuran, institute
State solution and be applied to Teflon mould, first drying at room temperature 24h, 40 DEG C of vacuum drying afterwards form film, finally cut out with dumbbell shape
The film is cut to dumbbell shape batten by knife, and the size of dumbbell shape batten centre narrow space part is：Long 15mm, wide 2mm, thickness
Spend 0.5mm.
Sample is stretched, relaxation cycles mechanical treatment when, length direction of the stretched operation along sample is carried out.
The preparation of high strength elastic body of the embodiment 4 based on function polyamide 1
High strength elastic body is made in function polyamide 1, its preparation method is as follows：The function polyamide 1 is carried out
One wheel stretching, relaxation cycles mechanical treatment obtain meso sample：The function polyamide 1 reaches when gradually improving stretch processing
Maximum strain value, the rate of extension of the function polyamide 1 is 10mm/min, the function polyamide when each stretch processing
After 1 reaches setting strain value, stop stretching and the relaxation of function polyamide 1 is replied until stress value is reduced to zero；The first round
The setting strain value that the function polyamide 1 reaches during stretch processing is followed successively by 50%, 100%, 150%, 200%, 300%,
400%th, 500%, 600%.Fig. 5 is that function polyamide 1 stretches in the first round, during relaxation cycles mechanical treatment in the present embodiment
Load-deformation curve, it can be seen that there is obvious surrender and hysteresis phenomenon.
In order to fully improve sample strength and resilience, carry out the is also needed after first round stretching, relaxation cycles mechanical treatment
Two wheel stretchings, relaxation cycles mechanical treatment obtain elastomer.Specific implementation method and first round stretching, relaxation cycles mechanical treatment
Except that setting strain value when stretching every time is respectively 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%
Until maximum strain value.
The size that each round sets strain value in drawing process each time can be according to maximum strain value and stretching, relaxation
The number of circulation carries out reasonable selection.
Fig. 6 is the stress-strain during the second wheel stretching, relaxation cycles mechanical treatment of function polyamide 1 in the present embodiment
Curve.No matter function polyamide 1 intensity or is returning after first time stretching, relaxation processes in the present embodiment as shown in Figure 6
Elasticity all obtains enough raisings, but also it is evident that only by one-off drawing, relaxation processes not fully, this is second
Significantly embodied in wheel stretching, relaxation cycles mechanical treatment.
Fig. 7 is final cyclic tension of the function polyamide 1 after two-wheeled stretching, relaxation cycles mechanical treatment in the present embodiment
Load-deformation curve, it can be seen that function polyamide 1 is stretched by two-wheeled, relaxation cycles mechanical treatment, and its intensity and resilience are all
The lifting of maximum is obtained, final fracture stress is compared to being initially to improve as many as 5 times, and resilience reaches 100%.
The preparation of high strength elastic body of the embodiment 5 based on function polyamide 2
High strength elastic body is made in function polyamide 2, its preparation method is as follows：The function polyamide 2 is carried out
One wheel stretching, relaxation cycles mechanical treatment obtain meso sample：The function polyamide 2 reaches when gradually improving stretch processing
Strain value is set, the rate of extension of the function polyamide 2 is 10mm/min, the function polyamide when each stretch processing
After 2 reach setting strain value, stop stretching and the relaxation of function polyamide 2 is replied until stress value is reduced to zero；The first round
The setting strain value that the function polyamide 2 reaches during stretch processing is followed successively by 100%, 200%, 300%, 400%, 500%,
600%.Fig. 8 is that the stress-strain during first round stretching, relaxation cycles mechanical treatment of function polyamide 2 is bent in the present embodiment
Line.
In order to fully improve the intensity of function polyamide 2 and resilience, also needed after first round stretching, relaxation cycles mechanical treatment
The second wheel stretching, relaxation cycles mechanical treatment are carried out to the meso sample and obtains elastomer.Specific implementation method and first
Wheel stretching, relaxation cycles mechanical treatment except that every time stretching when setting strain value be respectively 5%, 10%, 15%,
20%, 25%, 30%, 35%, 40%, 45% until maximum strain value.Fig. 9 is function polyamide 2 in the present embodiment second
Load-deformation curve during wheel stretching, relaxation cycles mechanical treatment.Figure 10 is that function polyamide 2 is drawn in two wheels in the present embodiment
Stretch, the final cyclic tension load-deformation curve after relaxation cycles mechanical treatment, it can be seen that function polyamide 2 in the present embodiment
Final fracture stress reach 72Mpa and resilience is good.
The preparation of high strength elastic body of the embodiment 6 based on function kymene
High strength elastic body is made in function kymene, its preparation method is consistent with embodiment 5.Figure 11 is the present embodiment
Middle function kymene stretches in the first round, load-deformation curve during relaxation cycles mechanical treatment.Figure 12 is in the present embodiment
Function kymene load-deformation curve during the second wheel stretching, relaxation cycles mechanical treatment.Figure 13 is work(in the present embodiment
Can cyclic tension load-deformation curve of the kymene after two wheel stretchings, relaxation cycles mechanical treatment.It can be seen that the present embodiment
Middle function kymene is up to 92Mpa and with good resilience with good mechanical strength.
Figure 14 is the simple tension load-deformation curve of function polyamide 1,2,3 before stretching, relaxation cycles mechanical treatment.
Figure 15 is the simple tension load-deformation curve of function polyamide 1,2,3 after stretching, relaxation cycles mechanical treatment.Can be seen that through
After overstretching, relaxation cycles mechanical treatment, its intensity is all greatly improved, its fracture strength be about it is untreated before 5 times.
Claims (5)
- A kind of 1. superhigh intensity thermoplastic elastomer (TPE), it is characterised in that：The elastomer is made up of function polyamide, the function The structural formula of polyamide is as follows：The function polyamide structure formula includes the first constitutional repeating unit and the second constitutional repeating unit, works as R1For-OH when For first constitutional repeating unit, work as R1ForWhen be second constitutional repeating unit, wherein 5≤n≤ 5000。
- 2. elastomer as claimed in claim 1, it is characterised in that：The mechanical property parameters of the elastomer are：Initial elasticity mould Measure 40~700Mpa, 30~1000Mpa of fracture strength, elongation at break 5~100%, rebound degree 60~100%.
- A kind of 3. method for producing elastomers as claimed in claim 1 or 2, it is characterised in that：The function polyamide is carried out Stretching, relaxation cycles mechanical treatment.
- 4. method for producing elastomers as claimed in claim 3, it is characterised in that：The preparation method comprises the following steps：S1, at room temperature, function polyamide is subjected to first round stretching, relaxation cycles mechanical treatment and obtains intermediate products：Institute State the first round stretching, relaxation cycles mechanical treatment include multi-drawing, relaxation cycles process, gradually improve stretch processing when described in The function polyamide needs what is reached during the setting strain value, wherein last time stretch processing that function polyamide needs to reach Set the maximum strain value ε that strain value can reach as the function polyamide in stretch processing first1；Each stretch processing After Shi Suoshu function polyamide reaches setting strain value, stop stretching and the relaxation of function polyamide is replied until stress value subtracts Small is zero；S2, at room temperature, the intermediate products are subjected to the second wheel stretching, relaxation cycles mechanical treatment and obtain elastomer production Product：The second wheel stretching, relaxation cycles mechanical treatment include multi-drawing, relaxation cycles process, gradually improve stretch processing The intermediate products need to reach during the setting strain value, wherein last time stretch processing that Shi Suoshu intermediate products need to reach The maximum strain value ε that sets strain value and can reach in stretch processing first as the intermediate products2；Each stretch processing After Shi Suoshu intermediate products reach setting strain value, stop stretching and intermediate products relaxation is replied until stress value is reduced to Zero.
- 5. method for producing elastomers as claimed in claim 3, it is characterised in that：The rate of extension of the sample is 10mm/ min。
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