CN114276655A - Degradable thermoplastic elastomer and preparation method thereof - Google Patents
Degradable thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN114276655A CN114276655A CN202110863921.0A CN202110863921A CN114276655A CN 114276655 A CN114276655 A CN 114276655A CN 202110863921 A CN202110863921 A CN 202110863921A CN 114276655 A CN114276655 A CN 114276655A
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004632 polycaprolactone Substances 0.000 claims abstract description 87
- 229920001610 polycaprolactone Polymers 0.000 claims abstract description 87
- 229920001896 polybutyrate Polymers 0.000 claims abstract description 83
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims abstract description 40
- 229920001971 elastomer Polymers 0.000 claims abstract description 19
- 239000000806 elastomer Substances 0.000 claims abstract description 18
- 230000001105 regulatory effect Effects 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- 230000001276 controlling effect Effects 0.000 claims abstract description 7
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 claims abstract description 5
- JYLRDAXYHVFRPW-UHFFFAOYSA-N butane-1,1-diol;terephthalic acid Chemical compound CCCC(O)O.OC(=O)C1=CC=C(C(O)=O)C=C1 JYLRDAXYHVFRPW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- -1 polysiloxane Polymers 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- HITZGLBEZMKWBW-UHFFFAOYSA-N ac1n8rtr Chemical group C1CC2OC2CC1CC[Si](O1)(O2)O[Si](O3)(C4CCCC4)O[Si](O4)(C5CCCC5)O[Si]1(C1CCCC1)O[Si](O1)(C5CCCC5)O[Si]2(C2CCCC2)O[Si]3(C2CCCC2)O[Si]41C1CCCC1 HITZGLBEZMKWBW-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Chemical group 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- DEQJBORXLQWRGV-UHFFFAOYSA-N 2-hydroxypropanoic acid;iron Chemical compound [Fe].CC(O)C(O)=O.CC(O)C(O)=O DEQJBORXLQWRGV-UHFFFAOYSA-N 0.000 claims description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims description 2
- 125000004018 acid anhydride group Chemical group 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 125000006264 diethylaminomethyl group Chemical group [H]C([H])([H])C([H])([H])N(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004225 ferrous lactate Substances 0.000 claims description 2
- 235000013925 ferrous lactate Nutrition 0.000 claims description 2
- 229940037907 ferrous lactate Drugs 0.000 claims description 2
- OVGXLJDWSLQDRT-UHFFFAOYSA-L magnesium lactate Chemical compound [Mg+2].CC(O)C([O-])=O.CC(O)C([O-])=O OVGXLJDWSLQDRT-UHFFFAOYSA-L 0.000 claims description 2
- 239000000626 magnesium lactate Substances 0.000 claims description 2
- 229960004658 magnesium lactate Drugs 0.000 claims description 2
- 235000015229 magnesium lactate Nutrition 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- BNCOGDMUGQWFQE-UHFFFAOYSA-N tris(ethenyl)silicon Chemical compound C=C[Si](C=C)C=C BNCOGDMUGQWFQE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011576 zinc lactate Substances 0.000 claims description 2
- 229940050168 zinc lactate Drugs 0.000 claims description 2
- 235000000193 zinc lactate Nutrition 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 15
- 239000008187 granular material Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 8
- 239000011258 core-shell material Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000004626 polylactic acid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910018557 Si O Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229920000747 poly(lactic acid) Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 230000007334 memory performance Effects 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 2
- 229920006238 degradable plastic Polymers 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 229910052624 sepiolite Inorganic materials 0.000 description 2
- 235000019355 sepiolite Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- IITMLUBEDLJWRH-UHFFFAOYSA-N 2-[3-(oxiran-2-ylmethoxy)propyl]-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1C(C1)COCCC[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 IITMLUBEDLJWRH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 210000001520 comb Anatomy 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
Abstract
The invention relates to a degradable thermoplastic elastomer and a preparation method thereof, wherein the elastomer comprises a copolymer (PBAT) of butanediol adipate and butanediol terephthalate, Polycaprolactone (PCL), multi-arm polysilsesquioxane grafted PBAT/PCL (POSS-g-PBAT/PCL) and a coupling agent. The POSS-g-PBAT/PCL accounts for 1-10% of the mass of the elastomer, and the mechanical property and the degradation property of the elastomer are regulated and controlled by regulating and controlling the content of the POSS-g-PBAT/PCL. The degradable thermoplastic elastomer prepared by the invention has high strength, high toughness and better rebound resilience and degradation performance.
Description
Technical Field
The invention relates to a degradable thermoplastic elastomer and a preparation method thereof, belonging to the field of degradable materials.
Background
At present, many articles in hotels are non-degradable plastic products, such as toothbrushes, combs, shower caps and the like. The materials of the comb and the toothbrush handle are generally obtained by injection molding by using non-degradable Polystyrene (PS) or polypropylene (PP). The material of the toothbrush filament is generally obtained by using non-degradable Polyamide (PA) and performing fiber forming and rounding (sharpening). The existing mass-produced degradable material polylactic acid (PLA) has the problems of high hardness, large brittleness, poor fluidity and stretchability and the like, is greatly limited in the process of continuously melt spinning and forming fibers of the body of the coarse denier monofilament for toothbrush filaments, and has no research and application report of the degradable brush filaments at present. Simply reducing the spinning speed, at a lower drawing speed, because the PLA molecular chain can not form highly oriented crystals, the obtained heavy denier fiber has lower strength, toughness and thermal stability, and can not meet the performance requirements of toothbrush filaments. How to balance the strength, resilience and biocompatibility of the toothbrush filament is the key to obtain the degradable toothbrush filament material.
In the field of biodegradable materials, a copolymer (PBAT) of butanediol adipate and butanediol terephthalate has excellent toughness, the elongation at break (750%) of the PBAT is higher than that of most degradable plastics, the melting point of the PBAT is 120 ℃, and the PBAT is easy to process and form. However, the hardness is high, the tensile strength (34 +/-2 MPa) needs to be improved, the problems of poor oxygen and water vapor barrier properties, high cost and the like limit the wide application of the composite material.
In order to further improve the mechanical properties of PBAT, various modification methods are reported in the literature, for example, a permeable network structure is formed in a PBAT and a stereo complex polylactic acid (sc-PLA) composite material prepared by a melt blending method, and the PBAT and the stereo complex polylactic acid (sc-PLA) composite material have higher yield stress and modulus (ZHao Hongwei, RSC Advances,2020,10(18): 10482-10490). There have also been reports of improving the mechanical and thermal properties of PBATs by adding inorganic nanoparticles, for example, clay nanoparticles (sepiolite, montmorillonite and fluororectorite) are incorporated into PBATs, and the nanoparticles are usedThe barrier effect of clay can improve the thermal stability of PBAT, the sepiolite nanoparticles can act as nucleating agent to promote crystallization of PBAT, and the reinforcement effect of nanomaterials can improve the elastic modulus and hardness of PBAT (Fukushima Kikku, Materials Science and Engineering C,2012, 32(6): 1331-1351). Direct preparation of CaCO by melt extrusion3Incorporated into PLA/PBAT composites, CaCO3The addition of (A) improves the mechanical properties of the composite, but its thermal stability is reduced (Rocha Daniel Belchior, Journal of Applied Polymer Science,2018,135(35): 46660). The nanometer SiO is treated by gamma-methacryloxypropyltrimethoxysilane (KH570)2Carrying out surface modification to the modified nano SiO2Filling a PLA/PBAT composite system, and finding out that nano SiO is modified along with the modification2The content is increased, the crystallization temperature (Tc) and the melting temperature (Tm) of the composite system are gradually reduced, the crystallinity is increased, and the strength and the toughness are also improved. But when SiO2When excessive, nano SiO will be generated2The particles are not uniformly dispersed and the mechanical properties are degraded (Zhou Zhibin, Journal of Chemical Engineering of Chinese university, 2016,30(6): 1411-. This indicates that inorganic nanoparticles are prone to agglomeration and non-uniform dispersion, and that the improvement of PBAT performance is limited due to the unsatisfactory interface compatibility with organic matrices. Therefore, the limitation that the defect of PBAT is overcome only by adding other polymers or inorganic nano-fillers is also shown, and the key point for improving the PBAT performance is to find a method which can play a role in enhancing the effect and improving the material stability.
In the field of biodegradable materials, Polycaprolactone (PCL) is a degradable material with low melting point (59-64 ℃) and good flexibility and shape memory performance. The linear polycaprolactone has no high elastic state and shape memory performance, and the crosslinked polycaprolactone has shape memory characteristic, and the larger the crosslinking degree is, the more the winding nodes are, the larger the elastic modulus is, and the better the shape memory performance is. A series of excellent performances enable the composite material to show good application prospects in the fields of biomedicine, textile materials and packaging.
Polysilsesquioxanes (POSS) are comparativesA special class of silicone polymers has the chemical composition (RSiO)1.5)nBetween Silica (SiO)2)nWith polysiloxanes (R)2SiO)nAnd the inorganic core is composed of frameworks alternately connected by Si-O, R is an organic group, and can be any one of amino, carboxyl, hydroxyl, epoxy, epoxycyclohexylethyl, glycidoxypropyl, anhydride, vinyl, acrylic, acryloxy, methacryloxy and anilinopropyl. The polymer structure of the polysilsesquioxane can be ring-shaped, cage-shaped or trapezoid, etc.
The planar annular polysilsesquioxane is organic and inorganic hybrid cyclotetrasiloxane, can be used for enhancing the adhesive force, scratch resistance, temperature resistance and damage resistance of coatings of epoxy, polyurethane and acrylate systems, and can also be used as a dispersing agent or a cosolvent of a nano material. The cage-shaped polysilsesquioxane has a three-dimensional inorganic-organic hybrid structure, is shaped like a cage, has a nanoscale three-dimensional size, and belongs to a nano compound. The Si-O bond energy is 445.2KJ/mol, and the energy required for destroying the Si-O bond in the POSS core is larger. In addition, according to the difference of R group types, the polymer can be subjected to grafting or copolymerization reaction, so that chemical bonding effect is generated between the polymer and the R group, uniform dispersion on a molecular layer is facilitated, the problems of inorganic particle agglomeration and weak bonding force of a two-phase interface are solved, and the performance of the polymer is improved.
The ladder-shaped polysilsesquioxane has a double main chain or multiple main chain structure connected by Si-O bonds, and the main chains are connected by chemical bonds through a bridge group to form a ladder-shaped structure. The unique chain structure of the composite material enables the composite material to be outstanding in the aspects of heat resistance, radiation resistance, chemical stability, mechanical property and the like. In addition, the type of modification reaction and the number of branched arms can be regulated and controlled by regulating and controlling the type of the R group and the type of the coupling agent, so that the hyperbranched degree of the POSS-g-polymer is regulated and controlled, and the mechanical property, the thermal stability and the flame retardance of the composite material can be regulated and controlled by regulating and controlling the content of the POSS-g-polymer.
Disclosure of Invention
The invention aims to provide a degradable thermoplastic elastomer and a preparation method thereof, wherein Polysilsesquioxane (POSS) is used for grafting PBAT/PCL, the hyperbranched degree of POSS-g-PBAT/PCL is regulated and controlled by changing the type and reaction conditions of POSS, the POSS-g-PBAT/PCL is uniformly mixed with PBAT and PCL, and then the degradable thermoplastic elastomer containing a POSS-g-PBAT/PCL core-shell structure or an interpenetrating network structure is finally formed through coupling reaction, and the mechanical property and the degradation property of the elastomer are regulated and controlled by regulating and controlling the content of POSS-g-PBAT/PCL.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a degradable thermoplastic elastomer has high strength, flexibility, high resilience, heat resistance and biodegradability, and comprises a copolymer (PBAT) of butanediol adipate and butanediol terephthalate, Polycaprolactone (PCL), multi-arm polysilsesquioxane grafted PBAT and PCL (POSS-g-PBAT/PCL) and a coupling agent; the POSS-g-PBAT/PCL accounts for 1-10% of the mass of the elastomer, and the mechanical property and the degradation property of the elastomer are regulated and controlled by regulating and controlling the content of the POSS-g-PBAT/PCL;
the preparation method of the degradable thermal elastomer comprises the following steps:
1) preparing POSS-g-PBAT/PCL;
2) taking a certain amount of POSS-g-PBAT/PCL, PBAT and PCL, adding into an internal mixer, and melting and uniformly mixing;
3) and adding a coupling agent to enable the materials to be crosslinked in the subsequent melting and mixing process, thereby obtaining the degradable thermoplastic elastomer.
The POSS-g-PBAT/PCL, the PBAT, the PCL and the coupling agent respectively account for 1-10 percent, 65-97 percent, 1-30 percent and 0.1-2.5 percent by mass.
Wherein the polysilsesquioxane is ring-shaped, cage-shaped or trapezoid; the polysiloxane is characterized in that the functional group is one or a combination of more of amino, carboxyl, hydroxyl, epoxy cyclohexyl ethyl, glycidyl ether oxygen propyl, acid anhydride group, vinyl, acrylic group, acryloxy, methacryloxy and aniline propyl.
Preferably, the polysilsesquioxane is one or a combination of several of glycidyloxypropylcyclotetrasiloxane, epoxycyclohexylethyl cage polysilsesquioxane, glycidyloxypropylcage polysilsesquioxane and ladder polysilsesquioxane with epoxycyclohexylethyl or glycidyloxypropyl as a side group.
The POSS-g-PBAT/PCL is obtained by reacting a functional group on POSS with PBAT and PCL under the action of a catalyst; the catalyst is one or a combination of several of aliphatic ammonium salt, amine, alcohol, phenol, carboxylic acid, zinc lactate, magnesium lactate and ferrous lactate.
The mixing temperature in the internal mixer in the step 2) is 80-120 ℃, and the time is 15-30 min.
The coupling agent is selected from one or a combination of more of gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560), gamma-methacryloxypropyltrimethoxysilane (KH570), diethylaminomethyl triethylaminosilane, trivinyl silane and vinyl trimethoxy silane.
Compared with the prior art, the invention has the beneficial effects that:
based on the characteristics of the PBAT and the PCL in performance, application and molecular structure, the Polysilsesquioxane (POSS) with multi-arm epoxy groups is adopted to modify the polymer, and the epoxy groups in the POSS and the hydroxyl groups in the polymer are utilized to react to form a branched polymer, so that the branched polymer is beneficial to forming a chemical micro-crosslinking structure, can be used as a compatibilizer, reduces the difference of glass transition temperatures between the PBAT and the PCL, and promotes two-phase compatibility. Meanwhile, the cross-linked network structure can enable the POSS nano compound to exist stably, and the motion range of surrounding molecular chains is limited, so that the mechanical property of the composite material is improved.
The invention designs the structure of the molecule according to the specific use requirement, utilizes the reactive group on the polysilsesquioxane to perform grafting reaction with PBAT and PCL, and connects the polysilsesquioxane with PBAT and PCL by covalent bond. The hyperbranched degree of POSS-g-PBAT/PCL is regulated and controlled by regulating and controlling the type of polysilsesquioxane, and then the POSS-g-PBAT/PCL is uniformly mixed with the PBAT and the PCL, and the degradable thermoplastic elastomer is prepared through coupling reaction. The mechanical property, heat resistance and degradation property of the elastomer are regulated and controlled by changing the hyperbranched degree, the coupling degree and the POSS-g-PBAT/PCL content.
The invention can realize the regulation and control of the mechanical property and the degradation property of the elastomer by changing the branching degree and the crosslinking degree of a molecular chain from the atom and molecular layer level, and is embodied in the following aspects:
firstly, the degradable thermoplastic elastomer prepared by the invention is prepared by POSS-g-PTAB/PCL with a core-shell structure or a hyperbranched structure, and POSS nano compounds are introduced into a polymer matrix in a covalent bond connection mode, so that the dispersion effect, stability and two-phase interface compatibility of the nano compounds POSS in the elastomer are improved, and meanwhile, the formed three-dimensional network structure can stop the development of microcrack tips to play a role in reinforcement; in addition, the existence of the hyperbranched structure POSS-g-PTAB/PCL can also reduce the viscosity of the polymer and improve the fluidity of the polymer during processing. Secondly, compared with linear macromolecules, the molecular chains can form a three-dimensional network structure through proper crosslinking or a certain branching degree, and the motion range of the molecular chains is limited, so that the molecular chains have better toughness and elasticity; in addition, the PCL component after crosslinking also has shape memory performance, so that the PCL component has better resilience after being stressed. Thirdly, the heat resistance of the elastomer can be improved by introducing Si-O covalent bonds with larger bond energy into the elastomer. Fourthly, the PBAT and the PCL which are selected materials are biodegradable materials, so that the elastomer can be endowed with better degradation performance, and the problem of white pollution can be relieved after the product is used.
Drawings
FIG. 1 shows the molecular structures of glycidol ether oxypropylcyclotetrasiloxane and grafted PBAT/PCL thereof.
FIG. 2 shows the molecular structures of epoxycyclohexylethyl cage polysilsesquioxane and its grafted PBAT/PCL.
FIG. 3 shows the molecular structure of trapezoidal polysilsesquioxane with glycidyl ether oxypropyl group as its side group and grafted PBAT/PCL.
FIG. 4 shows the molecular structure of epoxy cyclohexyl ethyl trapezoidal polysilsesquioxane and its grafted PBAT/PCL.
Detailed Description
The above-mentioned contents of the present invention are further described in detail by way of examples below, but it should not be understood that the scope of the above-mentioned subject matter of the present invention is limited to the following examples, and any technique realized based on the above-mentioned contents of the present invention falls within the scope of the present invention.
The experimental procedures used in the examples below are conventional procedures unless otherwise specified, and the reagents, methods and equipment used therein are conventional in the art unless otherwise specified.
The degradable thermoplastic elastomer consists of a copolymer (PBAT) of butanediol adipate and butanediol terephthalate, Polycaprolactone (PCL), multi-arm polysilsesquioxane grafted PBAT and PCL (POSS-g-PBAT/PCL) and a coupling agent. Wherein the POSS-g-PBAT/PCL accounts for 1-10% by mass, and the specific embodiment for preparing the POSS-g-PBAT/PCL is as follows:
example 1
Adding 50 parts of PBAT granules, 5 parts of PCL granules and 100 parts of dichloromethane into a reaction container, magnetically stirring for 6 hours at room temperature, then adding 1 part of glycidyl ether oxypropyl cyclotetrasiloxane and 0.1 part of ammonium hydroxide, and continuously magnetically stirring for 3 hours at room temperature. After the reaction is finished, performing rotary evaporation under the condition of negative pressure to remove a dichloromethane solvent, washing for 3 times by using absolute ethyl alcohol, and drying at low temperature to obtain a product of glycidyl ether oxypropyl cyclotetrasiloxane-g-PBAT/PCL (the molecular structural formulas of reactants and the product are shown in figure 1).
Example 2
Adding 50 parts of PBAT granules, 5 parts of PCL granules and 100 parts of dichloromethane into a reaction container, magnetically stirring for 6 hours at room temperature, then adding 1 part of epoxy cyclohexyl ethyl cage-shaped polysilsesquioxane and 0.1 part of ammonium hydroxide, and continuously magnetically stirring for 4 hours at room temperature. After the reaction is finished, rotationally evaporating under the negative pressure condition to remove a dichloromethane solvent, washing for 3 times by using absolute ethyl alcohol, and drying at low temperature to obtain a product epoxy cyclohexyl ethyl cage polysilsesquioxane-g-PBAT/PCL (the molecular structural formulas of reactants and the product are shown in figure 2).
Example 3
Adding 50 parts of PBAT granules, 5 parts of PCL granules and 100 parts of dichloromethane into a reaction container, magnetically stirring for 6 hours at room temperature, then adding 1 part of trapezoidal polysilsesquioxane with glycidyl ether oxypropyl as a side group and 0.1 part of ammonium hydroxide, and continuously magnetically stirring for 5 hours at room temperature. After the reaction is finished, performing rotary evaporation under the condition of negative pressure to remove a dichloromethane solvent, washing for 3 times by using absolute ethyl alcohol, and drying at low temperature to obtain the product of the trapezoidal polysilsesquioxane-g-PBAT/PCL (the molecular structural formulas of reactants and the product are shown in figure 3).
Example 4
Adding 50 parts of PBAT granules, 5 parts of PCL granules and 100 parts of dichloromethane into a reaction container, magnetically stirring for 6 hours at room temperature, then adding 1 part of trapezoidal polysilsesquioxane with epoxy cyclohexyl ethyl as a side group and 0.1 part of ammonium hydroxide, and continuously magnetically stirring for 5 hours at room temperature. After the reaction is finished, performing rotary evaporation under the condition of negative pressure to remove a dichloromethane solvent, washing for 3 times by using absolute ethyl alcohol, and drying at low temperature to obtain the product of the trapezoidal polysilsesquioxane-g-PBAT/PCL (the molecular structural formulas of reactants and the product are shown in figure 4).
Example 5
The product POSS-g-PTAB/PCL obtained in example 1 was added to an internal mixer in the order of 10 parts, 80 parts of PTAB pellets, 10 parts of PCL pellets and KH 5702 parts of a coupling agent, and melt-kneaded at 120 ℃ for 15 min. And preparing the degradable thermoplastic elastomer containing the POSS-g-PBAT/PCL core-shell structure or the interpenetrating network structure.
Example 6
The product POSS-g-PTAB/PCL 10 parts obtained in example 2, PTAB granules 80 parts, PCL granules 10 parts and coupling agent KH 5702 parts were added in sequence to an internal mixer, and melt-kneaded at 120 ℃ for 20 min. And preparing the degradable thermoplastic elastomer containing the POSS-g-PBAT/PCL core-shell structure or the interpenetrating network structure.
Example 7
The product POSS-g-PTAB/PCL 10 parts obtained in example 3, PTAB granules 80 parts, PCL granules 10 parts and coupling agent KH 5702 parts were added in sequence to an internal mixer, and melt-kneaded at 120 ℃ for 30 min. And preparing the degradable thermoplastic elastomer containing the POSS-g-PBAT/PCL core-shell structure or the interpenetrating network structure.
Example 8
The product POSS-g-PTAB/PCL obtained in example 4 was added to an internal mixer in the order of 10 parts, 80 parts of PTAB pellets, 10 parts of PCL pellets and KH 5702 parts of a coupling agent, and melt-kneaded at 120 ℃ for 30 min. And preparing the degradable thermoplastic elastomer containing the POSS-g-PBAT/PCL core-shell structure or the interpenetrating network structure.
Example 9
Preparation of control group samples: adding 80 parts of PTAB granules, 10 parts of PCL granules and 5702 parts of coupling agent KH into an internal mixer in sequence, and carrying out melt mixing at 120 ℃ for 15 min. The degradable thermoplastic elastomer containing the PBAT and the PCL melt blending crosslinking matter is prepared.
Example 10
(1) And (3) hardness testing: the sample was prepared into a square specimen of 30mm × 30mm by a small injection molding machine. According to GB/T531.1-2008 "method for Press hardness test of vulcanized or thermoplastic rubber part 1: shore Durometer method (Shore Durometer), measurement was performed using Shore Durometer type A. Each set of samples was measured 5 times and averaged.
(2) And (3) impact resilience testing: the sample was prepared into a square specimen of 30mm × 30mm × 2mm by a small injection molding machine. According to GB/T1681-. 3 impacts are required before the measurement to correct the mechanical properties of the rubber. Each set of samples was measured 5 times and averaged.
(3) And (3) detecting the tensile property: determination of the tensile Properties of plastics according to the test Standard GB/T1040.3-2006 section 3: test conditions for film and sheet elastomer obtained in each of the above examples was prepared into a shape required for testing tensile strength by a small injection molding machine. The total length of the specimen was 75mm, the length of the narrow parallel portion was 40mm, the width of the narrow portion was 5mm, the thickness was 2mm, and the gauge length was 25 mm. 3 tensile specimens are prepared per group and conditioned for at least 3 hours at a temperature of (23 + -2) deg.C and a relative humidity of 50% + -5%. The tensile strength and elongation at break of the samples were tested on an electronic tensile tester according to the standard ASTM D412-98a test method, with a tensile rate of 5 mm/min. Each set of samples was measured 3 times and averaged.
Table 1 test results of hardness, impact resilience, tensile strength and elongation at break of the samples
The above description is only a preferred embodiment of the present invention, and should not be taken as limiting the invention in any way, and any person skilled in the art can make any simple modification, equivalent replacement, and improvement on the above embodiment without departing from the technical spirit of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (7)
1. A degradable thermoplastic elastomer, characterized by: the elastomer has high strength, flexibility, high resilience, heat resistance and biodegradability, and comprises the components of a copolymer (PBAT) of butanediol adipate and butanediol terephthalate, Polycaprolactone (PCL), multi-arm polysilsesquioxane grafted PBAT and PCL (POSS-g-PBAT/PCL) and a coupling agent; the POSS-g-PBAT/PCL accounts for 1-10% of the mass of the elastomer, and the mechanical property and the degradation property of the elastomer are regulated and controlled by regulating and controlling the content of the POSS-g-PBAT/PCL;
the preparation method of the degradable thermal elastomer comprises the following steps:
1) preparing POSS-g-PBAT/PCL;
2) taking a certain amount of POSS-g-PBAT/PCL, PBAT and PCL, adding into an internal mixer, and melting and uniformly mixing;
3) and adding a coupling agent to enable the materials to be crosslinked in the subsequent melting and mixing process, thereby obtaining the degradable thermoplastic elastomer.
2. The degradable thermoplastic elastomer of claim 1, wherein: the POSS-g-PBAT/PCL, the PBAT, the PCL and the coupling agent respectively account for 1-10 percent, 65-97 percent, 1-30 percent and 0.1-2.5 percent by mass.
3. The degradable thermoplastic elastomer of claim 1, wherein: wherein the polysilsesquioxane is ring-shaped, cage-shaped or trapezoid; the polysiloxane is characterized in that the functional group is one or a combination of more of amino, carboxyl, hydroxyl, epoxy cyclohexyl ethyl, glycidyl ether oxygen propyl, acid anhydride group, vinyl, acrylic group, acryloxy, methacryloxy and aniline propyl.
4. The degradable thermoplastic elastomer of claim 3, wherein: the polysilsesquioxane is one or a combination of more of glycidol ether oxygen propyl cyclotetrasiloxane, epoxy cyclohexyl ethyl cage polysilsesquioxane, glycidyl ether oxygen propyl cage polysilsesquioxane and ladder polysilsesquioxane with epoxy cyclohexyl ethyl or glycidyl ether oxygen propyl as a side group.
5. The degradable thermoplastic elastomer of claim 1, wherein: the POSS-g-PBAT/PCL is obtained by reacting a functional group on POSS with PBAT and PCL under the action of a catalyst; the catalyst is one or a combination of several of aliphatic ammonium salt, amine, alcohol, phenol, carboxylic acid, zinc lactate, magnesium lactate and ferrous lactate.
6. The degradable thermoplastic elastomer of claim 1, wherein: the mixing temperature in the internal mixer in the step 2) is 80-120 ℃, and the time is 15-30 min.
7. The degradable thermoplastic elastomer of claim 1, wherein: the coupling agent is selected from one or a combination of more of gamma-aminopropyltriethoxysilane (KH550), gamma-glycidoxypropyltrimethoxysilane (KH560), gamma-methacryloxypropyltrimethoxysilane (KH570), diethylaminomethyl triethylaminosilane, trivinylsilane and vinyltrimethoxysilane.
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